WO2022210049A1 - ポリエステル樹脂 - Google Patents
ポリエステル樹脂 Download PDFInfo
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- WO2022210049A1 WO2022210049A1 PCT/JP2022/012818 JP2022012818W WO2022210049A1 WO 2022210049 A1 WO2022210049 A1 WO 2022210049A1 JP 2022012818 W JP2022012818 W JP 2022012818W WO 2022210049 A1 WO2022210049 A1 WO 2022210049A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/19—Hydroxy compounds containing aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
- C08G59/4269—Macromolecular compounds obtained by reactions other than those involving unsaturated carbon-to-carbon bindings
- C08G59/4276—Polyesters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/19—Hydroxy compounds containing aromatic rings
- C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
- H10W70/00—Package substrates; Interposers; Redistribution layers [RDL]
- H10W70/60—Insulating or insulated package substrates; Interposers; Redistribution layers
- H10W70/62—Insulating or insulated package substrates; Interposers; Redistribution layers characterised by their interconnections
- H10W70/65—Shapes or dispositions of interconnections
- H10W70/654—Top-view layouts
- H10W70/655—Fan-out layouts
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
- H10W70/00—Package substrates; Interposers; Redistribution layers [RDL]
- H10W70/60—Insulating or insulated package substrates; Interposers; Redistribution layers
- H10W70/67—Insulating or insulated package substrates; Interposers; Redistribution layers characterised by their insulating layers or insulating parts
- H10W70/69—Insulating materials thereof
- H10W70/695—Organic materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
- H10W74/00—Encapsulations, e.g. protective coatings
- H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
- H10W74/00—Encapsulations, e.g. protective coatings
- H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
- H10W74/00—Encapsulations, e.g. protective coatings
- H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
- H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins
- H10W74/473—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins containing a filler
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
Definitions
- the present invention relates to polyester resins. Furthermore, it relates to a resin composition, a resin sheet, a prepreg, a cured product, a printed wiring board, a semiconductor chip package, and a semiconductor device obtained using the polyester resin.
- a resin composition containing a crosslinkable resin such as an epoxy resin and its crosslinker (curing agent) provides a cured product with excellent insulation, heat resistance, adhesion, etc. Therefore, it is used as a material for electronic parts such as semiconductors and printed wiring boards. has been widely used as
- Patent Document 1 discloses an active ester resin, which is a reaction product of a divalent aromatic hydroxy compound and an aromatic diacid chloride, as a cross-linking agent for an epoxy resin.
- Patent Document 2 discloses a copolymerized polyester resin obtained by reacting an aromatic diol (such as a hydroxyalkylene ether of bisphenol) and an aliphatic diol with an aromatic carboxylic acid.
- the active ester resin described in Patent Document 1 has significantly better dielectric properties than conventional phenol-based cross-linking agents, but the transmission loss required for 5G applications is not at a sufficiently satisfactory level. Moreover, in order to further improve the dielectric properties using this resin, there is a method of adjusting the compounding ratio (mass ratio) with the crosslinkable resin. Dielectric properties can be greatly improved by increasing the blending ratio of the active ester resin to such an extent that the active ester groups are excessive relative to the epoxy groups. At the same time, however, the strongly acidic and strongly basic chemicals used in the desmear process hydrolyze the surplus active ester groups, resulting in brittleness of the structure, which is accompanied by serious side effects such as cracking and interfacial peeling failures. Therefore, it was difficult to adopt the method.
- the polyester resin described in Patent Document 2 is a thermoplastic resin having a Tg of 135° C. or higher, as described in Examples, and is used as a cross-linking agent for a cross-linkable resin by blending it in a resin composition. does not have physical properties.
- the diol component used for synthesizing the polyester resin is a diol component having two aliphatic hydroxy groups.
- An object of the present invention is to provide a polyester resin that, when combined with a crosslinkable resin, provides a cured product that exhibits excellent dielectric properties and good chemical resistance.
- R 1 represents a monovalent or divalent aromatic group
- R 2 represents a divalent aliphatic group
- R 3 represents a divalent aromatic group.
- (x1) a hydroxy compound containing at least a hydroxy compound having both an aromatic hydroxy group and an aliphatic hydroxy group; (x2) a divalent aromatic carboxylic acid compound or a divalent aromatic carboxylic acid halide compound; (x3)
- the hydroxy compound is a hydroxy compound having two or more aromatic hydroxy groups; 7.
- R 1a each independently represents a monovalent aromatic group
- R 1b each independently represents a divalent aromatic group
- R 2 each independently represents a divalent aliphatic group
- R 3 each independently represents a divalent aromatic group
- L each independently represents a single bond or a divalent linking group
- x1 and x2 are numbers satisfying 0 ⁇ x1 ⁇ 1, 0 ⁇ x2 ⁇ 1 and 0 ⁇ x1+x2 ⁇ 2
- n is a number ranging from 0 to 5
- N indicates the number of repetitions and indicates a number that satisfies 0 ⁇ N ⁇ 8.
- a resin cross-linking agent comprising the polyester resin according to any one of [1] to [19].
- a resin composition comprising the polyester resin (X) according to any one of [1] to [19] and a crosslinkable resin (Y).
- the resin according to [21] or [22], wherein the mass ratio ((X)/(Y)) of the polyester resin (X) to the crosslinkable resin (Y) is from 1.2 to 2.0. Composition.
- a resin sheet comprising a support and a layer of the resin composition according to any one of [21] to [27] provided on the support.
- a printed wiring board comprising an insulating layer made of a cured product of the resin composition according to any one of [21] to [26].
- a semiconductor chip package comprising a sealing layer made of a cured resin composition according to any one of [21] to [25] and [27].
- the semiconductor chip package according to [32] which is a fan-out type package.
- a semiconductor device comprising the printed wiring board of [31] or the semiconductor chip package of [32] or [33].
- a polyester resin that, in combination with a crosslinkable resin, provides a cured product that exhibits excellent dielectric properties and good chemical resistance.
- FIG. 1a shows a GPC chart of polyester resin (1) in Example 1.
- FIG. 1b shows an IR chart of polyester resin (1) in Example 1.
- FIG. 2a shows a GPC chart of polyester resin (2) in Example 2.
- FIG. 2b shows an IR chart of polyester resin (2) in Example 2.
- FIG. 3a shows a GPC chart of polyester resin (3) in Example 3.
- FIG. 3b shows an IR chart of polyester resin (3) in Example 3.
- FIG. 4a shows a GPC chart of polyester resin (4) in Example 4.
- FIG. 4b shows an IR chart of polyester resin (4) in Example 4.
- FIG. 5a shows a GPC chart of polyester resin (5) in Example 5.
- FIG. 5b shows an IR chart of polyester resin (5) in Example 5.
- FIG. 6a shows a GPC chart of polyester resin (6) in Example 6.
- FIG. 6a shows a GPC chart of polyester resin (6) in Example 6.
- FIG. 6b shows an IR chart of polyester resin (6) in Example 6.
- FIG. 7a shows a GPC chart of polyester resin (7) in Example 7.
- FIG. 7b shows an IR chart of polyester resin (7) in Example 7.
- FIG. 8a shows a GPC chart of polyester resin (8) in Example 8.
- FIG. 8b shows an IR chart of polyester resin (8) in Example 8.
- FIG. 9a shows a GPC chart of polyester resin (9) in Example 9.
- FIG. 9b shows an IR chart of polyester resin (9) in Example 9.
- FIG. 10a shows a GPC chart of polyester resin (10) in Comparative Example 1.
- FIG. 10b shows an IR chart of polyester resin (10) in Comparative Example 1.
- the term "optionally substituted" with respect to a compound or group refers to the case where the hydrogen atom of the compound or group is not substituted with a substituent, and the hydrogen atom of the compound or group It means both cases where some or all of the atoms are substituted with a substituent.
- substituted includes a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, monovalent heterocyclic group, alkylidene group, amino group, silyl group, acyl group, acyloxy group, carboxy group, sulfo group, cyano group, nitro group, hydroxy group, mercapto group and oxo group.
- the halogen atom used as a substituent includes, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- the alkyl group used as a substituent may be linear or branched.
- the number of carbon atoms in the alkyl group is preferably 1-20, more preferably 1-14, even more preferably 1-12, even more preferably 1-6, and particularly preferably 1-3.
- Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group and nonyl group. , and decyl groups.
- the cycloalkyl group used as a substituent preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms, and still more preferably 3 to 6 carbon atoms.
- Examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
- the alkoxy group used as a substituent may be linear or branched.
- the number of carbon atoms in the alkoxy group is preferably 1-20, more preferably 1-12, still more preferably 1-6.
- Examples of the alkoxy group include methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, Octyloxy, nonyloxy, and decyloxy groups are included.
- the cycloalkyloxy group used as a substituent preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms, and still more preferably 3 to 6 carbon atoms.
- Examples of the cycloalkyloxy groups include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, and cyclohexyloxy groups.
- the aryl group used as a substituent is a group obtained by removing one hydrogen atom on the aromatic ring from an aromatic hydrocarbon.
- the aryl group used as a substituent preferably has 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 14 carbon atoms, and still more preferably 6 to 10 carbon atoms.
- the aryl group includes, for example, phenyl group, naphthyl group, and anthracenyl group.
- the number of carbon atoms in the aryloxy group used as a substituent is preferably 6-24, more preferably 6-18, still more preferably 6-14, still more preferably 6-10.
- Aryloxy groups used as substituents include, for example, a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group.
- the number of carbon atoms in the arylalkyl group used as a substituent is preferably 7-25, more preferably 7-19, still more preferably 7-15, still more preferably 7-11.
- the arylalkyl groups include, for example, phenyl-C 1 -C 12 alkyl groups, naphthyl-C 1 -C 12 alkyl groups, and anthracenyl-C 1 -C 12 alkyl groups.
- the arylalkoxy group used as a substituent preferably has 7 to 25 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 15 carbon atoms, and still more preferably 7 to 11 carbon atoms.
- the arylalkoxy groups include, for example, phenyl-C 1 -C 12 alkoxy groups and naphthyl-C 1 -C 12 alkoxy groups.
- a monovalent heterocyclic group used as a substituent refers to a group obtained by removing one hydrogen atom from the heterocyclic ring of a heterocyclic compound.
- the number of carbon atoms in the monovalent heterocyclic group is preferably 3-21, more preferably 3-15, still more preferably 3-9.
- the monovalent heterocyclic group also includes a monovalent aromatic heterocyclic group (heteroaryl group).
- Examples of the monovalent heterocyclic ring include thienyl, pyrrolyl, furanyl, furyl, pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, triazinyl, pyrrolidyl, piperidyl, quinolyl, and isoquinolyl groups. is mentioned.
- the alkylidene group used as a substituent refers to a group obtained by removing two hydrogen atoms from the same carbon atom of alkane.
- the alkylidene group preferably has 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms, still more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
- alkylidene group examples include methylidene group, ethylidene group, propylidene group, isopropylidene group, butylidene group, sec-butylidene group, isobutylidene group, tert-butylidene group, pentylidene group, hexylidene group, heptylidene group, octylidene group and nonylidene group. and desylidene groups.
- the alkyl group represented by R may be linear or branched.
- Aryl groups represented by R include, for example, a phenyl group, a naphthyl group, and an anthracenyl group.
- the acyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 13 carbon atoms, and still more preferably 2 to 7 carbon atoms. Examples of the acyl group include acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, and benzoyl group.
- the alkyl group represented by R may be linear or branched.
- Aryl groups represented by R include, for example, a phenyl group, a naphthyl group, and an anthracenyl group.
- the acyloxy group preferably has 2 to 20 carbon atoms, more preferably 2 to 13 carbon atoms, and still more preferably 2 to 7 carbon atoms. Examples of the acyloxy group include acetoxy, propionyloxy, butyryloxy, isobutyryloxy, pivaloyloxy, and benzoyloxy groups.
- the above-mentioned substituent may further have a substituent (hereinafter sometimes referred to as "secondary substituent").
- secondary substituents As secondary substituents, unless otherwise specified, the same substituents as described above may be used.
- aromatic group refers to a group obtained by removing one or more hydrogen atoms from the aromatic ring of an aromatic compound.
- a monovalent aromatic group refers to a group in which one hydrogen atom has been removed from the aromatic ring of an aromatic compound
- divalent aromatic group refers to a group in which a hydrogen atom has been removed from the aromatic ring of an aromatic compound.
- aromatic ring means a ring according to Hückel's rule in which the number of electrons contained in the ⁇ electron system on the ring is 4n+2 (n is a natural number), a monocyclic aromatic ring, and two or more contains condensed aromatic rings in which monocyclic aromatic rings of are condensed.
- Aromatic rings may be carbocyclic or heterocyclic.
- the monovalent aromatic group includes, for example, an optionally substituted aryl group and an optionally substituted heteroaryl group
- the divalent aromatic group includes, for example, An arylene group optionally having a substituent and a heteroarylene group optionally having a substituent are exemplified.
- the number of carbon atoms in the aromatic group is preferably 3 or more, more preferably 4 or more or 5 or more, still more preferably 6 or more, and the upper limit is preferably 24 or less. , more preferably 18 or less or 14 or less, and still more preferably 10 or less.
- the number of carbon atoms does not include the number of carbon atoms of substituents.
- aliphatic group refers to a group from which one or more hydrogen atoms bonded to the aliphatic carbon atoms of an aliphatic compound have been removed.
- the monovalent aliphatic group refers to a group in which one hydrogen atom bonded to the aliphatic carbon of the aliphatic compound is removed, and the divalent aliphatic group is the aliphatic carbon of the aliphatic compound.
- a group in which two hydrogen atoms bonded to are removed.
- the monovalent aliphatic group for example, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkenyl group, a substituent
- the divalent aliphatic group include an optionally substituted alkylene group, an optionally substituted cycloalkylene group, An alkenylene group which may have a substituent and a cycloalkenylene group which may have a substituent may be mentioned.
- the number of carbon atoms in the aliphatic group is preferably 1-20, more preferably 1-14, 1-12 or 1-6, and still more preferably 1-3, unless otherwise specified. The number of carbon atoms does not include the number of carbon atoms of substituents.
- the polyester resin of the present invention is characterized by containing both the following skeleton (A) and skeleton (B).
- the polyester resin of the present invention provides a cured product that exhibits excellent dielectric properties and good chemical resistance in combination with a crosslinkable resin. be able to.
- the preferred range of the molecular weight of the polyester resin and the content ratio of the skeleton (A) to the skeleton (B) will be described later.
- -Skeleton (A)- Skeleton (A) is a skeleton represented by the formula: ( ⁇ )R 1 —O—C( ⁇ O)—R 3 — (wherein R 1 represents a monovalent or divalent aromatic group, R 3 represents a divalent aromatic group).
- the polyester resin of the present invention can be used as a cross-linking agent for a cross-linkable resin by blending it in a resin composition.
- R 1 represents a divalent aromatic group
- the polyester resin of the present invention has a molecular chain end (preferably both ends) having a skeleton (A) (wherein R 1 represents a monovalent aromatic group). is blocked by
- the polyester resin of the present invention also preferably has a skeleton (A) (in the formula, R 1 represents a divalent aromatic group) together with a skeleton (B), which will be described later, in its molecular chain.
- the monovalent aromatic group represented by R 1 is preferably an optionally substituted aryl group from the viewpoint of being able to enjoy the effects of the present invention more.
- the number of carbon atoms in the aryl group in R 1 is preferably 6-18, more preferably 6-14, and still more preferably 6-10.
- the number of carbon atoms does not include the number of carbon atoms of substituents.
- the monovalent aromatic group represented by R 1 is an optionally substituted phenyl group or an optionally substituted naphthyl group, and more A naphthyl group which may have a substituent is preferred.
- the substituents that the aryl group in R 1 may have are as described above.
- the substituent is preferably one or more selected from a halogen atom, an alkyl group, and an aryl group, and a fluorine atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. More preferably, one or more selected from
- the divalent aromatic group represented by R 1 is preferably an optionally substituted arylene group from the viewpoint of being able to enjoy the effects of the present invention more.
