WO2009084656A1 - Résine de polyuréthane-imide difficilement inflammable, composition de résine de celle-ci et film durci - Google Patents

Résine de polyuréthane-imide difficilement inflammable, composition de résine de celle-ci et film durci Download PDF

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Publication number
WO2009084656A1
WO2009084656A1 PCT/JP2008/073792 JP2008073792W WO2009084656A1 WO 2009084656 A1 WO2009084656 A1 WO 2009084656A1 JP 2008073792 W JP2008073792 W JP 2008073792W WO 2009084656 A1 WO2009084656 A1 WO 2009084656A1
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Prior art keywords
phosphorus
polycarbonate polyol
group
residue
resin
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English (en)
Japanese (ja)
Inventor
Ryoichi Takasawa
Hiroaki Yamaguchi
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Ube Corp
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Ube Industries Ltd
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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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
    • C08G18/4684—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing phosphorus
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/343—Polycarboxylic acids having at least three carboxylic acid groups
    • C08G18/346—Polycarboxylic acids having at least three carboxylic acid groups having four carboxylic acid groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention is a polyurethaneimide resin comprising a soft segment made of polycarbonate polyol and a hard segment having an imide bond or an imide bond and an amide bond, wherein the polycarbonate polyol contains a phosphorus atom in the molecule.
  • the present invention relates to a polyurethaneimide resin having improved flame resistance.
  • the present invention also relates to a resin composition containing the polyurethaneimide resin and a cured film obtained by curing the resin composition.
  • Patent Document 1 and Patent Document 2 describe a polyurethane imide resin (modified polyamide imide resin) including a soft segment having a carbonate bond and a hard segment having an amide imide group.
  • Patent Documents 3 and 4 describe a polyurethaneimide resin (modified polyimide resin) including a soft segment having a carbonate bond and a hard segment having an imide group.
  • polyurethaneimide resins have excellent properties such as low warpage, electrical insulation, printability, solder resistance, solvent resistance and mechanical strength in addition to flexibility and heat resistance.
  • it is suitably used as an insulating protective film of a flexible substrate.
  • these polyurethane imide resins, resin compositions and cured films have room for improvement in flame resistance.
  • the object of the present invention is to provide various properties such as flexibility, heat resistance, low warpage, electrical insulation, printability, solder resistance, solvent resistance and mechanical strength required as an insulating protective film of a flexible substrate. It is to provide a polyurethaneimide resin, a resin composition thereof and a cured film having improved flame resistance without deteriorating properties.
  • the present invention relates to the following matters.
  • Polycarbonate polyol Formula: -OCOO- A structural unit (I) represented by: Residue A (However, A represents an n-valent residue obtained by removing n alcoholic hydroxyl groups from a phosphorus compound having at least n alcoholic hydroxyl groups, where n is an integer of 2 or more.) And a structural unit (II) represented by A polyurethaneimide resin characterized by being a phosphorus-containing polycarbonate polyol characterized in that the terminal group is an alcoholic hydroxyl group.
  • the polyurethaneimide resin of the present invention is a polyurethaneimide resin configured to include a soft segment formed using a polycarbonate polyol containing a phosphorus atom in the molecule and a hard segment having an imide bond. .
  • a 1 represents a divalent residue obtained by removing two alcoholic hydroxyl groups from a phosphorus compound having at least two alcoholic hydroxyl groups.
  • R 1 represents a monovalent hydrocarbon group
  • R 2 independently represents a divalent hydrocarbon group
  • each of the hydrocarbon groups may have a cyclic structure in the structure. And may have heteroatoms.
  • 5 5.
  • a resin composition comprising the polyurethaneimide resin of 1 to 5 above.
  • the “polyurethaneimide resin” is a resin (modified polyurethane resin) which is a polyurethane resin and has an imide bond formed in the structure of a hard segment.
  • the “imide bond” is to form an imide ring.