- the number of carbon atoms in the arylene group in R 1 is preferably 6-18, more preferably 6-14, even more preferably 6-10.
- the number of carbon atoms does not include the number of carbon atoms of substituents.
- the divalent aromatic group represented by R 1 is a phenylene group which may have a substituent or a naphthylene group which may have a substituent, and more A phenylene group optionally having a substituent is preferred.
- the substituents that the arylene group in R 1 may have are as described above.
- the substituent is preferably one or more selected from a halogen atom, an alkyl group, an aryl group, an arylalkyl group, and a hydroxy group.
- a halogen atom an alkyl group
- an aryl group an arylalkyl group
- a hydroxy group a group having 6 to 10 carbon atoms, alkyl group having 1 to 6 carbon atoms
- hydroxy groups are more preferred.
- the divalent aromatic group represented by R 3 is preferably an optionally substituted arylene group from the viewpoint of being able to enjoy the effects of the present invention more.
- the number of carbon atoms in the arylene group in R 1 is preferably 6-18, more preferably 6-14, even more preferably 6-10.
- the number of carbon atoms does not include the number of carbon atoms of substituents.
- the divalent aromatic group represented by R 3 is a phenylene group which may have a substituent or a naphthylene group which may have a substituent, and more A phenylene group optionally having a substituent is preferred.
- the substituents that the arylene group in R 3 may have are as described above.
- the substituent is preferably one or more selected from a halogen atom, an alkyl group, and an aryl group, and a fluorine atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. More preferably, one or more selected from
- the polyester resin of the present invention preferably contains two or more skeletons (A) in the molecule.
- the average number of skeletons (A) contained in the molecule is preferably 2.2 or more, more preferably 2.4 or more, still more preferably 2.5 or more.
- the upper limit of the average number of the skeleton (A) is not particularly limited, but the preferred range of the molecular weight of the polyester resin described later, the preferred range of the molar ratio with the skeleton (B), and the equivalent weight of the oxycarbonyl group derived from the skeleton (A) It is preferable to satisfy the preferred range, which can be, for example, 10 or less, 8 or less.
- the polyester resin of the present invention has chemical resistance even when the blending ratio (mass ratio) with respect to the crosslinkable resin is increased to achieve the transmission loss required for 5G applications.
- a good cured product can be obtained, and the occurrence of crack defects and interfacial peeling defects can be suppressed.
- the polyester resin of the present invention preferably contains the skeleton (B) inside its molecular chain.
- the divalent aliphatic group represented by R 2 is preferably an optionally substituted alkylene group from the viewpoint of being able to enjoy the effects of the present invention more.
- the alkylene group for R 2 may be linear or branched, and preferably has 1 to 6 carbon atoms, more preferably 2 to 5 carbon atoms, and still more preferably 2 or 3 carbon atoms.
- the number of carbon atoms does not include the number of carbon atoms of substituents.
- the divalent aliphatic group represented by R 2 has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms.
- the substituents that the alkylene group for R 2 may have are as described above.
- the substituent is preferably one or more selected from a halogen atom, an alkyl group, and an aryl group, and a fluorine atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. More preferably, one or more selected from
- the divalent aromatic group represented by R 3 is as described for the skeleton (A), and preferred examples thereof are also the same.
- the content of the skeleton (B) in the polyester resin of the present invention is preferably within a predetermined range from the viewpoint of providing a cured product that exhibits excellent dielectric properties and good chemical resistance.
- the ratio of the number of oxycarbonyl groups derived from the skeleton (A) to the total number of oxycarbonyl groups derived from the skeleton (A) and the oxycarbonyl groups derived from the skeleton (B) [(A)/((A) + ( B))] is preferably 0.3 or more, more preferably 0.4 or more, and still more preferably 0.45 or more or 0.5 or more, and the ratio [(A) / ((A) + (B) )] is preferably 0.95 or less, more preferably 0.9 or less, and still more preferably 0.85 or less or 0.8 or less. preferred.
- the molar ratio of oxycarbonyl groups derived from skeleton (A) to oxycarbonyl groups derived from skeleton (B) is from 30:70 to 95:5. .
- the ratio ((A):(B)) is more preferably 40:60 to 90:10, more preferably 45:55 to 85:15 or 50:50 to 80:20.
- the equivalent weight of oxycarbonyl groups is preferably within a predetermined range from the viewpoint of providing a cured product that exhibits excellent dielectric properties and good chemical resistance when combined with a crosslinkable resin.
- the equivalent weight of all oxycarbonyl groups including the skeleton (A)-derived oxycarbonyl group and the skeleton (B)-derived oxycarbonyl group is preferably 170 g/eq. above, more preferably 180 g/eq. above, more preferably 190 g/eq. Above, 200g/eq. That's it.
- the upper limit of the equivalent weight of all oxycarbonyl groups is, for example, 500 g/eq. 450 g/eq. 400 g/eq. and so on.
- the equivalent weight of oxycarbonyl groups derived from the skeleton (A) is higher than the equivalent weight of all oxycarbonyl groups, preferably 220 g/eq. above, more preferably 240 g/eq. above, more preferably 260 g/eq. Above, 280 g/eq. or more or 300 g/eq. That's it.
- the upper limit of the equivalent weight of the oxycarbonyl group derived from the skeleton (A) is, for example, 1000 g/eq. less than 800 g/eq. 600 g/eq. 500 g/eq. and so on.
- the total oxycarbonyl group equivalent weight is 170 g/eq.
- the oxycarbonyl group equivalent derived from the skeleton (A) was 220 g/eq. That's it.
- the polyester resin of the present invention contains a structural unit i represented by the following formula (i).
- R 1b each independently represents a divalent aromatic group
- R 2 each independently represents a divalent aliphatic group
- L each independently represents a single bond or a divalent linking group
- m is an integer from 0 to 5
- y1 and y2 are each independently 0 or 1; * indicates a bond, which bond is bonded to R 3 , where R 3 represents a divalent aromatic group.
- the portion represented by *-C( O)-OR 1b- when y1 is 0 (* is bonded to R 3 ), and -R 1b- when y2 is 0
- the portion represented by *-C( O)-OR 2 - when y1 is 1 (* is bonded to R 3 ), -R 2 -O-C when y2 is 1
- the polyester resin of the present invention has a skeleton in addition to the above skeleton (A) (B). Accordingly, one or both of y1 and y2 (preferably one of y1 and y2) is 1 in at least one structural unit i contained in the polyester resin of the present invention.
- y1 and y2 are a hydroxy compound having two or more aromatic hydroxy groups and an aliphatic The value can be adjusted by converting an aromatic hydroxy group into an aliphatic hydroxy group through the action of a carbonate or the like.
- y1 and y2 are 1; y1 and y2 are zero.
- a preferred embodiment of the structural unit i will be described later in relation to the average number N of the structural units i per molecule of the polyester resin.
- R 1b corresponds to the divalent aromatic group represented by R 1 in skeleton (A), and preferred examples thereof are as described for R 1 .
- R 1b is a phenylene group optionally having a substituent or a naphthylene group optionally having a substituent, more preferably having a substituent is a good phenylene group. Suitable examples of substituents are also as described for R 1 .
- R 2 corresponds to R 2 in skeleton (B), and suitable examples thereof are as described for R 2 in skeleton (B).
- the divalent aliphatic group represented by R 2 has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms.
- R3 to which the bond is attached corresponds to R3 in skeleton ( A) and skeleton (B), and preferred examples thereof are As described for R3 .
- the divalent aromatic group represented by R 3 is a phenylene group which may have a substituent or a naphthylene group which may have a substituent, and more A phenylene group optionally having a substituent is preferred. Suitable examples of substituents are also as described for R 3 in skeleton (A) and skeleton (B).
- L represents a single bond or a divalent linking group.
- the divalent linking group represented by L is one or more selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms (for example, 1 to 3000, 1 to 1000, 1 to 100, 1 to 50) skeleton atoms, among which divalent aliphatic groups optionally having substituents or divalent aromatic groups optionally having substituents Group groups are preferred. Therefore, in a preferred embodiment, L is an optionally substituted divalent aliphatic group or an optionally substituted divalent aromatic group.
- Examples of the divalent aliphatic group for L include an alkylene group, a cycloalkylene group, an alkenylene group, a cycloalkenylene group, an alkapolyenylene group (the number of double bonds is preferably 2 to 10, more preferably 2 to 6 , More preferably 2 to 4, still more preferably 2), etc., alkylene group, cycloalkylene group, alkenylene group, cycloalkenylene group is preferable, alkylene group, cycloalkylene group is more preferable, cycloalkylene group is further preferable.
- the alkylene group for L may be linear or branched, and preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
- the number of carbon atoms does not include the number of carbon atoms of substituents.
- Examples of the alkylene group include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group and the like.
- the number of carbon atoms in the cycloalkylene group in L is preferably 3-15, more preferably 3-12, still more preferably 3-10.
- the number of carbon atoms does not include the number of carbon atoms of substituents.
- the cycloalkylene group includes, for example, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a decahydronaphthylene group, a norbornanylene group, a dicyclopentanylene group, and an adamantanylene group.
- the alkenylene group for L may be either linear or branched, and preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
- the number of carbon atoms does not include the number of carbon atoms of substituents.
- alkenylene groups include ethenylene, propenylene, butenylene, pentenylene, and hexenylene groups.
- the number of carbon atoms in the cycloalkenylene group in L is preferably 3-15, more preferably 3-12, still more preferably 3-10.
- the number of carbon atoms does not include the number of carbon atoms of substituents.
- the cycloalkenylene group includes, for example, a cyclopropenylene group, a cyclobutenylene group, a cyclopentenylene group, a cyclohexenylene group, a norbornenylene group, and the like.
- examples of the divalent aromatic group for L include an arylene group and a heteroarylene group, with an arylene group being preferred.
- the number of carbon atoms in the arylene group in L is preferably 6-24, more preferably 6-18, still more preferably 6-14.
- the number of carbon atoms does not include the number of carbon atoms of substituents.
- the arylene group includes, for example, a phenylene group, a naphthylene group, an anthracenylene group, a fluorenediyl group (eg, 9H-fluorene-9,9-diyl group), a phenanthenediyl group, an indandiyl group, a pyrenediyl group and the like.
- the heteroarylene group in L preferably has 3 to 21 carbon atoms, more preferably 3 to 15 carbon atoms, and still more preferably 3 to 9 carbon atoms.
- the number of carbon atoms does not include the number of carbon atoms of substituents.
- heteroarylene groups include pyrroldiyl, furandiyl, thiophenediyl, pyridinediyl, pyridazinediyl, pyrimidinediyl, pyrazinediyl, triazinediyl, piperidinediyl, triazolediyl, purinediyl, and carbazole.
- a diyl group, a quinolinediyl group, an isoquinolinediyl group, and the like can be mentioned.
- L is an optionally substituted alkylene having 1 to 12 carbon atoms from the viewpoint of providing a cured product that exhibits excellent dielectric properties and good chemical resistance. , an optionally substituted cycloalkylene group having 3 to 15 carbon atoms, or an optionally substituted arylene group having 6 to 24 carbon atoms.
- the substituents that the divalent group represented by L may have are as described above.
- the substituent is preferably one or more selected from a halogen atom, an alkyl group, and an aryl group, and a fluorine atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. More preferably, one or more selected from
- n is an integer of 0-5, preferably 0-3, more preferably 0-2.
- the divalent aromatic group represented by R1b is preferably an optionally substituted naphthylene group.
- N is preferably 0 ⁇ N ⁇ 8.
- the upper limit of N is more preferably 7 or less, 6 or less, 5 or less, 4.5 or less, 4 or less, 3.5 or less, 3.4 or less, 3.2 or less, or 3 or less.
- the average number is more preferably 0.2N or more, more preferably 0.3N or more, 0.4N or more, or 0.5N or more.
- the polyester resin of the present invention is represented by the following formula (1).
- R 1a each independently represents a monovalent aromatic group
- R 1b each independently represents a divalent aromatic group
- R 2 each independently represents a divalent aliphatic group
- R 3 each independently represents a divalent aromatic group
- L each independently represents a single bond or a divalent linking group
- x1 and x2 are numbers satisfying 0 ⁇ x1 ⁇ 1, 0 ⁇ x2 ⁇ 1 and 0 ⁇ x1+x2 ⁇ 2
- n represents a number ranging from 0 to 5
- N indicates the number of repetitions and indicates a number that satisfies 0 ⁇ N ⁇ 8.
- N structural units i described above are contained within the molecular chain.
- a skeleton represented by —R 2 —OC( ⁇ O)—R 3 — corresponds to the above skeleton (B).
- R 1a corresponds to the monovalent aromatic group represented by R 1 in skeleton (A), and suitable examples thereof are as described for R 1 .
- R 1a is an optionally substituted phenyl group or an optionally substituted naphthyl group, more preferably substituted is a good naphthyl group. Suitable examples of substituents are also as described for R 1 .
- R 1b corresponds to the divalent aromatic group represented by R 1 in skeleton (A), and preferred examples thereof are as described for R 1 .
- R 1b is a phenylene group optionally having a substituent or a naphthylene group optionally having a substituent, more preferably having a substituent is a good phenylene group. Suitable examples of substituents are also as described for R 1 .
- R 2 corresponds to R 2 in skeleton (B), and suitable examples thereof are as described for R 2 in skeleton (B).
- the divalent aliphatic group represented by R 2 has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms.
- R 3 corresponds to R 3 in skeleton (A) and skeleton (B), and suitable examples thereof are as described for R 3 in skeleton (A) and skeleton (B).
- the divalent aromatic group represented by R 3 is a phenylene group which may have a substituent or a naphthylene group which may have a substituent, and more A phenylene group optionally having a substituent is preferred. Suitable examples of substituents are also as described for R 3 in skeleton (A) and skeleton (B).
- L represents a single bond or a divalent linking group, and is as described for structural unit i, including suitable examples.
- L is an optionally substituted divalent aliphatic group or an optionally substituted divalent aromatic group.
- L is an optionally substituted alkylene having 1 to 12 carbon atoms from the viewpoint of providing a cured product that exhibits excellent dielectric properties and good chemical resistance.
- substituents are also as described for L in structural unit i.
- x1 and x2 represent numbers satisfying 0 ⁇ x1 ⁇ 1, 0 ⁇ x2 ⁇ 1 and 0 ⁇ x1+x2 ⁇ 2.
- x1 and x2 respectively correspond to the average values of y1 and y2 in the above structural unit i, and like y1 and y2, the raw material hydroxy compound (component (x1) described later) used when synthesizing the polyester resin by converting the aromatic hydroxy group of a hydroxy compound having two or more aromatic hydroxy groups to an aliphatic hydroxy group, and by varying the degree of conversion, can be adjusted.
- the procedure for synthesizing the polyester resin will be described later.
- the sum of x1 and x2 (x1+x2) is preferably 0.1 or more, more preferably 0, from the viewpoint of providing a cured product exhibiting excellent dielectric properties and good chemical resistance in combination with the crosslinkable resin. .3 or more, more preferably 0.5 or more, 0.6 or more, or 0.8 or more, and the upper limit of the sum (x1+x2) is preferably 1.5 or less, more preferably 1.4 or less, and still more preferably is 1.2 or less or 1 or less. Therefore, in one preferred embodiment, x1 and x2 in formula (1) satisfy 0.1 ⁇ x1+x2 ⁇ 1.5, more preferably 0.5 ⁇ x1+x2 ⁇ 1.2.
- x1 and x2 are the following conditions (a) It is particularly preferable to satisfy any one of (c).
- Conditions (a) to (c) all indicate that the raw material hydroxy compound used in synthesizing the polyester resin contains at least a hydroxy compound having both an aromatic hydroxy group and an aliphatic hydroxy group.
- the values of x1 and x2 may be determined within the preferable range of the sum (x1+x2).
- n represents a number in the range of 0-5, preferably 0-3, more preferably 0-2.
- the divalent aromatic group represented by R1b is preferably an optionally substituted naphthylene group.
- R 1a is an optionally substituted phenyl group or an optionally substituted naphthyl group
- ii) R 2 is a divalent aliphatic group having 2 to 5 carbon atoms
- R3 is an optionally substituted phenylene group
- n is 0 and R 1b is an optionally substituted naphthylene group, or
- n is 1 to 5 and R 1b has a substituent L is an optionally substituted phenylene group, and L is an optionally substituted alkylene group having 1 to 12 carbon atoms, an optionally substituted cycloalkylene group having 3 to 15 carbon atoms, or It is an optionally substituted arylene group having 6 to 24 carbon atoms.
- R 1a is a phenyl group optionally having one or more substituents selected from halogen atoms, alkyl groups and aryl groups, or 1 selected from halogen atoms, alkyl groups and aryl groups A naphthyl group optionally having one or more substituents
- ii) R 2 is an alkylene group having 2 to 5 carbon atoms optionally having one or more substituents selected from halogen atoms, alkyl groups and aryl groups
- iii ) R3 is a phenylene group optionally having one or more substituents selected from halogen atoms, alkyl groups, and aryl groups;
- n is 0 and R1b is a naphthylene group optionally having one or more substituents selected from a halogen atom, an alkyl group, an aryl group, an arylalkyl group, and a hydroxy group or
- N indicates the number of repetitions and indicates a number that satisfies 0 ⁇ N ⁇ 8.
- the N corresponds to the average number of structural units i contained per molecule in the polyester resin of the present invention, and its preferred range is as described above.
- the number average molecular weight (Mn) of the polyester resin of the present invention is preferably 5,000 or less, more preferably 4,000 or less, and still more preferably 3,500 or less, or 3,000, from the viewpoint of being used as a cross-linking agent for a cross-linkable resin by blending it into a resin composition. It is below.
- the lower limit of Mn is not particularly limited as long as it contains both the skeleton (A) and the skeleton (B), and may be, for example, 500 or more, 600 or more.
- the Mn of the polyester resin of the present invention can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.
- the preferred range of Mn is based on the value measured according to the method described in the section (GPC measurement conditions) below.
- the polyester resin of the present invention is (x1) a hydroxy compound containing at least a hydroxy compound having both an aromatic hydroxy group and an aliphatic hydroxy group; (x2) a divalent aromatic carboxylic acid compound or a divalent aromatic carboxylic acid halide compound; (x3) Obtained by condensation reaction with a monovalent hydroxy compound having an aromatic hydroxy group.
- -(x1) hydroxy compound- Component (x1) is a hydroxy compound containing at least a hydroxy compound having both an aromatic hydroxy group and an aliphatic hydroxy group, and is represented by the following formula (2).
- a polyester resin containing both the skeleton (A) and the skeleton (B) can be synthesized.
- (x1) the hydroxy compound is (x1-1) a hydroxy compound having two or more aromatic hydroxy groups (represented by the following formula (3)); (x1-2) can be prepared by reacting with an aliphatic carbonate or an aliphatic oxide (containing R 2 as an aliphatic group).
- Any aromatic polyol may be used as the component (x1-1) in order to achieve the desired structure of the polyester resin.
- Preferred examples and ranges of R 1b , L and n are as described above.
- two aromatic hydroxy groups (R 1b —OH) are specified, and the divalent aromatic group represented by R 1b has a hydroxy group as a substituent.
- aromatic polyols include polyaddition reaction products of unsaturated aliphatic cyclic compounds containing two double bonds in one molecule and phenols, and various bisphenol compounds, as components in which n is 1 or more. etc.
- polyaddition reaction products of unsaturated aliphatic cyclic compounds and phenols include unsaturated aliphatic cyclic compounds such as dicyclopentadiene, tetrahydroindene, norbornadiene, limonene, and vinylcyclohexene, even if they have substituents.
- polyaddition reaction products with good phenols e.g., phenol, cresol, xylenol, ethylphenol, propylphenol, vinylphenol, allylphenol, phenylphenol, benzylphenol, halophenol, etc.
- Cyclopetadiene-phenol polyadducts and the like can be mentioned.
- bisphenol compounds include bisphenol A, bisphenol F, bisphenol AF, bisphenol AP, bisphenol B, bisphenol BP, bisphenol C, bisphenol M and the like.
- aromatic polyols include diols (benzenediol, naphthalenediol, etc.) in which two hydroxy groups are bonded to carbon atoms on an aromatic ring as components in which n is 0.
- Any aliphatic carbonate or aliphatic oxide may be used as the component (x1-2) depending on R 2 in the target skeleton (B).
- R 2 in the target skeleton (B) is an alkylene group having 2 carbon atoms
- ethylene carbonate or ethylene oxide may be used
- R 2 in the target skeleton (B) has the number of carbon atoms.
- propylene carbonate or propylene oxide may be used.
- the hydroxy compound (x1) is a hydroxy compound having both an aromatic hydroxy group and an aliphatic hydroxy group. is preferably 10 mol % or more, more preferably 20 mol % or more, still more preferably 30 mol % or more, 40 mol % or more, or 50 mol % or more. Therefore, in one preferred embodiment, (x1) the hydroxy compound contains 10 mol % or more of a hydroxy compound having both an aromatic hydroxy group and an aliphatic hydroxy group.
- the (x2) component is a divalent aromatic carboxylic acid compound or a divalent aromatic carboxylic acid halide compound and is represented by the following formula (4).
- R3 is as described above, and X represents a hydroxy group or a halogen atom.
- any divalent aromatic carboxylic acid (halide) compound may be used depending on the desired R 3 in the skeleton (A) and skeleton (B). Suitable examples of R3 are as described above.
- R 3 in the target skeleton (A) and skeleton (B) is a phenylene group optionally having substituents
- isophthalic acid (chloride) optionally having substituents
- Optionally substituted terephthalic acid (chloride) may be used.
- the (x3) component is a monovalent hydroxy compound having an aromatic hydroxy group and is represented by the following formula (5).
- R 1a is as described above.
- Any aromatic monool may be used as the component (x3) in order to achieve the desired structure of the polyester resin.
- Suitable examples of R 1a are as described above.
- an aromatic monool when the monovalent aromatic group R 1 in the target skeleton (A) is an optionally substituted naphthyl group, Naphthol may be used, and when the monovalent aromatic group R 1 in the target skeleton (A) is a phenyl group which may have a substituent, even if it has a substituent A good phenol should be used.
- condensation proceeds.
- degree of condensation between the (x2) component and the (x1) component can be adjusted by changing the conditions such as the ratio of each component, and the resulting polyester resin structure (formula ( The number of iterations N) in 1) can be adjusted.
- the condensation reaction may proceed in a solventless system without using a solvent, or may proceed in an organic solvent system using an organic solvent.
- organic solvents used in the condensation reaction include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetic acid ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate.
- An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
- a base may be used in the condensation reaction.
- the base include alkali metal hydroxides such as sodium hydroxide (caustic soda) and potassium hydroxide; tertiary amines such as triethylamine, pyridine and N,N-dimethyl-4-aminopyridine (DMAP); mentioned.
- a base may be used individually by 1 type, and may be used in combination of 2 or more type.
- a condensing agent or an interlayer transfer catalyst may also be used in the condensation reaction.
- any conventionally known ones that can be used in the esterification reaction may be used.
- the reaction temperature in the condensation reaction is not particularly limited as long as the condensation reaction proceeds, and may be in the range of 0 to 80°C, for example.
- the reaction time in the condensation reaction is not particularly limited as long as the desired structure of the polyester resin is achieved, and may be, for example, in the range of 30 minutes to 8 hours.
- the polyester resin may be purified after the condensation reaction.
- a purification step such as washing with water or microfiltration may be performed in order to remove by-product salts and excess starting materials from the system.
- water is added in an amount necessary for dissolving the by-product salt, the mixture is allowed to stand and the liquids are separated, and the aqueous layer is discarded. Further, if necessary, an acid is added for neutralization, and washing with water is repeated.
- the polyester resin can be obtained by removing impurities by precision filtration through a dehydration step using chemicals or azeotropic distillation, and optionally removing the organic solvent by distillation.
- the organic solvent may be used as a solvent for the resin composition without being completely removed.
- the polyester resin of the present invention when combined with a crosslinkable resin, can provide a cured product that exhibits excellent dielectric properties and good chemical resistance.
- the polyester resin of the present invention can also provide a cured product with good chemical resistance even when the blending ratio (mass ratio) with respect to the crosslinkable resin is increased to achieve the transmission loss required for 5G applications. Furthermore, it is possible to suppress the occurrence of crack defects and interfacial peeling defects. Therefore, in one preferred embodiment, the polyester resin of the present invention can be suitably used as a resin cross-linking agent.
- a resin composition can be produced using the polyester resin of the present invention.
- the present invention also provides such resin compositions.
- the resin composition of the present invention contains a polyester resin (X) and a crosslinkable resin (Y), and the polyester resin (X) is the polyester resin of the present invention, that is, the skeleton (A) and the skeleton (B) below. It is characterized by being a polyester resin containing both.
- polyester resin (X) including suitable examples of the skeleton (A) and the skeleton (B), a suitable range of the oxycarbonyl group equivalent weight, and a suitable aspect of the structural unit/general formula, can be found in the [Polyester resin] section above. as explained above.
- the type of the crosslinkable resin (Y) is not particularly limited as long as it can be crosslinked in combination with the polyester resin (X).
- the crosslinkable resin (Y) is a thermosetting resin and a radically polymerizable resin from the viewpoint that a cured product that exhibits excellent dielectric properties and good chemical resistance can be obtained. It is preferably one or more selected from the group consisting of resins.
- thermosetting resin and the radically polymerizable resin known resins used for forming insulating layers of printed wiring boards and semiconductor chip packages may be used.
- Thermosetting resins and radically polymerizable resins that can be used as the crosslinkable resin (Y) are described below.
- thermosetting resins examples include epoxy resins, benzocyclobutene resins, epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, polyimide resins, benzoxazine resins, unsaturated polyester resins, phenol resins, melamine resins, and silicone resins. resins, phenoxy resins, and the like.
- Thermosetting resins may be used singly or in combination of two or more.
- the crosslinkable resin (Y) preferably contains an epoxy resin from the viewpoint of being able to provide a cured product that is remarkably excellent in both dielectric properties and chemical resistance. .
- the type of epoxy resin is not particularly limited as long as it has one or more (preferably two or more) epoxy groups in one molecule.
- epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, and naphthol type epoxy resin.
- naphthalene type epoxy resin naphthylene ether type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene skeleton type epoxy resin, dicyclopentadiene type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanediene Examples include methanol-type epoxy resins, trimethylol-type epoxy resins, and halogenated epoxy resins. According to the resin composition of the present invention containing the polyester resin (X), a cured product exhibiting excellent dielectric properties and good chemical resistance can be obtained regardless of the type of epoxy resin.
- Epoxy resins can be classified into liquid epoxy resins at a temperature of 20° C. (hereinafter referred to as “liquid epoxy resins”) and solid epoxy resins at a temperature of 20° C. (hereinafter referred to as “solid epoxy resins”).
- the crosslinkable resin (Y) the resin composition of the present invention may contain only a liquid epoxy resin, may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin. .
- the blending ratio (liquid:solid) is in the range of 20:1 to 1:20 (preferably 10:1 to 1:10, more preferably 3:1 to 1:3).
- the epoxy group equivalent of the epoxy resin is preferably 50 g/eq. ⁇ 2000g/eq. , more preferably 60 g/eq. ⁇ 1000 g/eq. , more preferably 80 g/eq. ⁇ 500 g/eq. is.
- the epoxy group equivalent is the mass of an epoxy resin containing one equivalent of epoxy groups, and can be measured according to JIS K7236.
- the weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, still more preferably 400 to 1,500.
- the Mw of the epoxy resin can be measured as a polystyrene-equivalent value by the GPC method.
- the type of the radically polymerizable resin is not particularly limited as long as it has one or more (preferably two or more) radically polymerizable unsaturated groups in one molecule.
- the radically polymerizable resin for example, one selected from a maleimide group, a vinyl group, an allyl group, a styryl group, a vinylphenyl group, an acryloyl group, a methacryloyl group, a fumaroyl group, and a maleoyl group as a radically polymerizable unsaturated group. Resins having the above are mentioned.
- the crosslinkable resin (Y) is maleimide resin, (meth)acrylic, from the viewpoint of being able to provide a cured product that is remarkably excellent in both dielectric properties and chemical resistance. It preferably contains one or more selected from resins and styryl resins.
- maleimide resin As the maleimide resin, as long as it has one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl groups) in one molecule, is not particularly limited.
- maleimide resins include "BMI-3000J”, “BMI-5000”, “BMI-1400”, “BMI-1500”, “BMI-1700”, and “BMI-689” (all of which are Co., Ltd.), a maleimide resin containing an aliphatic skeleton having 36 carbon atoms derived from dimer diamine; a maleimide resin containing an indane skeleton, described in the Japan Institute of Invention and Innovation Public Technical Report No.
- the type of (meth)acrylic resin is not particularly limited as long as it has one or more (preferably two or more) (meth)acryloyl groups in one molecule.
- (meth)acryloyl group is a generic term for acryloyl group and methacryloyl group.
- methacrylic resins examples include “A-DOG” (manufactured by Shin-Nakamura Chemical Co., Ltd.), “DCP-A” (manufactured by Kyoeisha Chemical Co., Ltd.), “NPDGA”, “FM-400”, “R-687”, “ (Meth)acrylic resins such as THE-330”, “PET-30”, and “DPHA” (all manufactured by Nippon Kayaku Co., Ltd.).
- the type of the styryl resin is not particularly limited as long as it has one or more (preferably two or more) styryl groups or vinylphenyl groups in one molecule.
- styryl resins include styryl resins such as "OPE-2St”, “OPE-2St 1200", and “OPE-2St 2200” (all manufactured by Mitsubishi Gas Chemical Company).
- the resin composition of the present invention may contain only a thermosetting resin, may contain only a radically polymerizable resin, or may contain a combination of a thermosetting resin and a radically polymerizable resin.
- the mass ratio ((X)/(Y)) of the polyester resin (X) to the crosslinkable resin (Y) may be 1 or more, preferably 1.1 or more, more preferably 1 .2 or more.
- chemical resistance is good even when the blending ratio (mass ratio) to the crosslinkable resin is increased to the above range.
- a cured product can be obtained, and the transmission loss required for 5G applications can be achieved while suppressing the occurrence of crack defects and interfacial peeling defects.
- the upper limit of the mass ratio ((X)/(Y)) may be, for example, 2 or less, 1.9 or less, or 1.8 or less. Therefore, in one embodiment, the mass ratio of polyester resin (X) to crosslinkable resin (Y) ((X)/(Y)) is from 1.2 to 2.0.
- the resin composition of the present invention may further contain an inorganic filler.
- an inorganic filler By containing an inorganic filler, the coefficient of linear thermal expansion and dielectric loss tangent can be further reduced.
- inorganic fillers include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, Strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate and the like.
- silica is preferred.
- examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica.
- silica spherical silica is preferable.
- An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.
- Commercially available inorganic fillers include, for example, “UFP-30” (manufactured by Denka Kagaku Kogyo Co., Ltd.); ”, “SO-C2”, “SO-C1”, “SC-C2” (all manufactured by Admatechs); company) and the like.
- the average particle size of the inorganic filler is preferably 5 ⁇ m or less, more preferably 2 ⁇ m or less, and even more preferably 1 ⁇ m or less, from the viewpoint of making the surface of the cured product (insulating layer) less rough and facilitating the formation of fine wiring.
- the lower limit of the average particle diameter is not particularly limited, and may be, for example, 0.01 ⁇ m or more, 0.02 ⁇ m or more, or 0.03 ⁇ m or more.
- the average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory.
- the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering particle size distribution analyzer, and the median diameter thereof can be used as the average particle size for measurement.
- the measurement sample one obtained by ultrasonically dispersing an inorganic filler in water can be preferably used.
- LA-950 manufactured by Horiba Ltd. can be used as the laser diffraction scattering type particle size distribution analyzer.
- Inorganic fillers include aminosilane coupling agents, ureidosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, vinylsilane coupling agents, styrylsilane coupling agents, and acrylate silane coupling agents. It is preferable to improve moisture resistance and dispersibility by treating the surface with a surface treatment agent such as an agent, an isocyanate silane coupling agent, a sulfide silane coupling agent, an organosilazane compound, or a titanate coupling agent.