  • the polyurethaneimide resin of the present invention may be one containing “imide bond and amide bond”.
  • the imide bond is preferably formed with an aromatic imide ring formed together with an aromatic ring.
  • a polyurethaneimide resin having improved flame resistance in a polyurethaneimide resin comprising a soft segment made of polycarbonate polyol and a hard segment having an imide bond.
  • various properties such as flexibility, heat resistance, low warpage, electrical insulation, printability, solder resistance, solvent resistance, and mechanical strength required as an insulating protective film of a flexible substrate are provided.
  • a polyurethane imide resin, a resin composition thereof, and a cured film having improved combustion resistance without being reduced can be obtained.
  • the flame-resistant polyurethane imide resin, the resin composition and the cured film of the present invention are also suitably used as electronic / electrical materials, inks, paints, coating materials, adhesives, belt materials, sealing materials, printing rolls, and the like. be able to.
  • a phosphorus compound having at least n alcoholic hydroxyl groups may be referred to as a phosphorus compound A (OH) n as appropriate for the sake of simplicity.
  • the polyurethane imide resin of the present invention is a polyurethane imide resin comprising a soft segment made of polycarbonate polyol and a hard segment having an imide bond.
  • a polyurethane resin is generally obtained by a reaction between a polycarbonate polyol constituting a soft segment and a polyvalent isocyanate constituting a hard segment.
  • the soft segment is formed using a polycarbonate polyol (preferably polycarbonate diol), and the hard segment is, for example, (i) a polyisocyanate and a tri- or higher functional polycarboxylic acid or a derivative thereof.
  • a method of forming an imide bond (or an imide bond and an amide bond) on a hard segment by reaction with (ii) a polyisocyanate and a polyol comprising an imide bond (or an imide bond and an amide bond) It is formed by using a method of introducing an imide bond (or an imide bond and an amide bond) into the hard segment by reaction.
  • the polyurethaneimide resin of the present invention is a polycarbonate polyol constituting a soft segment, Formula: -OCOO- A structural unit (I) represented by: Residue A (However, A represents an n-valent residue obtained by removing n alcoholic hydroxyl groups from a phosphorus compound having at least n alcoholic hydroxyl groups, where n is an integer of 2 or more.) And a structural unit (II) represented by It can be easily obtained by using a phosphorus-containing polycarbonate polyol whose terminal group is an alcoholic hydroxyl group.
  • the polycarbonate polyol used to constitute the soft segment of the polyurethaneimide resin of the present invention Formula: -OCOO- And a structural unit (II) represented by the residue A, and a structural unit (I) represented by formula (I), that is, a carbonate structural unit (oxycarbonyloxy group).
  • the residue A represents an n-valent residue obtained by removing n alcoholic hydroxyl groups from a phosphorus compound ⁇ that is, phosphorus compound A (OH) n ⁇ having at least n alcoholic hydroxyl groups.
  • n is an integer of 2 or more, preferably 6 or less, and more preferably 2, 3 and 4.
  • the phosphorus-containing polycarbonate polyol is represented by the general formula (1):
  • a 1 represents a divalent residue obtained by removing two alcoholic hydroxyl groups from a phosphorus compound having at least two alcoholic hydroxyl groups.
  • a 2 represents a trivalent residue obtained by removing three alcoholic hydroxyl groups from a phosphorus compound having at least three alcoholic hydroxyl groups.
  • A When A is present in the polymer chain, A is linked to n structural units (I), and when present at the end of the polymer, at least one OH and at least one structural unit (I). To form a terminal alcoholic hydroxyl group.
  • residues A contained in the phosphorus-containing polycarbonate polyol may all be the same or different. If they are different, n may contain a different residue A, and n may be the same or may contain a residue A having a different structure.
  • the residue A itself does not contain an alcoholic hydroxyl group.
  • the residue A itself contains one or more alcoholic hydroxyl groups.
  • the phosphorus-containing polycarbonate polyol used in the present invention may optionally contain a residue B derived from a polyol component.
  • Residue B is a residue contained in a polymer bonded to a —OCOO— structural unit in a general polycarbonate.
  • an OH group It is a residue excluding.
  • residue B is divalent, structural unit:
  • the residue B is a group that is introduced into the phosphorus-containing polycarbonate polyol together with the residue A in [First method] or [Second method] described later.
  • the terminal group of the phosphorus-containing polycarbonate polyol is an alcoholic hydroxyl group.
  • the alcoholic hydroxyl group means that the carbon to which the hydroxyl group is directly bonded is an aliphatic carbon, that is, not directly bonded to carbon constituting an aromatic ring member such as a benzene ring. For example, it is bonded to a carbon atom of an aliphatic hydrocarbon group or alicyclic hydrocarbon group.
  • an aromatic group may be included as a structural element other than the carbon atom to which the hydroxyl group is bonded, and the aliphatic hydrocarbon group or alicyclic group.
  • a part of the hydrocarbon group may be substituted with oxygen, sulfur, or nitrogen.
  • the alcoholic hydroxyl group is more preferably a hydroxyl group that can be represented by the following chemical formula.
  • X is each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms.
  • the terminal alcoholic hydroxyl group of the phosphorus-containing polycarbonate polyol is an OH group bonded to the residue A or, when it coexists, an OH group bonded to the residue B derived from the polyol component.
  • the phosphorus-containing polycarbonate polyol contains the structural unit (I), the structural unit (II) represented by the residue A, and the residue B as an arbitrary structural unit, and preferably consists essentially of these.
  • the terminal group has —AOH (ie, an alcoholic hydroxyl group bonded to the residue A) and, when the residue B is present, has —BOH (ie, an alcoholic hydroxyl group bonded to the residue B), preferably Consists essentially of these. Therefore, when both residue A and residue B are divalent, a preferred phosphorus-containing polycarbonate polyol has an alternating repeating structure of residue A or residue B and structural unit (I), and the terminal is —AOH Or -BOH.
  • the ratio of residue A / residue B is greater than 0/1, preferably 0.1 / 1 or greater.
  • the ratio of residue A / residue B may be 1/0, that is, residue B may not be present.
  • the phosphorus compound A (OH) n is not particularly limited as long as it is a phosphorus compound containing a phosphorus atom and having two or more alcoholic hydroxyl groups.
  • Examples of the compound having two alcoholic hydroxyl groups include a phosphine compound represented by the following general formula (3), an aminophosphonate represented by the general formula (4), and a phosphorus system represented by the general formula (5).
  • a polyol compound etc. are mentioned. Any of those commercially available can be used.
  • the phosphine compound represented by the general formula (3) is preferably used from the viewpoints of easy availability, handling, and reactivity.
  • R 1 represents a monovalent hydrocarbon group (aliphatic or aromatic), preferably 1 to 25, more preferably 2 to 25, and still more preferably 1 to 2-18 carbon atoms.
  • a monovalent hydrocarbon group preferably an alkyl group or a monovalent hydrocarbon group containing an aromatic ring having 6 to 20 carbon atoms;
  • R 2 is a group bonded to an alcoholic hydroxyl group;
  • phosphine compound represented by the general formula (3) include n-butyl-bis (3-hydroxypropyl) phosphine oxide, n-propyl-bis (3-hydroxypropyl) phosphine oxide, ethyl-bis (3-hydroxypropyl) phosphine oxide, methyl-bis (3-hydroxypropyl) phosphine oxide, phenyl-bis (3-hydroxypropyl) phosphine oxide, ethyl-bis (2-hydroxyethyl) phosphine oxide, methyl-bis (2 -Hydroxyethyl) phosphine oxide, phenyl-bis (2-hydroxyethyl) phosphine oxide, methyl-bis (hydroxymethyl) phosphine oxide, phenyl-bis (hydroxymethyl) phosphine oxide and the like.