- a surface treatment agent such as an agent, an isocyanate silane coupling agent, a sulfide silane coupling agent, an organosilazane compound, or a titanate coupling agent.
- the content of the inorganic filler in the resin composition may be determined according to the properties required for the resin composition.
- the component is 100% by mass, it is, for example, 5% by mass or more, 10% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more.
- the upper limit of the content of the inorganic filler is not particularly limited, but may be, for example, 90% by mass or less, or 80% by mass or less.
- the resin composition of the present invention may further contain a resin cross-linking agent other than the polyester resin (X).
- Resin crosslinking agents other than the polyester resin (X) include “TD2090”, “TD2131” (manufactured by DIC), “MEH-7600”, “MEH-7851”, “MEH-8000H” (manufactured by Meiwa Kasei Co., Ltd.), “NHN”, “CBN”, “GPH-65”, “GPH-103” (manufactured by Nippon Kayaku), “SN170”, “SN180”, “SN190”, “SN475", “SN485", “SN495" , “SN375”, “SN395" (manufactured by Nippon Steel Chemical & Materials Co., Ltd.), “LA7052”, “LA7054”, “LA3018”, “LA1356” (manufactured by DIC) and other phenolic curing agents; “F-a” , “Pd” (manufactured by Shikoku Kasei Co., Ltd.), “HFB2006M” (manufactured by Showa Polymer Co.
- the content of the resin cross-linking agent in the resin composition may be determined according to the properties required for the resin composition.
- the nonvolatile component in the resin composition is 100% by mass, it is preferably 40% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and the lower limit is 0.01% by mass. 0.05% by mass or more, 0.1% by mass or more, or the like.
- the resin composition of the present invention may further contain a cross-linking accelerator.
- a cross-linking accelerator By including a cross-linking accelerator, the cross-linking time and cross-linking temperature can be adjusted efficiently.
- cross-linking accelerators examples include organic phosphine compounds such as “TPP”, “TPP-K”, “TPP-S”, and “TPTP-S” (manufactured by Hokko Chemical Industry Co., Ltd.); , “Cl1Z”, “Cl1Z-CN”, “Cl1Z-CNS”, “Cl1Z-A”, “2MZ-OK”, “2MA-OK”, “2PHZ” (manufactured by Shikoku Kasei Co., Ltd.) and other imidazole compounds; Amine adduct compounds such as Novacure (manufactured by Asahi Chemical Industry Co., Ltd.) and Fujicure (manufactured by Fuji Chemical Industry Co., Ltd.); 1,8-diazabicyclo[5,4,0]undecene-7,4-dimethylaminopyridine, benzyldimethylamine, 2, Amine compounds such as 4,6-tris(dimethylaminomethyl)phenol and 4-dimethyl
- the content of the cross-linking accelerator in the resin composition may be determined according to the properties required for the resin composition.
- the component is 100% by mass, it is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass or less, and the lower limit is 0.001% by mass or more and 0.01% by mass or more. , 0.05% by mass or more, and the like.
- the resin composition of the present invention may further contain any additive.
- additives include, for example, organic fillers such as rubber particles; radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators; phenoxy resins, polyvinyl acetal resins, polysulfone resins, Thermoplastic resins such as polyether sulfone resins, polyphenylene ether resins, polyether ether ketone resins, and polyester resins; Organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; Colorants such as diazo yellow, crystal violet, titanium oxide and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol and phenothiazine; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; Adhesives: Antifoaming agents such as silicone antifoaming agents, acrylic antifoaming agents, fluorine antifoaming agents,
- the resin composition of the present invention may further contain an organic solvent as a volatile component.
- organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, ethylene glycol; acetic acid 2- Ether ester solvents such as ethoxyethyl, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, ⁇ -butyrolactone, and methyl methoxypropionate; Ester alcohol solvent; ether alcohol solvent such as
- the content of the organic solvent in the resin composition may be determined according to the properties required for the resin composition. When it is 100% by mass, it can be, for example, 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less.
- the resin composition of the present invention is prepared by appropriately mixing the necessary components among the above components, and if necessary, kneading means such as three rolls, ball mills, bead mills and sand mills, or super mixers, planetary mixers and the like. It can be prepared by kneading or mixing with a stirring means.
- kneading means such as three rolls, ball mills, bead mills and sand mills, or super mixers, planetary mixers and the like. It can be prepared by kneading or mixing with a stirring means.
- the resin composition of the present invention containing a combination of the polyester resin (X) and the crosslinkable resin (Y) can provide a cured product that exhibits excellent dielectric properties and good chemical resistance.
- the cured product of the resin composition of the present invention exhibits a low dielectric constant (Dk).
- the dielectric constant (Dk) of the cured product of the resin composition of the present invention is preferably 3.0 or less, 2 .9 or less or 2.8 or less.
- the cured product of the resin composition of the present invention exhibits a low dielectric loss tangent (Df).
- Df dielectric loss tangent
- the dielectric loss tangent (Df) of the cured product of the resin composition of the present invention is preferably 0.01 or less, 0 It can be 0.008 or less, 0.0075 or less, or 0.007 or less.
- the cured product of the resin composition of the present invention exhibits high chemical resistance (alkali resistance, acid resistance).
- the weight change rate of the cured product of the resin composition of the present invention can preferably be 1% or less, 0.8% or less, 0.6% or less, 0.5% or less or 0.4% or less.
- the strength change rate can be preferably 1% or less, 0.8% or less, 0.6% or less, 0.5% or less, or 0.4% or less.
- the resin composition of the present invention can also provide a cured product with good chemical resistance even when the blending ratio (mass ratio) of the polyester resin (X) to the crosslinkable resin (Y) is high. It is possible to achieve the transmission loss required for 5G applications while suppressing the occurrence of crack defects and interface peeling defects. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (a resin composition for an insulating layer of a printed wiring board), and can be used for interlayer insulation of a printed wiring board. It can be used more preferably as a resin composition for forming a layer (resin composition for insulating interlayers of printed wiring boards).
- the resin composition of the present invention can also be suitably used when the printed wiring board is a component built-in circuit board.
- the resin composition of the present invention can also be suitably used as a resin composition for encapsulating a semiconductor chip (resin composition for semiconductor encapsulation), and remarkably reduces peeling defects from vias and wiring patterns. Therefore, it can be suitably used as a resin composition for a rewiring layer (resin composition for a rewiring layer) as an insulating layer for forming the rewiring layer.
- the resin composition of the present invention can be used in a wide range of applications that require resin compositions, such as resin sheets, sheet-like laminated materials such as prepreg, solder resists, underfill materials, die bonding materials, hole-filling resins, and component-embedding resins. can be used for
- the resin composition of the present invention can be applied in the form of a varnish, it is preferably used in the form of a sheet-like laminated material containing the resin composition.
- the resin sheets and prepregs shown below are preferable.
- the resin sheet includes a support and a resin composition layer provided on the support (hereinafter simply referred to as "resin composition layer”), and the resin composition layer is the resin composition layer of the present invention. It is characterized by being formed from a resin composition of
- the preferred thickness of the resin composition layer differs depending on the application, and may be determined appropriately according to the application.
- the thickness of the resin composition layer is preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, 120 ⁇ m or less, 100 ⁇ m or less, 80 ⁇ m or less, 60 ⁇ m or less, or 50 ⁇ m or less from the viewpoint of thinning printed wiring boards and semiconductor chip packages.
- the lower limit of the thickness of the resin composition layer is not particularly limited, it can be usually 1 ⁇ m or more, 5 ⁇ m or more, or the like.
- the support examples include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.
- plastic material examples include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA). , cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, and the like.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA).
- TAC triacetyl cellulose
- PES polyether sulfide
- polyether ketone polyimide
- examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred.
- a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. may be used.
- the support may be subjected to matte treatment, corona treatment, or antistatic treatment on the surface to be bonded to the resin composition layer. Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used.
- the release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. .
- SK-1 manufactured by Lintec Co., Ltd., "SK-1", “ AL-5”, “AL-7”, Toray's "Lumirror T60”, Teijin's "Purex”, and Unitika's "Unipeel”.
- the thickness of the support is not particularly limited, it is preferably in the range of 5 ⁇ m to 75 ⁇ m, more preferably in the range of 10 ⁇ m to 60 ⁇ m.
- the thickness of the release layer-attached support as a whole is preferably within the above range.
- a metal foil with a supporting base material which is a thin metal foil laminated with a supporting base material that can be peeled off, may be used.
- the metal foil with a supporting substrate includes a supporting substrate, a release layer provided on the supporting substrate, and a metal foil provided on the releasing layer.
- the resin composition layer is provided on the metal foil.
- the material of the supporting base material is not particularly limited, but examples thereof include copper foil, aluminum foil, stainless steel foil, titanium foil, copper alloy foil and the like.
- copper foil When copper foil is used as the supporting substrate, it may be an electrolytic copper foil or a rolled copper foil.
- the release layer is not particularly limited as long as it can release the metal foil from the support base material, for example, Cr, Ni, Co, Fe, Mo, Ti, W, an alloy layer of an element selected from the group consisting of P; organic A film etc. are mentioned.
- metal foil with a supporting base material for example, copper foil and copper alloy foil are preferable as the material of the metal foil.
- the thickness of the supporting substrate is not particularly limited, but is preferably in the range of 10 ⁇ m to 150 ⁇ m, more preferably in the range of 10 ⁇ m to 100 ⁇ m. Also, the thickness of the metal foil may be, for example, in the range of 0.1 ⁇ m to 10 ⁇ m.
- the resin sheet may further contain optional layers as needed.
- optional layers include a protective film provided on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support).
- the thickness of the protective film is not particularly limited, it is, for example, 1 ⁇ m to 40 ⁇ m.
- the resin sheet is produced by, for example, using a liquid resin composition as it is or preparing a resin varnish by dissolving the resin composition in an organic solvent, coating it on a support using a die coater or the like, and drying it. It can be produced by forming a resin composition layer.
- organic solvent examples include the same organic solvents as those described as components of the resin composition.
- An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
- Drying may be carried out by known methods such as heating and blowing hot air.
- the drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less.
- the temperature is 50° C. to 150° C. for 3 minutes to 10 minutes.
- a resin composition layer can be formed by drying for minutes.
- the resin sheet can be rolled up and stored.
- the resin sheet has a protective film, it can be used by peeling off the protective film.
- the prepreg is formed by impregnating a sheet-like fiber base material with the resin composition of the present invention.
- the sheet-like fiber base material used for the prepreg is not particularly limited, and those commonly used as prepreg base materials such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used.
- the thickness of the sheet-like fiber base material is preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, still more preferably 30 ⁇ m or less, and particularly preferably 20 ⁇ m or less, from the viewpoint of thinning printed wiring boards and semiconductor chip packages.
- the lower limit of the thickness of the sheet-like fiber base material is not particularly limited. Usually, it is 10 ⁇ m or more.
- a prepreg can be manufactured by a known method such as a hot melt method or a solvent method.
- the thickness of the prepreg can be in the same range as the resin composition layer in the resin sheet described above.
- the sheet-like laminated material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board (for a printed wiring board). for insulating interlayers of wiring boards).
- the sheet-like laminated material of the present invention can also be suitably used for sealing semiconductor chips (for semiconductor sealing), and can significantly reduce peeling defects from vias and wiring patterns, so that rewiring is possible. It can be suitably used for a rewiring formation layer as an insulating layer for forming layers.
- the printed wiring board of the present invention includes an insulating layer made of a cured product of the resin composition of the present invention.
- a printed wiring board can be manufactured, for example, using the above resin sheet by a method including the following steps (I) and (II).
- (I) A step of laminating a resin sheet on the inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate
- (II) Curing (for example, thermosetting) the resin composition layer to form an insulating layer process
- the “inner layer substrate” used in step (I) is a member that serves as a printed wiring board substrate, and includes, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. etc.
- the substrate may also have a conductor layer on one or both sides thereof, and the conductor layer may be patterned.
- An inner layer substrate having conductor layers (circuits) formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board.”
- an intermediate product on which an insulating layer and/or a conductor layer are to be further formed when manufacturing a printed wiring board is also included in the "inner layer substrate" as used in the present invention.
- an inner layer board with built-in components may be used.
- Lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side.
- the member for thermocompression bonding the resin sheet to the inner layer substrate include heated metal plates (such as SUS end plates) and metal rolls (SUS rolls).
- the thermocompression member may be directly pressed onto the resin sheet, or may be pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the uneven surface of the inner layer substrate.
- Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method.
- the thermocompression temperature is preferably in the range of 60° C. to 160° C., more preferably 80° C. to 140° C.
- the thermocompression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. .29 MPa to 1.47 MPa
- the heat pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds.
- Lamination can be carried out under reduced pressure conditions, preferably at a pressure of 26.7 hPa or less.
- Lamination can be done with a commercially available vacuum laminator.
- Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, a batch vacuum pressurized laminator, and the like.
- the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side.
- the pressing conditions for the smoothing treatment may be the same as the thermocompression bonding conditions for the lamination described above.
- Smoothing treatment can be performed with a commercially available laminator. Lamination and smoothing may be performed continuously using the above-mentioned commercially available vacuum laminator.
- the support may be removed between step (I) and step (II), or may be removed after step (II).
- the conductor layer may be formed using the metal foil without peeling off the support.
- the supporting substrate and the release layer
- a conductor layer can be formed using metal foil.
- step (II) the resin composition layer is cured (for example, thermally cured) to form an insulating layer made of the cured resin composition.
- Curing conditions for the resin composition layer are not particularly limited, and conditions that are usually employed when forming an insulating layer of a printed wiring board may be used.
- the curing temperature is preferably 120° C. to 250° C., more preferably 150° C. to 240° C., and even more preferably 150° C. to 240° C. is between 180°C and 230°C.
- the curing time can be preferably 5 minutes to 240 minutes, more preferably 10 minutes to 150 minutes, even more preferably 15 minutes to 120 minutes.
- the resin composition layer may be preheated at a temperature lower than the curing temperature before thermally curing the resin composition layer.
- the resin composition layer is cured at a temperature of 50° C. to 120° C., preferably 60° C. to 115° C., more preferably 70° C. to 110° C. for 5 minutes or more, It may be preheated for preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, even more preferably 15 minutes to 100 minutes.
- steps (III) to (V) may be carried out according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards.
- the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or step ( It may be carried out between IV) and step (V). If necessary, the steps (I) to (V) of forming the insulating layer and the conductor layer may be repeated to form a multilayer wiring board.
- the printed wiring board of the present invention can be manufactured using the prepreg described above.
- the manufacturing method is basically the same as in the case of using a resin sheet.
- the step (III) is a step of drilling holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer.
- Step (III) may be performed using, for example, a drill, laser, plasma, or the like, depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.
- Step (IV) is a step of roughening the insulating layer.
- removal of smear (desmear) is also performed in this step (IV).
- the procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are commonly used in forming insulating layers of printed wiring boards can be employed.
- the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid in this order.
- the swelling liquid used in the roughening treatment is not particularly limited, but examples thereof include alkaline solutions, surfactant solutions, etc., preferably alkaline solutions, more preferably sodium hydroxide solutions and potassium hydroxide solutions. preferable.
- Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU” manufactured by Atotech Japan.
- the swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30.degree. C. to 90.degree. C. for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40° C. to 80° C. for 5 minutes to 15 minutes.
- the oxidizing agent used for the roughening treatment is not particularly limited, but examples include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide.
- the roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 100° C. for 10 to 30 minutes.
- the permanganate concentration in the alkaline permanganate solution is preferably 5% by mass to 10% by mass.
- Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan.
- an acidic aqueous solution is preferable, and commercially available products include, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan.
- the treatment with the neutralizing solution can be performed by immersing the treated surface roughened with the oxidizing agent in the neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From the viewpoint of workability, etc., a method of immersing an object roughened with an oxidizing agent in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferable.
- the step (V) is a step of forming a conductor layer, and forms the conductor layer on the insulating layer.