  • n-butyl-bis (3-hydroxypropyl) phosphine oxide is preferable because it is commercially available as PO-4500 manufactured by Nippon Chemical Industry Co., Ltd.
  • each R 3 is independently a monovalent hydrocarbon having 1 to 20 carbon atoms (preferably a monovalent aliphatic having 1 to 18 carbon atoms, particularly 1 to 6 carbon atoms). Represents a hydrocarbon group or a monovalent hydrocarbon group containing an aromatic ring having 6 to 20 carbon atoms), and these groups may have an ether bond or an ester bond, and may contain a hydroxyl group.
  • Each R 4 is independently a divalent hydrocarbon group having 1 to 20 carbon atoms (preferably a divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, particularly 1 to 6 carbon atoms, Or a divalent hydrocarbon group containing an aromatic ring having 6 to 20 carbon atoms), which can have an ether bond or an ester bond in the group, and may contain a hydroxyl group.
  • aminophosphonate polyol represented by the general formula (4) include diisopropyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, diisobutyl-N, N-bis (2-hydroxyethyl) amino.
  • preferable examples include diethyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate commercially available from ADEKA Corporation as “ADEKA POLYOL FC-450”.
  • each R 5 and R 6 is independently a divalent hydrocarbon group having 1 to 20 carbon atoms (preferably a divalent hydrocarbon group having 1 to 18 carbon atoms, particularly 1 to 6 carbon atoms).
  • m and n are each independently an integer of 0 to 1000, provided that at least one of them is 1 or more.
  • EXOLIT water-soluble hydroxy group-containing oligomeric phosphorus polyols commercially available as “OP550” and the like.
  • This material can be prepared, for example, from a reaction product in a 2: 2: 8: 1 molar ratio of dimethylmethylphosphonate, phosphorus pentoxide, ethylene oxide and water.
  • a hydrocarbon group to which OH is not bonded has an OH group.
  • a compound in which the hydrocarbon group to which OH is bonded in the above formulas (3) to (5) further has an OH group is not bonded.
  • Examples of the phosphorus compound A (OH) n having three alcoholic hydroxyl groups include compounds in which, in the above formula (3), R 1 has an OH group or one of R 2 further has an OH group. it can.
  • Examples of the compound in which R 1 has OH include 4-hydroxybutyl-bis (3-hydroxypropyl) phosphine oxide, tris (3-hydroxypropyl) phosphine oxide, 2-hydroxyethyl-bis (3-hydroxypropyl).
  • Phosphine oxide, hydroxymethyl-bis (3-hydroxypropyl) phosphine oxide, tris (2-hydroxyethyl) phosphine oxide, hydroxymethyl-bis (2-hydroxyethyl) phosphine oxide, tris (hydroxymethyl) phosphine oxide, etc. be able to.
  • the following formula (6) can be used as the phosphorus-containing polycarbonate polyol.
  • the polycarbonate diol containing a phosphorus atom in the molecule preferably has a number average molecular weight of about 500 to 10,000.
  • m / (m + n) is 0.01 to 1.0.
  • m and n indicate the ratio of the repeating units in parentheses in the molecule, and the fact that the repeating units are blocked is limited. It doesn't mean.
  • m is 1 to 100
  • n is 0 to 100.
  • the method for preparing the phosphorus-containing polycarbonate polyol used in the present invention will be described below.
  • a divalent alcohol compound may be further added to the reaction.
  • the polycarbonate polyol is preferably a polycarbonate diol represented by the formula (7).
  • R represents an alkylene group having 2 to 25 carbon atoms (preferably 2 to 15), and k represents an integer of 1 to 150.
  • this polycarbonate diol any known method may be used.