- the conductor material used for the conductor layer is not particularly limited.
- the conductor layer contains one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal.
- the conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper- nickel alloys and copper-titanium alloys).
- single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, nickel-chromium alloys, copper- Nickel alloys and copper/titanium alloy alloy layers are preferred, and single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel/chromium alloy alloy layers are more preferred, and copper single metal layers are preferred.
- a metal layer is more preferred.
- the conductor layer may have a single layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated.
- the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.
- the thickness of the conductor layer is generally 3 ⁇ m to 35 ⁇ m, preferably 5 ⁇ m to 30 ⁇ m, depending on the desired printed wiring board design.
- the conductor layer may be formed by plating.
- a conductive layer having a desired wiring pattern can be formed by plating the surface of an insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. It is preferably formed by a method.
- a semi-additive method is shown below.
- a plating seed layer is formed on the surface of the insulating layer by electroless plating.
- a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to a desired wiring pattern.
- the mask pattern is removed. After that, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.
- the conductor layer may be formed using metal foil.
- step (V) is preferably performed between step (I) and step (II).
- step (I) the support is removed and a metal foil is laminated on the exposed surface of the resin composition layer.
- Lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I).
- step (II) is performed to form an insulating layer.
- a conductor layer having a desired wiring pattern can be formed by conventional known techniques such as the subtractive method and the modified semi-additive method.
- a metal foil can be manufactured by a known method such as an electrolysis method or a rolling method.
- Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Kinzoku Mining Co., Ltd., and the like.
- the metal foil may be used to form the conductor layer.
- the semiconductor chip package of the present invention includes a sealing layer made of a cured product of the resin composition of the present invention.
- the semiconductor chip package of the present invention may also include an insulating layer (rewiring forming layer) for forming a rewiring layer, which is made of a cured product of the resin composition of the present invention.
- a semiconductor chip package can be produced, for example, using the resin composition and resin sheet of the present invention by a method including the following steps (1) to (6).
- the resin composition and resin sheet of the present invention may be used to form the sealing layer in step (3) or the rewiring layer in step (5).
- An example of forming a sealing layer or a rewiring forming layer using a resin composition or a resin sheet will be shown below.
- a semiconductor package can be manufactured according to a known technique.
- the material used for the base material is not particularly limited. Glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel plates (SPCC); 4 substrate); and a substrate made of bismaleimide triazine resin (BT resin).
- the material of the temporary fixing film is not particularly limited as long as it can be peeled off from the semiconductor chip in step (4) and can temporarily fix the semiconductor chip.
- a commercially available product can be used as the temporary fixing film.
- Commercially available products include Riva Alpha manufactured by Nitto Denko Corporation.
- Temporarily fixing the semiconductor chip can be performed using a known device such as a flip chip bonder and a die bonder.
- the layout and the number of arrangement of the semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the production number of the target semiconductor package, etc. For example, a matrix of multiple rows and multiple columns can be aligned and temporarily fixed.
- the resin composition layer of the resin sheet of the present invention is laminated on a semiconductor chip, or the resin composition of the present invention is applied onto a semiconductor chip and cured (for example, thermally cured) to form a sealing layer.
- lamination of a semiconductor chip and a resin sheet can be performed by removing the protective film of the resin sheet and then heat-pressing the resin sheet to the semiconductor chip from the support side.
- the member for thermocompression bonding the resin sheet to the semiconductor chip include a heated metal plate (such as a SUS panel) or a metal roll (SUS roll).
- a heated metal plate such as a SUS panel
- SUS roll metal roll
- the lamination of the semiconductor chip and the resin sheet may be carried out by a vacuum lamination method, and the lamination conditions are the same as the lamination conditions described in relation to the printed wiring board manufacturing method, and the preferred ranges are also the same.
- the resin composition is thermally cured to form a sealing layer.
- the heat curing conditions are the same as the heat curing conditions described in relation to the printed wiring board manufacturing method.
- the resin sheet support may be peeled off after the resin sheet is laminated on the semiconductor chip and thermally cured, or the support may be peeled off before the resin sheet is laminated on the semiconductor chip.
- the application conditions are the same as those for forming the resin composition layer described in relation to the resin sheet of the present invention. , and the preferred ranges are also the same.
- Step (4)- The method of peeling off the substrate and the temporary fixing film can be appropriately changed according to the material of the temporary fixing film.
- the heating conditions are usually 100 to 250° C. for 1 to 90 seconds or 5 to 15 minutes.
- the irradiation dose of ultraviolet rays is usually 10 mJ/cm 2 to 1000 mJ/cm 2 .
- the material for forming the rewiring layer is not particularly limited as long as it has insulating properties when the rewiring layer (insulating layer) is formed. Photosensitive resins and thermosetting resins are preferred. A rewiring formation layer may be formed using the resin composition and resin sheet of the present invention.
- a via hole may be formed in the rewiring layer in order to connect the semiconductor chip and a conductor layer, which will be described later, between layers.
- the via hole may be formed by a known method depending on the material of the rewiring formation layer.
- Step (6)- The formation of the conductor layer on the rewiring formation layer may be carried out in the same manner as the step (V) described in relation to the printed wiring board manufacturing method.
- the steps (5) and (6) may be repeated to alternately build up the conductor layers (rewiring layers) and the rewiring formation layers (insulating layers).
- a semiconductor chip package In manufacturing a semiconductor chip package, (7) forming a solder resist layer on a conductor layer (rewiring layer), (8) forming bumps, (9) separating a plurality of semiconductor chip packages into individual semiconductor chips. A further step of dicing into packages and singulating may be performed. These steps may be performed according to various methods known to those skilled in the art for use in the manufacture of semiconductor chip packages.
- a semiconductor package can be a fan-in. Regardless of whether it is a (Fan-In) type package or a fan-out (Fan-Out) type package, a semiconductor chip package that suppresses the occurrence of crack defects and interface peeling defects and has extremely low transmission loss can be realized.
- the semiconductor chip package of the present invention is a fan-out type package.
- the resin composition and resin sheet of the present invention can be applied to both fan-out panel level packages (FOPLP) and fan-out wafer level packages (FOWLP).
- the semiconductor package of the present invention is a fan-out panel level package (FOPLP).
- the semiconductor package of the present invention is a fan-out wafer level package (FOWLP).
- the semiconductor device of the present invention includes a layer made of a cured product of the resin composition layer of the present invention.
- the semiconductor device of the present invention can be manufactured using the printed wiring board or semiconductor chip package of the present invention.
- semiconductor devices examples include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, televisions, etc.) and vehicles (such as motorcycles, automobiles, trains, ships, aircraft, etc.).
- polyester resin (1)- 37.4 g of hydroxy compound (1) obtained in (1) above 1-naphthol 14 and .4 g, 30.5 g of isophthalic acid chloride, 0.41 g of an interlayer transfer catalyst, and 190 g of methyl isobutyl ketone were charged, and stirred while blowing nitrogen gas to completely dissolve them.
- 60.0 g of a 20% aqueous solution of caustic soda was added dropwise, taking 1 hour to raise the temperature to 60° C. while paying attention to heat generation. After that, after continuing stirring at 60° C.
- the obtained polyester resin (1) was measured by a gel permeation chromatography (GPC) method and an infrared spectroscopic analysis (IR) method based on the following GPC measurement conditions and IR measurement conditions.
- the polyester resin (1) had a number average molecular weight of 872 measured by GPC and a Tg of 65° C. measured by DSC.
- a GPC chart of the polyester resin (1) is shown in FIG. 1a, and an IR chart is shown in FIG. 1b.
- TSKgel F-10, F-4, F-1, A-5000, A-1000, A-500 (manufactured by Tosoh Corporation)
- Sample 0.2% by mass of tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (10 ⁇ l)
- polyester resin (2) (1) Synthesis of raw material hydroxy compound (2) 99.0 g of dicyclopentadiene-phenol polyadduct ("J-DPP85" manufactured by JFE Chemical Co., hydroxyl equivalent: 165 g/eq.) and 30.6 g of propylene carbonate (reagent) were charged, and stirred while blowing nitrogen gas to reach 100%. The temperature was raised to ° C. and dissolved completely. 2.7 g of a 48% KOH aqueous solution was added to the mixture, and the temperature was raised to 180° C. while stirring. During this time, carbon dioxide was generated and the resin solution foamed violently.
- J-DPP85 dicyclopentadiene-phenol polyadduct
- propylene carbonate reagent
- polyester resin (2)- 38.8 g of the hydroxy compound (2) obtained in (1) above 1-naphthol 14 and .4 g, 30.5 g of isophthalic acid chloride, 0.42 g of an interlayer transfer catalyst, and 190 g of methyl isobutyl ketone were charged, and stirred while blowing nitrogen gas to completely dissolve them.
- 60.0 g of a 20% aqueous solution of caustic soda was added dropwise, taking 1 hour to raise the temperature to 60° C. while paying attention to heat generation. After that, after continuing stirring at 60° C.
- the obtained polyester resin (2) was measured by GPC and IR in the same manner as in Example 1.
- the polyester resin (2) had a number average molecular weight of 825 by GPC and a Tg of 50° C. as measured by DSC.
- a GPC chart of the polyester resin (2) is shown in FIG. 2a, and an IR chart is shown in FIG. 2b.
- the obtained polyester resin (2) had the desired molecular structure.
- polyester resin (3) was prepared in the same manner as in Example 2, except that 9.4 g of phenol was used instead of 14.4 g of 1-naphthol in the esterification reaction. 62 g was obtained.
- the obtained polyester resin (3) was measured by GPC and IR in the same manner as in Example 1.
- the polyester resin (3) had a number average molecular weight of 895 by GPC and a Tg of 49° C. as measured by DSC.
- the GPC chart of the polyester resin (3) is shown in FIG. 3a, and the IR chart is shown in FIG. 3b.
- the obtained polyester resin (4) was measured by GPC and IR in the same manner as in Example 1.
- the number average molecular weight of the polyester resin (4) measured by GPC was 680, and Tg measured by DSC was 45°C.
- the GPC chart of the polyester resin (4) is shown in FIG. 4a, and the IR chart is shown in FIG. 4b.
- polyester resin (5)- 25.8 g of the hydroxy compound (5) obtained in (1) above and 14.4 g of 1-naphthol were placed in a 2-liter four-neck round flask equipped with a stirrer, thermometer, dropping funnel, and nitrogen gas inlet.
- 30.5 g of isophthalic chloride, 0.37 g of an interlayer transfer catalyst, and 170 g of methyl isobutyl ketone were charged and completely dissolved by stirring while blowing nitrogen gas.
- 60.0 g of a 20% aqueous solution of caustic soda was added dropwise, taking 1 hour to raise the temperature to 60° C. while paying attention to heat generation.
- the obtained polyester resin (5) was measured by GPC and IR in the same manner as in Example 1.
- the number average molecular weight of the polyester resin (5) measured by GPC was 722, and Tg measured by DSC was 51°C.
- a GPC chart of the polyester resin (5) is shown in FIG. 5a, and an IR chart is shown in FIG. 5b.
- polyester resin (6) 62 g of the desired polyester resin (6) was obtained in the same manner as in Example 1, except that terephthalic acid chloride was used instead of isophthalic acid chloride in the esterification reaction. .
- the obtained polyester resin (6) was measured by GPC and IR in the same manner as in Example 1.
- the polyester resin (6) had a number average molecular weight of 928 by GPC and a Tg of 67° C. as measured by DSC.
- a GPC chart of the polyester resin (6) is shown in FIG. 6a, and an IR chart is shown in FIG. 6b.
- the obtained polyester resin (6) had the desired molecular structure.
- the obtained polyester resin (7) was measured by GPC and IR in the same manner as in Example 1.
- the polyester resin (7) had a number average molecular weight of 803 by GPC and a Tg of 75° C. as measured by DSC.
- a GPC chart of the polyester resin (7) is shown in FIG. 7a, and an IR chart is shown in FIG. 7b.
- polyester resin (8)- 34.9 g of the hydroxy compound (8) obtained in (1) above pentafluorophenol 18 and .4 g, 30.5 g of isophthalic acid chloride, 0.42 g of an interlayer transfer catalyst, and 180 g of methyl isobutyl ketone were charged, and stirred while blowing nitrogen gas to completely dissolve them.
- 60.0 g of a 20% aqueous solution of caustic soda was added dropwise, taking 1 hour to raise the temperature to 60° C. while paying attention to heat generation. After that, after continuing stirring at 60° C.
- the obtained polyester resin (8) was measured by GPC and IR in the same manner as in Example 1.
- the polyester resin (8) had a number average molecular weight of 1293 by GPC and a Tg of 46° C. as measured by DSC.
- a GPC chart of the polyester resin (8) is shown in FIG. 8a, and an IR chart is shown in FIG. 8b.
- polyester resin (9) (1) Synthesis of benzyl-modified 2,7-dihydroxynaphthalene A 2-liter four-necked round vessel equipped with a stirrer, thermometer, nitrogen gas inlet, and Dean-Stark tube. A flask was charged with 64.0 g of 2,7-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.), 86.4 g of benzyl alcohol (manufactured by Junsei Chemical Co., Ltd.), and 4-toluenesulfonic acid monohydrate (manufactured by Junsei Chemical Co., Ltd.). 50 g was charged, and the temperature was raised to 160° C. while stirring while blowing nitrogen gas.
- polyester resin (9)- 38.4 g of the hydroxy compound (9) obtained in (2) above 1-naphthol 14 and .4 g, 30.5 g of isophthalic acid chloride, 0.41 g of an interlayer transfer catalyst, and 170 g of methyl isobutyl ketone were charged, and stirred while blowing nitrogen gas to completely dissolve them.
- 60.0 g of a 20% aqueous solution of caustic soda was added dropwise, taking 1 hour to raise the temperature to 60° C. while paying attention to heat generation. After that, after continuing stirring at 60° C.
- the obtained polyester resin (9) was measured by GPC and IR in the same manner as in Example 1.
- the number average molecular weight of the polyester resin (9) measured by GPC was 872, and the Tg measured by DSC was 65°C.
- a GPC chart of the polyester resin (9) is shown in FIG. 9a, and an IR chart is shown in FIG. 9b.
- the obtained polyester resin (10) was measured by GPC and IR in the same manner as in Example 1.
- the polyester resin (10) had a number average molecular weight of 947 measured by GPC and a Tg of 60° C. measured by DSC.
- a GPC chart of the polyester resin (10) is shown in FIG. 10a, and an IR chart is shown in FIG. 10b.
- polyester resins (1) to (10) synthesized in Examples 1 to 9 and Comparative Example 1 the general formulas related to the theoretical structures are shown, and each structural unit etc. are summarized in Tables 1-1 and 1-2. shown.
- resin sheet A resin composition is coated on a polyethylene terephthalate film (thickness: 38 ⁇ m, hereinafter abbreviated as "PET film") with a die coater so that the thickness of the resin composition layer after drying is 40 ⁇ m. and dried at 120° C. for 2 minutes to prepare a resin sheet.
- PET film polyethylene terephthalate film
- CP521 manufactured by Kanto Applied Electronics Development Co., Ltd.