  • transesterification reaction of a dihydric alcohol (HO—R—OH) having an alkylene group having 4 to 25 carbon atoms (preferably 4 to 15 carbon atoms) corresponding to R in the formula (7) with a carbonate compound For example, transesterification reaction of a dihydric alcohol (HO—R—OH) having an alkylene group having 4 to 25 carbon atoms (preferably 4 to 15 carbon atoms) corresponding to R in the formula (7) with a carbonate compound, To 25 (preferably 2 to 15) of a cyclic carbonate having an alkylene group, or a product produced by a reaction of the aliphatic dihydric alcohol with a chloroformate or phosgene can be used. .
  • the polycarbonate diol manufactured by transesterification with the dihydric alcohol which has the said C4-C25 (preferably 4-15) alkylene group and a carbonate compound is preferable.
  • Examples of the carbonate compound include aliphatic or aromatic carbonates (carbonate esters) such as dialkyl carbonate, diaryl carbonate, alkylene carbonate, and alkylaryl carbonate. Specific examples include dimethyl carbonate, diethyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, diphenyl carbonate, methylphenyl carbonate, ethylene carbonate, and propylene carbonate. Copolymer polycarbonates in which two or more dihydric alcohols having an alkylene group are used in combination can also be used.
  • k is an integer from 1 to 150.
  • This polycarbonate polyol may be a commercially available product.
  • Preferable examples of this polycarbonate polyol include ETERNACOLL (registered trademark) series manufactured by Ube Industries, Ltd., Kuraray polyol series manufactured by Kuraray Co., Ltd., and PACCEL (registered trademark) series manufactured by Daicel Chemical Industries. These polycarbonate polyols can be used alone or in combination of two or more.
  • the number average molecular weight of these polycarbonate polyols is preferably 500 or more, more preferably 2000 to 20000. When the number average molecular weight of the polycarbonate polyol is small, the molecular weight of the phosphorus-containing polycarbonate polyol to be produced is lowered. On the other hand, when the number average molecular weight is large, the viscosity is high and handling becomes difficult.
  • the above-mentioned (3) to (5) are preferably mentioned.
  • the first method is, for example, a method in which polycarbonate polyol and phosphorus compound A (OH) n are charged and reacted at a predetermined ratio, or a molten polycarbonate polyol and phosphorus compound A (OH) n are continuously mixed at a predetermined ratio.
  • the reaction can be carried out batchwise or continuously depending on the method of supplying to the reaction.
  • the charging ratio for the transesterification reaction between the phosphorus compound A (OH) n and the polycarbonate polyol is 0.001 to 10 mol, preferably 0.01 to 1 mol, of the polycarbonate polyol with respect to 1 mol of the phosphorus compound A (OH) n. Particularly preferred is 0.05 to 0.5 mol.
  • the charging ratio of the polycarbonate polyol is small, the molecular weight of the produced phosphorus-containing polycarbonate polyol is lowered.
  • the charging ratio is high, the phosphorus content of the phosphorus-containing polycarbonate polyol is lowered.
  • the reaction temperature is 50 to 300 ° C, preferably 50 to 250 ° C, more preferably 100 to 180 ° C.
  • the reaction pressure is not particularly limited.
  • the reaction atmosphere is usually an inert gas atmosphere such as nitrogen, argon or helium.
  • the first method it is preferable to use a transesterification catalyst as necessary. If the polycarbonate polyol is obtained by reacting a carbonate compound and the corresponding diol, and the transesterification catalyst remains active in the polycarbonate polyol, it is allowed to react without adding the transesterification catalyst. However, in other cases, it is preferable to newly add a transesterification catalyst for reaction.
  • the amount of the transesterification catalyst used is preferably 1 to 5000 ppm, more preferably 10 to 1000 ppm on a weight basis with respect to the total amount charged.
  • the transesterification catalyst is not particularly limited as long as it is a compound that catalyzes the transesterification reaction.
  • titanium compounds such as titanium tetrachloride and tetraalkoxy titanium (tetra-n-butoxy titanium, tetraisopropoxy titanium, etc.), metal tin, tin hydroxide, tin chloride, dibutyltin laurate, dibutyltin oxide, butyltin
  • a tin compound such as tris (ethylhexanoate) is preferred.
  • tetraalkoxytitanium tetra-n-butoxytitanium, tetraisopropoxytitanium, etc.
  • dibutyltin laurate dibutyltin oxide
  • butyltin tris ethylhexanoate
  • Tetra-n-butoxy titanium, tetraisopropoxy titanium, etc. are particularly preferred.
  • a divalent residue derived from the polycarbonate polyol used as a raw material for the reaction for example, a polycarbonate diol of the above formula (7) is used as the residue B.
  • the residue B includes the group —R—.
  • a divalent alcohol compound is added to the reaction, a residue obtained by removing two OH from the alcohol compound is further included.
  • the charging ratio is preferably 0.5 to 1 mol of carbonate compound or phosgene with respect to 1 mol of the polyol component (total of phosphorus compound A (OH) n and further added divalent alcohol).
  • Examples of the carbonate compound used include aliphatic or aromatic carbonates (carbonates) such as dialkyl carbonates, diaryl carbonates, alkylene carbonates, and alkylaryl carbonates. Specific examples include dimethyl carbonate, diethyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, diphenyl carbonate, methylphenyl carbonate, ethylene carbonate, and propylene carbonate.
  • carbonates such as dialkyl carbonates, diaryl carbonates, alkylene carbonates, and alkylaryl carbonates.
  • Specific examples include dimethyl carbonate, diethyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, diphenyl carbonate, methylphenyl carbonate, ethylene carbonate, and propylene carbonate.
  • This reaction is a transesterification reaction and can be performed according to a known transesterification method for producing a polycarbonate polyol. That is, in the presence of a transesterification catalyst, if necessary, by carrying out a transesterification reaction while continuously extracting an aliphatic or aromatic compound having a by-produced hydroxyl group out of the reaction system, the phosphorus-containing compound used in the present invention A polycarbonate polyol can be suitably prepared.
  • the transesterification catalyst is not particularly limited as long as it is a compound that catalyzes the transesterification reaction.
  • titanium compounds such as titanium tetrachloride and tetraalkoxy titanium (tetra-n-butoxy titanium, tetraisopropoxy titanium, etc.), metal tin, tin hydroxide, tin chloride, dibutyltin laurate, dibutyltin oxide, butyltin
  • a tin compound such as tris (ethylhexanoate) is preferred.
  • tetraalkoxytitanium tetra-n-butoxytitanium, tetraisopropoxytitanium, etc.
  • dibutyltin laurate dibutyltin oxide
  • butyltin tris ethylhexanoate
  • Tetra-n-butoxy titanium, tetraisopropoxy titanium, etc. are particularly preferred.
  • the amount used is preferably 1 to 5000 ppm, more preferably 10 to 1000 ppm, based on the weight of the polyol.
  • the conditions for the transesterification reaction are not particularly limited as long as the target product can be produced, but at 80 to 250 ° C. (especially 110 to 200 ° C.) under normal pressure so that the target product can be produced efficiently. About 1 to 24 hours, then react under reduced pressure at 80 to 250 ° C. (especially 110 to 240 ° C.) for about 0.1 to 20 hours, and further gradually increase the degree of vacuum at the same temperature to finally become 20 mmHg or less. The reaction is preferably carried out under reduced pressure for about 0.1 to 20 hours. In order to extract by-product phenol and by-product alcohol, it is preferable to provide a distillation column in the reactor, and the reaction may be carried out under the flow of an inert gas (nitrogen, helium, argon, etc.).
  • an inert gas nitrogen, helium, argon, etc.
  • the second method when a divalent alcohol compound is added to the reaction, a residue obtained by removing two OHs from the alcohol compound is included as a residue B in the obtained phosphorus-containing polycarbonate polyol.