- E8362B manufactured by Agilent Technologies
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Abstract
Description
[1] 下記骨格(A)と骨格(B)の両方を含有するポリエステル樹脂。
<骨格(A)> 式:(-)R1-O-C(=O)-R3-で表される骨格
<骨格(B)> 式:-R2-O-C(=O)-R3-で表される骨格
(式中、
R1は、1価又は2価の芳香族基を示し、
R2は、2価の脂肪族基を示し、
R3は、2価の芳香族基を示す。)
[2] 分子鎖末端部が、骨格(A)(式中、R1は、1価の芳香族基を示す。)で封鎖されている、[1]に記載のポリエステル樹脂。
[3] 骨格(A)由来のオキシカルボニル基と骨格(B)由来のオキシカルボニル基のモル比率((A):(B))が、30:70~95:5の範囲である、[1]又は[2]に記載のポリエステル樹脂。
[4] 全オキシカルボニル基当量が170g/eq.以上であり、且つ、
骨格(A)由来のオキシカルボニル基当量が220g/eq.以上である、[1]~[3]の何れかに記載のポリエステル樹脂。
[5] R2で表される2価の脂肪族基の炭素原子数が2~5である、[1]~[4]の何れかに記載のポリエステル樹脂。
[6] (x1)芳香族性ヒドロキシ基と脂肪族性ヒドロキシ基の両方を有するヒドロキシ化合物を少なくとも含むヒドロキシ化合物と、
(x2)2価芳香族カルボン酸化合物又は2価芳香族カルボン酸ハライド化合物と、
(x3)芳香族性ヒドロキシ基を有する1価ヒドロキシ化合物と
の縮合反応物である、[1]~[5]の何れかに記載のポリエステル樹脂。
[7] (x1)ヒドロキシ化合物が、
芳香族性ヒドロキシ基を2個以上有するヒドロキシ化合物と、
脂肪族カーボネート又は脂肪族オキサイドと
の反応物である、請求項6に記載のポリエステル樹脂。
[8] (x1)ヒドロキシ化合物が、芳香族性ヒドロキシ基と脂肪族性ヒドロキシ基の両方を有するヒドロキシ化合物を10mоl%以上含む、[6]又は[7]に記載のポリエステル樹脂。
[9] 下記式(i)で表される構造単位iを含有する、[1]~[8]の何れかに記載のポリエステル樹脂。
R1bは、それぞれ独立に、2価の芳香族基を示し、
R2は、それぞれ独立に、2価の脂肪族基を示し、
Lは、それぞれ独立に、単結合又は2価の連結基を示し、
mは、0~5の整数であり、
y1及びy2は、それぞれ独立に、0又は1であり、
*は結合手を示し、該結合手はR3と結合しており、ここでR3は、2価の芳香族基を示す。)
[10] ポリエステル樹脂が1分子当たり含有する構造単位iの平均数をNとしたとき、0<N≦8を満たす、[9]に記載のポリエステル樹脂。
[11] ポリエステル樹脂が1分子当たり含有する構造単位iの平均数をNとしたとき、ポリエステル樹脂1分子当たりに含有される下記式(i-a)で表される構造単位i-a及び式(i-b)で表される構造単位i-bの合計の平均数が0.1N以上である、[9]又は[10]に記載のポリエステル樹脂。
R1b、R2、L、m及び*は上記と同じである。)
[12] 下記式(1)で表される、[1]~[11]の何れかに記載のポリエステル樹脂。
R1aは、それぞれ独立に、1価の芳香族基を示し、
R1bは、それぞれ独立に、2価の芳香族基を示し、
R2は、それぞれ独立に、2価の脂肪族基を示し、
R3は、それぞれ独立に、2価の芳香族基を示し、
Lは、それぞれ独立に、単結合又は2価の連結基を示し、
x1及びx2は、0≦x1≦1、0≦x2≦1及び0<x1+x2<2を満たす数を示し、
nは、0~5の範囲の数であり、
Nは、繰り返し数を示し、0<N≦8を満たす数を示す。)
[13] x1及びx2が、0.1≦x1+x2≦1.5を満たす、[12]に記載のポリエステル樹脂。
[14] x1及びx2が、下記条件(a)~(c)の何れか1つを満たす、[12]又は[13]に記載のポリエステル樹脂。
(a)x1=0、0<x2≦1
(b)x2=0、0<x1≦1
(c)ポリエステル樹脂の分子数をZ個としたとき、Z×N個のx1とx2の組み合わせ中、少なくとも1個のx1とx2の組み合わせにおいて、x1及びx2の一方のみが0である
[15] R1aが、置換基を有していてもよいフェニル基、又は、置換基を有していてもよいナフチル基である、[12]~[14]の何れかに記載のポリエステル樹脂。
[16] R2で表される2価の脂肪族基の炭素原子数が2~5である、[9]~[15]の何れかに記載のポリエステル樹脂。
[17] R1bが、置換基を有していてもよいフェニレン基、又は、置換基を有していてもよいナフチレン基である、[9]~[16]の何れかに記載のポリエステル樹脂。
[18] Lが、置換基を有していてもよい2価の脂肪族基、又は、置換基を有していてもよい2価の芳香族基である、[9]~[17]の何れかに記載のポリエステル樹脂。
[19] 数平均分子量が5000以下である、[1]~[18]の何れかに記載のポリエステル樹脂。
[20] [1]~[19]の何れかに記載のポリエステル樹脂を含む、樹脂架橋剤。
[21] [1]~[19]の何れかに記載のポリエステル樹脂(X)と、架橋性樹脂(Y)とを含む樹脂組成物。
[22] 架橋性樹脂(Y)が、熱硬化性樹脂及びラジカル重合性樹脂からなる群から選択される1種以上である、[21]に記載の樹脂組成物。
[23] 架橋性樹脂(Y)に対するポリエステル樹脂(X)の質量比((X)/(Y))が、1.2~2.0である、[21]又は[22]に記載の樹脂組成物。
[24] さらに無機充填材を含む、[21]~[23]の何れかに記載の樹脂組成物。
[25] さらに有機溶媒を含む、[21]~[24]の何れかに記載の樹脂組成物。
[26] プリント配線板の絶縁層用である、[21]~[25]の何れかに記載の樹脂組成物。
[27] 半導体封止用である、[21]~[25]の何れかに記載の樹脂組成物。
[28] 支持体と、該支持体上に設けられた[21]~[27]の何れかに記載の樹脂組成物の層とを含む、樹脂シート。
[29] シート状繊維基材に、[21]~[27]の何れかに記載の樹脂組成物を含浸させてなる、プリプレグ。
[30] [21]~[27]の何れかに記載の樹脂組成物の硬化物。
[31] [21]~[26]の何れかに記載の樹脂組成物の硬化物からなる絶縁層を含む、プリント配線板。
[32] [21]~[25]、[27]の何れかに記載の樹脂組成物の硬化物からなる封止層を含む、半導体チップパッケージ。
[33] ファンアウト(Fan-Out)型パッケージである、[32]に記載の半導体チップパッケージ。
[34] [31]に記載のプリント配線板又は[32]若しくは[33]に記載の半導体チップパッケージを含む、半導体装置。
本明細書において、化合物又は基についていう「置換基を有していてもよい」という用語は、該化合物又は基の水素原子が置換基で置換されていない場合、及び、該化合物又は基の水素原子の一部又は全部が置換基で置換されている場合の双方を意味する。
本発明のポリエステル樹脂は、下記骨格(A)と骨格(B)の両方を含有することを特徴とする。
<骨格(A)> 式:(-)R1-O-C(=O)-R3-で表される骨格
<骨格(B)> 式:-R2-O-C(=O)-R3-で表される骨格
(式中、
R1は、1価又は2価の芳香族基を示し、
R2は、2価の脂肪族基を示し、
R3は、2価の芳香族基を示す。)
骨格(A)は、式:(-)R1-O-C(=O)-R3-で表される骨格(式中、R1は、1価又は2価の芳香族基を示し、R3は、2価の芳香族基を示す。)である。
骨格(B)は、式:-R2-O-C(=O)-R3-で表される骨格(式中、R2は、2価の脂肪族基を示し、R3は、2価の芳香族基を示す。)である。
R1bは、それぞれ独立に、2価の芳香族基を示し、
R2は、それぞれ独立に、2価の脂肪族基を示し、
Lは、それぞれ独立に、単結合又は2価の連結基を示し、
mは、0~5の整数であり、
y1及びy2は、それぞれ独立に、0又は1であり、
*は結合手を示し、該結合手はR3と結合しており、ここでR3は、2価の芳香族基を示す。)
R1aは、それぞれ独立に、1価の芳香族基を示し、
R1bは、それぞれ独立に、2価の芳香族基を示し、
R2は、それぞれ独立に、2価の脂肪族基を示し、
R3は、それぞれ独立に、2価の芳香族基を示し、
Lは、それぞれ独立に、単結合又は2価の連結基を示し、
x1及びx2は、0≦x1≦1、0≦x2≦1及び0<x1+x2<2を満たす数を示し、
nは、0~5の範囲の数を示し、
Nは、繰り返し数を示し、0<N≦8を満たす数を示す。)
(a)x1=0、0<x2≦1
(b)x2=0、0<x1≦1
(c)ポリエステル樹脂の分子数をZ個としたとき、Z×N個のx1とx2の組み合わせ中、少なくとも1個のx1とx2の組み合わせにおいて、x1及びx2の一方のみが0である。
i)R1aが、置換基を有していてもよいフェニル基、又は、置換基を有していてもよいナフチル基であり、
ii)R2が、炭素原子数2~5の2価の脂肪族基であり、
iii)R3が、置換基を有していてもよいフェニレン基であり、
iv)(a)nが0であり、R1bが置換基を有していてもよいナフチレン基である、又は、(b)nが1~5であり、R1bが置換基を有していてもよいフェニレン基であり、Lが置換基を有していてもよい炭素原子数1~12のアルキレン基、置換基を有していてもよい炭素原子数3~15のシクロアルキレン基、若しくは置換基を有していてもよい炭素原子数6~24のアリーレン基である。
i)R1aが、ハロゲン原子、アルキル基、及びアリール基から選択される1以上の置換基を有していてもよいフェニル基、又は、ハロゲン原子、アルキル基、及びアリール基から選択される1以上の置換基を有していてもよいナフチル基であり、
ii)R2が、ハロゲン原子、アルキル基、及びアリール基から選択される1以上の置換基を有していてもよい炭素原子数2~5のアルキレン基であり、
iii)R3が、ハロゲン原子、アルキル基、及びアリール基から選択される1以上の置換基を有していてもよいフェニレン基であり、
iv)(a)nが0であり、R1bがハロゲン原子、アルキル基、アリール基、アリールアルキル基、及びヒドロキシ基から選択される1以上の置換基を有していてもよいナフチレン基である、又は、(b)nが1~5であり、R1bがハロゲン原子、アルキル基、アリール基、アリールアルキル基、及びヒドロキシ基から選択される置換基を有していてもよいフェニレン基であり、Lがハロゲン原子、アルキル基、及びアリール基から選択される1以上の置換基を有していてもよい炭素原子数1~12のアルキレン基;ハロゲン原子、アルキル基、及びアリール基から選択される1以上の置換基を有していてもよい炭素原子数3~15のシクロアルキレン基;若しくはハロゲン原子、アルキル基、及びアリール基から選択される1以上の置換基を有していてもよい炭素原子数6~24のアリーレン基である。
(x1)芳香族性ヒドロキシ基と脂肪族性ヒドロキシ基の両方を有するヒドロキシ化合物を少なくとも含むヒドロキシ化合物と、
(x2)2価芳香族カルボン酸化合物又は2価芳香族カルボン酸ハライド化合物と、
(x3)芳香族性ヒドロキシ基を有する1価ヒドロキシ化合物と
を縮合反応させて得られる。
(x1)成分は、芳香族性ヒドロキシ基と脂肪族性ヒドロキシ基の両方を有するヒドロキシ化合物を少なくとも含むヒドロキシ化合物であり、下記式(2)で表される。該(x1)ヒドロキシ化合物を用いることにより、骨格(A)と骨格(B)の両方を含有するポリエステル樹脂を合成することができる。
(x1-1)芳香族性ヒドロキシ基を2個以上有するヒドロキシ化合物(下記式(3)で表される)と、
(x1-2)脂肪族カーボネート又は脂肪族オキサイド(脂肪族基としてR2を含む)と
を反応させることにより調製することができる。
(x2)成分は、2価芳香族カルボン酸化合物又は2価芳香族カルボン酸ハライド化合物であり、下記式(4)で表される。
(x3)成分は、芳香族性ヒドロキシ基を有する1価ヒドロキシ化合物であり、下記式(5)で表される。
本発明のポリエステル樹脂を用いて樹脂組成物を製造することができる。本発明は、斯かる樹脂組成物も提供する。
<骨格(A)> 式:(-)R1-O-C(=O)-R3-で表される骨格
<骨格(B)> 式:-R2-O-C(=O)-R3-で表される骨格
(式中、
R1は、1価又は2価の芳香族基を示し、
R2は、2価の脂肪族基を示し、
R3は、2価の芳香族基を示す。)
本発明の樹脂組成物は、ワニス状態で塗布して使用することもできるが、該樹脂組成物を含有するシート状積層材料の形態で用いることが好適である。
本発明のプリント配線板は、本発明の樹脂組成物の硬化物からなる絶縁層を含む。
(I)内層基板上に、樹脂シートを、樹脂シートの樹脂組成物層が内層基板と接合するように積層する工程
(II)樹脂組成物層を硬化(例えば熱硬化)して絶縁層を形成する工程
本発明の半導体チップパッケージは、本発明の樹脂組成物の硬化物からなる封止層を含む。本発明の半導体チップパッケージはまた、先述のとおり、本発明の樹脂組成物の硬化物からなる、再配線層を形成するための絶縁層(再配線形成層)を含んでもよい。
(1)基材に仮固定フィルムを積層する工程、
(2)半導体チップを、仮固定フィルム上に仮固定する工程、
(3)半導体チップ上に封止層を形成する工程、
(4)基材及び仮固定フィルムを半導体チップから剥離する工程、
(5)半導体チップの基材及び仮固定フィルムを剥離した面に、絶縁層としての再配線形成層を形成する工程、及び
(6)再配線形成層上に、導体層としての再配線層を形成する工程
基材に使用する材料は特に限定されない。基材としては、シリコンウェハ;ガラスウェハ;ガラス基板;銅、チタン、ステンレス、冷間圧延鋼板(SPCC)等の金属基板;ガラス繊維にエポキシ樹脂等をしみこませ熱硬化処理した基板(例えばFR-4基板);ビスマレイミドトリアジン樹脂(BT樹脂)からなる基板などが挙げられる。
半導体チップの仮固定は、フリップチップボンダー、ダイボンダー等の公知の装置を用いて行うことができる。半導体チップの配置のレイアウト及び配置数は、仮固定フィルムの形状、大きさ、目的とする半導体パッケージの生産数等に応じて適宜設定することができ、例えば、複数行で、かつ複数列のマトリックス状に整列させて仮固定することができる。
本発明の樹脂シートの樹脂組成物層を、半導体チップ上に積層、又は本発明の樹脂組成物を半導体チップ上に塗布し、硬化(例えば熱硬化)させて封止層を形成する。
基材及び仮固定フィルムを剥離する方法は、仮固定フィルムの材質等に応じて適宜変更することができ、例えば、仮固定フィルムを加熱、発泡(又は膨張)させて剥離する方法、及び基材側から紫外線を照射させ、仮固定フィルムの粘着力を低下させ剥離する方法等が挙げられる。
再配線形成層(絶縁層)を形成する材料は、再配線形成層(絶縁層)形成時に絶縁性を有していれば特に限定されず、半導体チップパッケージの製造のしやすさの観点から、感光性樹脂、熱硬化性樹脂が好ましい。本発明の樹脂組成物、樹脂シートを用いて再配線形成層を形成してもよい。
再配線形成層上への導体層の形成は、プリント配線板の製造方法に関連して説明した工程(V)と同様に実施してよい。なお、工程(5)及び工程(6)を繰り返し行い、導体層(再配線層)及び再配線形成層(絶縁層)を交互に積み上げて(ビルドアップ)もよい。
本発明の半導体装置は、本発明の樹脂組成物層の硬化物からなる層を含む。本発明の半導体装置は、本発明のプリント配線板又は半導体チップパッケージを用いて製造することができる。
(1)原料ヒドロキシ化合物(1)の合成
攪拌装置、温度計、滴下漏斗、窒素ガス吹込み口が装着された2リットル四つ口丸フラスコに、ジシクロペンタジエン-フェノール重付加物(JFEケミカル社製「J-DPP85」、水酸基当量165g/eq.)99.0gとエチレンカーボネート(試薬)26.4gを仕込み、窒素ガスを吹き込みながら攪拌して100℃まで昇温し完全に溶解させた。そのなかに48%KOH水溶液2.6gを添加して、攪拌しながら180℃まで昇温した。その間、炭酸ガスが発生して樹脂溶液が激しく発泡した。その発泡が完全に停止したことを確認した後、さらにその温度で1時間攪拌を続けた後に、メチルイソブチルケトン300gを添加して完全に溶解した。そこに蒸留水70gとリン酸水素二ナトリウム7.0gを加えて中和して、さらに同量の蒸留水で3回水洗した。その後共沸脱水した後に精密ろ過し、最後に180℃で減圧蒸留して、目的の原料ヒドロキシ化合物(1)94gを得た。この化合物の水酸基当量は185g/eq.(理論値187g/eq.;x1+x2=1に対応)であったので、目的の分子構造を有するものであることが確認された。