  • the phosphorus-containing polycarbonate polyol does not contain the residue B, and the phosphorus-containing structural unit represented by the structural unit (I) of the carbonate structural unit and the residue A ( II).
  • the second method has an advantage that the structural unit (II) represented by the residue A can be controlled relatively freely from a low ratio to a high ratio, and as a result, it can be manufactured from a product having a low phosphorus content to a high product. .
  • divalent alcohol compound examples include 2-methyl-1,3-propanediol, 1,3-butanediol, 2,4-heptanediol, 2,2-diethyl-1,3-propanediol, 2-methyl- 2-propyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2- Compounds in which an alkylene group such as butyl-2-ethyl-1,3-propanediol is a trimethylene group; Compounds in which an alkylene group such as 1,4-butanediol is a tetramethylene group; 1,5-pentanediol, 3- Compounds in which the alkylene group is a pentamethylene group, such as methyl-1,5-pentanediol and
  • the phosphorus-containing polycarbonate polyol has a number average molecular weight of about 500 to 10,000, preferably about 500 to 5,000, more preferably about 500 to 3,000. For this reason, when the hydroxyl value (molecular weight) of the reaction product is out of the target range, that is, when the molecular weight is small, the reaction is conducted while distilling further diol under reduced pressure, and when the molecular weight is large, the diol is added and further added. It is preferable to adjust the molecular weight by a known method such as transesterification. If necessary, it is preferable to deactivate the remaining transesterification catalyst with water or a phosphorus compound (phosphoric acid, butyl phosphate, dibutyl phosphate, etc.) after adjusting the molecular weight.
  • a phosphorus compound phosphoric acid, butyl phosphate, dibutyl phosphate, etc.
  • substantially all of the raw material phosphorus compound A (OH) n can be transesterified and introduced into the polycarbonate polyol molecule.
  • substantially all means 90% or more, preferably 95% or more, more preferably 98% or more. This point can be easily confirmed by the fact that the peak of the phosphorus compound A (OH) n substantially disappears by GPC analysis of the reaction mixture.
  • the reaction mixture when “substantially all” the phosphorus compound A (OH) n as a raw material is subjected to a transesterification reaction, the reaction mixture should be used as it is as a raw material for producing the polyurethaneimide resin of the present invention. Is preferred.
  • the hard segment in the polyurethane resin of the present invention preferably contains structural units represented by the following formulas (H1) to (H4).
  • D represents any of a direct bond, —O—, —CH 2 —, —CO—, and —SO 2 —).
  • the method for synthesizing the polyurethaneimide resin of the present invention is not limited, but can be easily obtained by the conventionally known method (i) or (ii) as described above.
  • the method (i) is a production method in which at least 1) a phosphorus-containing polycarbonate polyol, 2) a polyvalent isocyanate compound, 3a) a tri- or higher functional polycarboxylic acid or a derivative thereof is reacted in a solvent.
  • a phosphorus-containing polycarbonate polyol and a polyvalent isocyanate compound are reacted at 20 to 150 ° C., preferably 60 to 120 ° C. for 0.1 to 12 hours, and then a tri- or higher functional polycarboxylic acid or derivative thereof is added, and 80 to 250 ° C.
  • the reaction can be preferably carried out at 120 to 200 ° C. for 0.5 to 24 hours.
  • a catalyst such as an acid or a base can be used.
  • the method (ii) is a production method in which at least 1) a phosphorus-containing polycarbonate polyol, 2) a polyvalent isocyanate compound, and 3b) a polyol containing an imide bond are reacted in a solvent.
  • a diol component such as a phosphorus-containing polycarbonate polyol or a polyol containing an imide bond and a polyvalent isocyanate compound are reacted at 20 to 150 ° C., preferably 60 to 120 ° C. for 0.1 to 12 hours.