攪拌装置、温度計、滴下漏斗、窒素ガス吹込み口が装着された0.5リットル四つ口丸フラスコに、上記(1)で得られたヒドロキシ化合物(1)37.4g、1-ナフトール14.4g、イソフタル酸クロリド30.5g、層間移動触媒0.41g、メチルイソブチルケトン190gを仕込み、窒素ガスを吹き込みながら攪拌して完全に溶解させた。30℃で20%苛性ソーダ水溶液60.0gを、発熱に注意しながら、最終的に60℃まで昇温するように1時間要して滴下した。その後、さらに60℃で2時間攪拌を続けた後に、蒸留水50gを添加して、副生無機塩を完全に溶解した後に、その液を分液漏斗に移して静置分液して下層(水層)を棄却した。さらに水洗を3回繰り返し完全に中和した後に共沸蒸留で脱水し、精密ろ過した。その溶液を200℃で真空蒸留して溶媒を除去することによって目的のポリエステル樹脂(1)67gを得た。
測定装置:東ソー株式会社製「HLC-8420GPC」
カラム:東ソー株式会社製ガードカラム「HXL-L」+東ソー株式会社製「TSK-GEL SuperHZ2000」+東ソー株式会社製「TSK-GEL SuperHZ2000」+東ソー株式会社製「TSK-GEL SuperHZ3000」+東ソー株式会社製「TSK-GEL SuperHZ4000」
検出器:RI(示差屈折計)
データ処理:東ソー株式会社製「GPCワークステーション EcoSEC-WorkStation」
カラム温度:40℃
展開溶媒:テトラヒドロフラン
流速:0.35ml/分
標準:前記「GPCワークステーション EcoSEC-WorkStation」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
TSKgel F-10、F-4、F-1、A-5000、A-1000、A-500(東ソー株式会社製)
試料:樹脂固形分換算で0.2質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(10μl)
測定装置:JASCO株式会社製「FT/IR-4600」
(1)原料ヒドロキシ化合物(2)の合成
攪拌装置、温度計、滴下漏斗、窒素ガス吹込み口が装着された2リットル四つ口丸フラスコに、ジシクロペンタジエン-フェノール重付加物(JFEケミカル社製「J-DPP85」、水酸基当量165g/eq.)99.0gとプロピレンカーボネート(試薬)30.6gを仕込み、窒素ガスを吹き込みながら攪拌して100℃まで昇温し完全に溶解させた。そのなかに48%KOH水溶液2.7gを添加して、攪拌しながら180℃まで昇温した。その間、炭酸ガスが発生して樹脂溶液が激しく発泡した。その発泡が完全に停止したことを確認した後、さらにその温度で1時間攪拌を続けた後に、メチルイソブチルケトン300gを添加して完全に溶解した。そこに蒸留水70gとリン酸水素二ナトリウム7.0gを加えて中和して、さらに同量の蒸留水で3回水洗した。その後共沸脱水した後に精密ろ過し、最後に180℃で減圧蒸留して目的の原料ヒドロキシ化合物(2)96gを得た。この化合物の水酸基当量は192g/eq.(理論値194g/eq.;x1+x2=1に対応)であったので、目的の分子構造を有するものであることが確認された。
攪拌装置、温度計、滴下漏斗、窒素ガス吹込み口が装着された0.5リットル四つ口丸フラスコに、上記(1)で得られたヒドロキシ化合物(2)38.8g、1-ナフトール14.4g、イソフタル酸クロリド30.5g、層間移動触媒0.42g、メチルイソブチルケトン190gを仕込み、窒素ガスを吹き込みながら攪拌して完全に溶解させた。30℃で20%苛性ソーダ水溶液60.0gを、発熱に注意しながら、最終的に60℃まで昇温するように1時間要して滴下した。その後、さらに60℃で2時間攪拌を続けた後に、蒸留水50gを添加して、副生無機塩を完全に溶解した後に、その液を分液漏斗に移して静置分液して下層(水層)を棄却した。さらに水洗を3回繰り返し完全に中和した後に共沸蒸留で脱水し、精密ろ過した。その溶液を200℃で真空蒸留して溶媒を除去することによって目的のポリエステル樹脂(2)67gを得た。
エステル化反応において1-ナフトール14.4gに代えてフェノール9.4gを使用した以外は、実施例2と同様にして、目的のポリエステル樹脂(3)62gを得た。
(1)原料ヒドロキシ化合物(4)の合成
攪拌装置、温度計、滴下漏斗、窒素ガス吹込み口が装着された2リットル四つ口丸フラスコに、ビスフェノールF(本州化学工業社製「Bis-F」、水酸基当量100g/eq.)80.0gとエチレンカーボネート(試薬)49.3gを仕込み、窒素ガスを吹き込みながら攪拌して100℃まで昇温し完全に溶解させた。そのなかに48%KOH水溶液3.7gを添加して、攪拌しながら180℃まで昇温した。その間、炭酸ガスが発生して樹脂溶液が激しく発泡した。その発泡が完全に停止したことを確認した後、さらにその温度で1時間攪拌を続けた後に、メチルイソブチルケトン200gを添加して完全に溶解した。そこに蒸留水70gとリン酸水素二ナトリウム7.0gを加えて中和して、さらに同量の蒸留水で3回水洗した。その後共沸脱水した後に精密ろ過し、最後に180℃で減圧蒸留して目的の原料ヒドロキシ化合物(4)110gを得た。この化合物の水酸基当量は132g/eq.(理論値131g/eq.;x1+x2=1.4に対応)であったので、目的の分子構造を有するものであることが確認された。
攪拌装置、温度計、滴下漏斗、窒素ガス吹込み口が装着された0.5リットル四つ口丸フラスコに、上記(1)で得られたヒドロキシ化合物(4)26.2g、フェノール9.4g、イソフタル酸クロリド30.5g、層間移動触媒0.33g、メチルイソブチルケトン150gを仕込み、窒素ガスを吹き込みながら攪拌して完全に溶解させた。30℃で20%苛性ソーダ水溶液60.0gを、発熱に注意しながら、最終的に60℃まで昇温するように1時間要して滴下した。その後、さらに60℃で2時間攪拌を続けた後に、蒸留水50gを添加して、副生無機塩を完全に溶解した後に、その液を分液漏斗に移して静置分液して下層(水層)を棄却した。さらに水洗を3回繰り返し完全に中和した後に共沸蒸留で脱水し、精密ろ過した。その溶液を200℃で真空蒸留して溶媒を除去することによって目的のポリエステル樹脂(4)48gを得た。
(1)原料ヒドロキシ化合物(5)の合成
攪拌装置、温度計、滴下漏斗、窒素ガス吹込み口が装着された2リットル四つ口丸フラスコに、ビスフェノールF(本州化学工業社製「Bis-F」、水酸基当量100g/eq.)80.0gとプロピレンカーボネート(試薬)40.8gを仕込み、窒素ガスを吹き込みながら攪拌して100℃まで昇温し完全に溶解させた。そのなかに48%KOH水溶液2.5gを添加して、攪拌しながら180℃まで昇温した。その間、炭酸ガスが発生して樹脂溶液が激しく発泡した。その発泡が完全に停止したことを確認した後、さらにその温度で1時間攪拌を続けた後に、メチルイソブチルケトン200gを添加して完全に溶解した。そこに蒸留水70gとリン酸水素二ナトリウム7.0gを加えて中和して、さらに同量の蒸留水で3回水洗した。その後共沸脱水した後に精密ろ過し、最後に180℃で減圧蒸留して目的の原料ヒドロキシ化合物(5)87gを得た。この化合物の水酸基当量は131g/eq.(理論値129g/eq.;x1+x2=1に対応)であったので、目的の分子構造を有するものであることが確認された。
攪拌装置、温度計、滴下漏斗、窒素ガス吹込み口が装着された2リットル四つ口丸フラスコに、上記(1)で得られたヒドロキシ化合物(5)25.8g、1-ナフトール14.4g、イソフタル酸クロリド30.5g、層間移動触媒0.37g、メチルイソブチルケトン170gを仕込み、窒素ガスを吹き込みながら攪拌して完全に溶解させた。30℃で20%苛性ソーダ水溶液60.0gを、発熱に注意しながら、最終的に60℃まで昇温するように1時間要して滴下した。その後、さらに60℃で2時間攪拌を続けた後に、蒸留水50gを添加して、副生無機塩を完全に溶解した後に、その液を分液漏斗に移して静置分液して下層(水層)を棄却した。さらに水洗を3回繰り返し完全に中和した後に共沸蒸留で脱水し、精密ろ過した。その溶液を200℃で真空蒸留して溶媒を除去することによって目的のポリエステル樹脂(5)51gを得た。
エステル化反応においてイソフタル酸クロリドに代えてテレフタル酸クロリドを使用した以外は、実施例1と同様にして、目的のポリエステル樹脂(6)62gを得た。
(1)原料ヒドロキシ化合物(7)の合成
攪拌装置、温度計、滴下漏斗、窒素ガス吹込み口が装着された2リットル四つ口丸フラスコに、ビスフェノールフルオレン(大阪ガスケミカル社製「BPF」、水酸基当量175g/eq.)70.0gとエチレンカーボネート(試薬)17.6gを仕込み、窒素ガスを吹き込みながら攪拌して150℃まで昇温し完全に溶解させた。そのなかに48%KOH水溶液1.8gを添加して、攪拌しながら180℃まで昇温した。その間、炭酸ガスが発生して樹脂溶液が激しく発泡した。その発泡が完全に停止したことを確認した後、さらにその温度で1時間攪拌を続けた後に、メチルイソブチルケトン200gを添加して完全に溶解した。そこに蒸留水70gとリン酸水素二ナトリウム7.0gを加えて中和して、さらに同量の蒸留水で3回水洗した。その後共沸脱水した後に精密ろ過して、最後に180℃で減圧蒸留して目的の原料ヒドロキシ化合物(7)70gを得た。この化合物の水酸基当量は195g/eq.(理論値197g/eq.;x1+x2=1に対応)であったので、目的の分子構造を有するものであることが確認された。
攪拌装置、温度計、滴下漏斗、窒素ガス吹込み口が装着された0.5リットル四つ口丸フラスコに、上記(1)で得られたヒドロキシ化合物(7)39.4g、1-ナフトール14.4g、イソフタル酸クロリド30.5g、層間移動触媒0.43g、メチルイソブチルケトン195gを仕込み、窒素ガスを吹き込みながら攪拌して完全に溶解させた。30℃で20%苛性ソーダ水溶液60.0gを、発熱に注意しながら、最終的に60℃まで昇温するように1時間要して滴下した。その後、さらに60℃で2時間攪拌を続けた後に、蒸留水50gを添加して、副生無機塩を完全に溶解した後に、その液を分液漏斗に移して静置分液して下層(水層)を棄却した。さらに水洗を3回繰り返し完全に中和した後に共沸蒸留で脱水し、精密ろ過した。その溶液を200℃で真空蒸留して溶媒を除去することによって目的のポリエステル樹脂(7)65gを得た。
(1)原料ヒドロキシ化合物(8)の合成
攪拌装置、温度計、滴下漏斗、窒素ガス吹込み口が装着された2リットル四つ口丸フラスコに、2、2-ビス(4-ヒドロキシフェニル)ヘキサフルオロプロパン(ビスフェノールAF、水酸基当量168g/eq.)100.8gとエチレンカーボネート(試薬)15.8gを仕込み、窒素ガスを吹き込みながら攪拌して100℃まで昇温し完全に溶解させた。そのなかに48%KOH水溶液2.4gを添加して、攪拌しながら180℃まで昇温した。その間、炭酸ガスが発生して樹脂溶液が激しく発泡した。その発泡が完全に停止したことを確認した後、さらにその温度で1時間攪拌を続けた後に、メチルイソブチルケトン200gを添加して完全に溶解した。そこに蒸留水70gとリン酸水素二ナトリウム10.0gを加えて中和して、さらに同量の蒸留水で3回水洗した。その後共沸脱水した後に精密ろ過して、最後に180℃で減圧蒸留して目的の原料ヒドロキシ化合物(8)95gを得た。この化合物の水酸基当量は177g/eq.(理論値175g/eq.;x1+x2=0.6に対応)であったので、目的の分子構造を有するものであることが確認された。
攪拌装置、温度計、滴下漏斗、窒素ガス吹込み口が装着された0.5リットル四つ口丸フラスコに、上記(1)で得られたヒドロキシ化合物(8)34.9g、ペンタフルオロフェノール18.4g、イソフタル酸クロリド30.5g、層間移動触媒0.42g、メチルイソブチルケトン180gを仕込み、窒素ガスを吹き込みながら攪拌して完全に溶解させた。30℃で20%苛性ソーダ水溶液60.0gを、発熱に注意しながら、最終的に60℃まで昇温するように1時間要して滴下した。その後、さらに60℃で2時間攪拌を続けた後に、蒸留水50gを添加して、副生無機塩を完全に溶解した後に、その液を分液漏斗に移して静置分液して下層(水層)を棄却した。さらに水洗を3回繰り返し完全に中和した後に共沸蒸留で脱水し、精密ろ過した。その溶液を200℃で真空蒸留して溶媒を除去することによって目的のポリエステル樹脂(8)62gを得た。
(1)ベンジル変性2,7-ジヒドロキシナフタレンの合成
攪拌装置、温度計、窒素ガス吹込み口、ディーンスターク管が装着された2リットル四つ口丸フラスコに、2,7-ジヒドロキシナフタレン(東京化成工業社製)64.0gとベンジルアルコール(純正化学社製)86.4g、4-トルエンスルホン酸・一水和物(純正化学社製)1.50gを仕込み、窒素ガスを吹き込みながら攪拌して160℃まで昇温した。その間、脱水による発泡と水の留出が見られた。その発泡が完全に停止したことを確認した後、さらにその温度で1時間攪拌を続けた後に、メチルイソブチルケトン200gを添加して完全に溶解した。そこに蒸留水70gと50%苛性ソーダ使用液0.9gを加えて中和して、さらに同量の蒸留水で3回水洗した。その後共沸脱水した後に精密ろ過し、最後に180℃で減圧蒸留して、目的のベンジル変性ジヒドロキシナフタレン(1)130gを得た。この化合物の水酸基当量は168g/eq.(理論値170g/eq.)であったので、目的の分子構造を有するものであることが確認された。
攪拌装置、温度計、滴下漏斗、窒素ガス吹込み口が装着された2リットル四つ口丸フラスコに、上記(1)で合成したベンジル変性ジヒドロキシナフタレン102.0gとエチレンカーボネート(試薬)26.4gを仕込み、窒素ガスを吹き込みながら攪拌して100℃まで昇温し完全に溶解させた。そこに48%KOH水溶液2.6gを添加して、攪拌しながら180℃まで昇温した。その間、炭酸ガスが発生して樹脂溶液が激しく発泡した。その発泡が完全に停止したことを確認した後、さらにその温度で1時間攪拌を続けた後に、メチルイソブチルケトン300gを添加して完全に溶解した。そこに蒸留水70gとリン酸水素二ナトリウム7.0gを加えて中和して、さらに同量の蒸留水で3回水洗した。その後共沸脱水した後に精密ろ過し、最後に180℃で減圧蒸留して、目的の原料ヒドロキシ化合物(9)96gを得た。この化合物の水酸基当量は190g/eq.(理論値 192g/eq.;x1+x2=1に対応)であったので、目的の分子構造を有するものであることが確認された。
攪拌装置、温度計、滴下漏斗、窒素ガス吹込み口が装着された0.5リットル四つ口丸フラスコに、上記(2)で得られたヒドロキシ化合物(9)38.4g、1-ナフトール14.4g、イソフタル酸クロリド30.5g、層間移動触媒0.41g、メチルイソブチルケトン170gを仕込み、窒素ガスを吹き込みながら攪拌して完全に溶解させた。30℃で20%苛性ソーダ水溶液60.0gを、発熱に注意しながら、最終的に60℃まで昇温するように1時間要して滴下した。その後、さらに60℃で2時間攪拌を続けた後に、蒸留水50gを添加して、副生無機塩を完全に溶解した後に、その液を分液漏斗に移して静置分液して下層(水層)を棄却した。さらに水洗を3回繰り返し完全に中和した後に共沸蒸留で脱水し、精密ろ過した。その溶液を200℃で真空蒸留して溶媒を除去することによって目的のポリエステル樹脂(9)65gを得た。
攪拌装置、温度計、滴下漏斗、窒素ガス吹込み口が装着された0.5リットル四つ口丸フラスコに、ジシクロペンタジエン-フェノール重付加物(JFEケミカル社製「J-DPP85」、水酸基当量165g/eq.)33g、1-ナフトール14.4g、イソフタル酸クロリド30.5g、層間移動触媒0.39g、メチルイソブチルケトン130gを仕込み、窒素ガスを吹き込みながら攪拌して完全に溶解させた。30℃で20%苛性ソーダ水溶液60.0gを、発熱に注意しながら、最終的に60℃まで昇温するように1時間要して滴下した。その後、さらに60℃で2時間攪拌を続けた後に、蒸留水50gを添加して、副生無機塩を完全に溶解した後に、その液を分液漏斗に移して静置分液して下層(水層)を棄却した。さらに水洗を3回繰り返し完全に中和した後に共沸蒸留で脱水し、精密ろ過した。その溶液を200℃で真空蒸留して溶媒を除去することによって目的のポリエステル樹脂(10)56gを得た。
(1)樹脂組成物の調製
合成したポリエステル樹脂(1)~(10)を用いて、下記表2に示す組成の樹脂組成物を調製した。
樹脂組成物をポリエチレンテレフタレートフィルム(厚さ38μm、以下「PETフィルム」と略称する。)上に、乾燥後の樹脂組成物層の厚さが40μmとなるようにダイコーターにて塗布し、120℃で2分間乾燥させて、樹脂シートを作製した。
作製した樹脂シートを190℃で90分間加熱して樹脂組成物層を熱硬化させた。次いで、PETフィルムを剥離してシート状の硬化物を得た。
硬化物を、幅2mm、長さ80mmの試験片に切断し、空洞共振器摂動法誘電率測定装置(関東応用電子開発社製「CP521」)及びネットワークアナライザー(アジレントテクノロジー社製「E8362B」)を使用して、空洞共振法で測定周波数5.8GHz、23℃にて比誘電率と誘電正接の測定を行った。各硬化物について、2本の試験片について測定を行い(n=2)、平均値を算出した。
(a)重量変化率の評価
硬化物を、幅10mm、長さ50mmの試験片に切断し、100℃に加熱したオーブンで30分間乾燥させた後、重量(M1)を測定した。次いで、試験片を10重量%水酸化ナトリウム水溶液、10重量%硫酸にそれぞれ40℃で24時間浸漬した。その後、浸漬した試験片を水で十分に洗浄後、100℃に加熱したオーブンで30分間乾燥し、重量(M2)を測定した。測定した重量M1及びM2に基づき、薬品浸漬後の重量変化率(%)(=(M1-M2)/M1×100)を算出した。
硬化物を、幅10mm、長さ50mmの試験片に切断し、100℃に加熱したオーブンで30分間乾燥させた後、引張強度(S1)を測定した。なお、引張強度は、JIS K7161に準拠し、温度25℃、湿度60%RH、引っ張り速度50mm/分にてテンシロン万能試験機(株式会社エー・アンド・デイ製)により測定した。次いで、試験片を10重量%水酸化ナトリウム水溶液、10重量%硫酸にそれぞれ40℃で24時間浸漬した。その後、浸漬した試験片を水で十分に洗浄後、100℃に加熱したオーブンで30分間乾燥し、引張強度(S2)を測定した。測定した強度S1及びS2に基づき、薬品浸漬後の強度変化率(%)(=(S1-S2)/S1×100)を算出した。
Claims (34)
- 下記骨格(A)と骨格(B)の両方を含有するポリエステル樹脂。
<骨格(A)> 式:(-)R1-O-C(=O)-R3-で表される骨格
<骨格(B)> 式:-R2-O-C(=O)-R3-で表される骨格
(式中、
R1は、1価又は2価の芳香族基を示し、
R2は、2価の脂肪族基を示し、
R3は、2価の芳香族基を示す。) - 分子鎖末端部が、骨格(A)(式中、R1は、1価の芳香族基を示す。)で封鎖されている、請求項1に記載のポリエステル樹脂。
- 骨格(A)由来のオキシカルボニル基と骨格(B)由来のオキシカルボニル基のモル比率((A):(B))が、30:70~95:5の範囲である、請求項1又は2に記載のポリエステル樹脂。
- 全オキシカルボニル基当量が170g/eq.以上であり、且つ、
骨格(A)由来のオキシカルボニル基当量が220g/eq.以上である、請求項1~3の何れか1項に記載のポリエステル樹脂。 - R2で表される2価の脂肪族基の炭素原子数が2~5である、請求項1~4の何れか1項に記載のポリエステル樹脂。
- (x1)芳香族性ヒドロキシ基と脂肪族性ヒドロキシ基の両方を有するヒドロキシ化合物を少なくとも含むヒドロキシ化合物と、
(x2)2価芳香族カルボン酸化合物又は2価芳香族カルボン酸ハライド化合物と、
(x3)芳香族性ヒドロキシ基を有する1価ヒドロキシ化合物と
の縮合反応物である、請求項1~5の何れか1項に記載のポリエステル樹脂。 - (x1)ヒドロキシ化合物が、
芳香族性ヒドロキシ基を2個以上有するヒドロキシ化合物と、
脂肪族カーボネート又は脂肪族オキサイドと
の反応物である、請求項6に記載のポリエステル樹脂。 - (x1)ヒドロキシ化合物が、芳香族性ヒドロキシ基と脂肪族性ヒドロキシ基の両方を有するヒドロキシ化合物を10mоl%以上含む、請求項6又は7に記載のポリエステル樹脂。
- ポリエステル樹脂が1分子当たり含有する構造単位iの平均数をNとしたとき、0<N≦8を満たす、請求項9に記載のポリエステル樹脂。
- x1及びx2が、0.1≦x1+x2≦1.5を満たす、請求項12に記載のポリエステル樹脂。
- x1及びx2が、下記条件(a)~(c)の何れか1つを満たす、請求項12又は13に記載のポリエステル樹脂。
(a)x1=0、0<x2≦1
(b)x2=0、0<x1≦1
(c)ポリエステル樹脂の分子数をZ個としたとき、Z×N個のx1とx2の組み合わせ中、少なくとも1個のx1とx2の組み合わせにおいて、x1及びx2の一方のみが0である - R1aが、置換基を有していてもよいフェニル基、又は、置換基を有していてもよいナフチル基である、請求項12~14の何れか1項に記載のポリエステル樹脂。
- R2で表される2価の脂肪族基の炭素原子数が2~5である、請求項9~15の何れか1項に記載のポリエステル樹脂。
- R1bが、置換基を有していてもよいフェニレン基、又は、置換基を有していてもよいナフチレン基である、請求項9~16の何れか1項に記載のポリエステル樹脂。
- Lが、置換基を有していてもよい2価の脂肪族基、又は、置換基を有していてもよい2価の芳香族基である、請求項9~17の何れか1項に記載のポリエステル樹脂。
- 数平均分子量が5000以下である、請求項1~18の何れか1項に記載のポリエステル樹脂。
- 請求項1~19の何れか1項に記載のポリエステル樹脂を含む、樹脂架橋剤。
- 請求項1~19の何れか1項に記載のポリエステル樹脂(X)と、架橋性樹脂(Y)とを含む樹脂組成物。
- 架橋性樹脂(Y)が、熱硬化性樹脂及びラジカル重合性樹脂からなる群から選択される1種以上である、請求項21に記載の樹脂組成物。
- 架橋性樹脂(Y)に対するポリエステル樹脂(X)の質量比((X)/(Y))が、1.2~2.0である、請求項21又は22に記載の樹脂組成物。
- さらに無機充填材を含む、請求項21~23の何れか1項に記載の樹脂組成物。
- さらに有機溶媒を含む、請求項21~24の何れか1項に記載の樹脂組成物。
- プリント配線板の絶縁層用である、請求項21~25の何れか1項に記載の樹脂組成物。
- 半導体封止用である、請求項21~25の何れか1項に記載の樹脂組成物。
- 支持体と、該支持体上に設けられた請求項21~27の何れか1項に記載の樹脂組成物の層とを含む、樹脂シート。
- シート状繊維基材に、請求項21~27の何れか1項に記載の樹脂組成物を含浸させてなる、プリプレグ。
- 請求項21~27の何れか1項に記載の樹脂組成物の硬化物。
- 請求項21~26の何れか1項に記載の樹脂組成物の硬化物からなる絶縁層を含む、プリント配線板。
- 請求項21~25、27の何れか1項に記載の樹脂組成物の硬化物からなる封止層を含む、半導体チップパッケージ。
- ファンアウト(Fan-Out)型パッケージである、請求項32に記載の半導体チップパッケージ。
- 請求項31に記載のプリント配線板又は請求項32若しくは33に記載の半導体チップパッケージを含む、半導体装置。
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP22780264.2A EP4318568A4 (en) | 2021-03-29 | 2022-03-18 | Polyester resin |
| CN202280025045.7A CN117098794A (zh) | 2021-03-29 | 2022-03-18 | 聚酯树脂 |
| KR1020237033681A KR20230163426A (ko) | 2021-03-29 | 2022-03-18 | 폴리에스테르 수지 |
| JP2023510991A JP7435906B2 (ja) | 2021-03-29 | 2022-03-18 | ポリエステル樹脂 |
| US18/454,865 US20230391949A1 (en) | 2021-03-29 | 2023-08-24 | Polyester resin |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-055986 | 2021-03-29 | ||
| JP2021055986 | 2021-03-29 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US18/454,865 Continuation US20230391949A1 (en) | 2021-03-29 | 2023-08-24 | Polyester resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2022210049A1 true WO2022210049A1 (ja) | 2022-10-06 |
Family
ID=83456125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2022/012818 Ceased WO2022210049A1 (ja) | 2021-03-29 | 2022-03-18 | ポリエステル樹脂 |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20230391949A1 (ja) |
| EP (1) | EP4318568A4 (ja) |
| JP (1) | JP7435906B2 (ja) |
| KR (1) | KR20230163426A (ja) |
| CN (1) | CN117098794A (ja) |
| TW (1) | TW202309133A (ja) |
| WO (1) | WO2022210049A1 (ja) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2024075486A (ja) * | 2022-11-22 | 2024-06-03 | 味の素株式会社 | 化合物 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118043373A (zh) * | 2021-10-01 | 2024-05-14 | 味之素株式会社 | 聚酯树脂 |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006003584A (ja) * | 2004-06-17 | 2006-01-05 | Ricoh Co Ltd | 静電荷現像用トナー及び現像剤 |
| JP2007254557A (ja) * | 2006-03-22 | 2007-10-04 | Toyo Ink Mfg Co Ltd | 熱硬化性樹脂およびその製造方法、さらにそれを用いた熱硬化性組成物および硬化物 |
| JP2009235165A (ja) | 2008-03-26 | 2009-10-15 | Dic Corp | エポキシ樹脂組成物、及びその硬化物 |
| WO2013128872A1 (ja) * | 2012-02-29 | 2013-09-06 | 三洋化成工業株式会社 | トナーバインダーおよびトナー |
| JP2014025022A (ja) | 2012-07-30 | 2014-02-06 | Teijin Ltd | 共重合芳香族ポリエステルの製造方法 |
| JP2016223033A (ja) * | 2015-06-01 | 2016-12-28 | 三洋化成工業株式会社 | セラミック繊維用処理剤 |
| JP2018090560A (ja) * | 2016-02-03 | 2018-06-14 | 田岡化学工業株式会社 | フルオレン骨格を有するビスフェノール類及びその製造方法、並びに該ビスフェノール類から誘導されるポリアリレート樹脂、(メタ)アクリレート化合物及びエポキシ樹脂 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4085091A (en) * | 1976-12-16 | 1978-04-18 | E. I. Dupont De Nemours And Company | Thermally stable, rigid polyesters from thermally stable, rigid dibasic acids and aromatic dihydroxy compounds |
| US5300621A (en) * | 1992-02-13 | 1994-04-05 | Teijin Limited | Semicrystalline aromatic polyester, process for its production and resin composition containing it |
| TWI572665B (zh) * | 2012-10-17 | 2017-03-01 | Dainippon Ink & Chemicals | 活性酯樹脂、環氧樹脂組成物、其硬化物、預浸體、 電路基板以及積層膜 |
| TWI579334B (zh) * | 2015-11-24 | 2017-04-21 | Far Eastern New Century Corp | Modified copolyester composition |
| US20190225744A1 (en) * | 2016-07-06 | 2019-07-25 | Dic Corporation | Active ester resin composition and cured product of same |
-
2022
- 2022-03-18 EP EP22780264.2A patent/EP4318568A4/en active Pending
- 2022-03-18 JP JP2023510991A patent/JP7435906B2/ja active Active
- 2022-03-18 CN CN202280025045.7A patent/CN117098794A/zh active Pending
- 2022-03-18 WO PCT/JP2022/012818 patent/WO2022210049A1/ja not_active Ceased
- 2022-03-18 KR KR1020237033681A patent/KR20230163426A/ko active Pending
- 2022-03-25 TW TW111111344A patent/TW202309133A/zh unknown
-
2023
- 2023-08-24 US US18/454,865 patent/US20230391949A1/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006003584A (ja) * | 2004-06-17 | 2006-01-05 | Ricoh Co Ltd | 静電荷現像用トナー及び現像剤 |
| JP2007254557A (ja) * | 2006-03-22 | 2007-10-04 | Toyo Ink Mfg Co Ltd | 熱硬化性樹脂およびその製造方法、さらにそれを用いた熱硬化性組成物および硬化物 |
| JP2009235165A (ja) | 2008-03-26 | 2009-10-15 | Dic Corp | エポキシ樹脂組成物、及びその硬化物 |
| WO2013128872A1 (ja) * | 2012-02-29 | 2013-09-06 | 三洋化成工業株式会社 | トナーバインダーおよびトナー |
| JP2014025022A (ja) | 2012-07-30 | 2014-02-06 | Teijin Ltd | 共重合芳香族ポリエステルの製造方法 |
| JP2016223033A (ja) * | 2015-06-01 | 2016-12-28 | 三洋化成工業株式会社 | セラミック繊維用処理剤 |
| JP2018090560A (ja) * | 2016-02-03 | 2018-06-14 | 田岡化学工業株式会社 | フルオレン骨格を有するビスフェノール類及びその製造方法、並びに該ビスフェノール類から誘導されるポリアリレート樹脂、(メタ)アクリレート化合物及びエポキシ樹脂 |
Non-Patent Citations (2)
| Title |
|---|
| "Journal of Technical Disclosure No. 2020-500211", JAPAN INSTITUTE FOR PROMOTING INVENTION AND INNOVATION |
| See also references of EP4318568A4 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2024075486A (ja) * | 2022-11-22 | 2024-06-03 | 味の素株式会社 | 化合物 |
| JP7694625B2 (ja) | 2022-11-22 | 2025-06-18 | 味の素株式会社 | 化合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117098794A (zh) | 2023-11-21 |
| JPWO2022210049A1 (ja) | 2022-10-06 |
| KR20230163426A (ko) | 2023-11-30 |
| EP4318568A4 (en) | 2025-01-01 |
| EP4318568A1 (en) | 2024-02-07 |
| JP7435906B2 (ja) | 2024-02-21 |
| US20230391949A1 (en) | 2023-12-07 |
| TW202309133A (zh) | 2023-03-01 |
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