  • composition containing an imide bond after synthesizing a prepolymer by reacting a phosphorus-containing polycarbonate polyol and a polyvalent isocyanate compound at 20 to 150 ° C., preferably 60 to 120 ° C. for 0.1 to 12 hours.
  • the obtained polyol can be added and subjected to a chain extension reaction at 20 to 150 ° C., preferably 60 to 120 ° C. for 1 to 24 hours.
  • a catalyst usually used for urethane reaction can also be used.
  • the polyisocyanate used here is preferably diisocyanate. Any diisocyanate compound may be used as long as it has two isocyanate groups in one molecule.
  • an aliphatic, alicyclic or aromatic diisocyanate preferably an aliphatic, alicyclic or aromatic diisocyanate having 2 to 30 carbon atoms excluding an isocyanate group, specifically 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexame Thiylene diisocyanate, lysine diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,3-bis (isocyanate methyl) ) -Cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, tolylene
  • aromatic tricarboxylic acid, aromatic tetracarboxylic acid, and derivatives thereof have good heat resistance and mechanical properties. At the same time, the effect of improving the combustion resistance is excellent, which is preferable.
  • trimellitic anhydride 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic Acid dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-benzenedicarboxylic acid anhydride) hexafluoropropane, pyromellitic dianhydride, 1,4-bis (3,4-benzenedicarboxylic anhydride) benzene, 2,2-bis [4- (3,4-phenoxydicarboxylic anhydride)
  • 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride, and 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride and trimellitic anhydride are preferred because the resulting polyurethaneimide resin has excellent solubility in organic solvents.
  • the polyol comprised by including the imide bond used by the method of (ii) has two or more hydroxyl groups which react with an isocyanate group at the terminal and has at least an imide bond in the molecule
  • a bifunctional hydroxyl-terminated imide oligomer represented by the following general formula (H5) can be suitably used.
  • this bifunctional hydroxyl-terminated imide oligomer is not limited, it can be easily obtained by a known method.
  • Patent Document 4 has a detailed description.
  • X represents a residue obtained by removing a carboxyl group of tetracarboxylic acid
  • Y represents a residue obtained by removing an amino group of diamine
  • Z represents a divalent aliphatic or aromatic hydrocarbon group
  • n is the number of repetitions of the polyimide structure and represents an integer of 0 to 20.
  • the soft segment is a segment formed from a phosphorus-containing polycarbonate polyol (preferably polycarbonate diol), and the hard segment is a polyisocyanate compound and a polycarboxylic acid having three or more functions.
  • the hard segment is a segment formed from a derivative thereof or a segment formed from a polyol composed of a polyisocyanate compound and an imide bond.
  • a typical example of the polyurethaneimide resin produced by the method (i) has the following structure.
  • E represents a residue A, a residue A 1 , a residue B or the like derived from a phosphorus-containing polycarbonate polyol
  • G represents a residue obtained by removing two isocyanate groups from a diisocyanate compound
  • X represents Represents a residue excluding the carboxyl group of tetracarboxylic acid
  • m represents the repeating number of the polycarbonate polyol structure. The part enclosed in square brackets [] means a repeating unit.
  • a typical example of the polyurethaneimide resin produced by the method (ii) has the following structure.
  • E represents a residue A, a residue A 1 , a residue B or the like derived from a phosphorus-containing polycarbonate polyol
  • G represents a residue obtained by removing two isocyanate groups from a diisocyanate compound
  • X represents a tetra
  • Y represents the residue except the amino group of diamine
  • Z represents a bivalent aliphatic or aromatic hydrocarbon group.
  • m represents the repeating number of the polycarbonate polyol structure.
  • n is the repeating number of the polyimide structure and represents an integer of 0 to 20.
  • parenthesis [] means a repeating unit, respectively, and two repeating units may be couple
  • the polyurethaneimide resin of the present invention has a total soft weight of 10 to 90% by weight, preferably 20 to 80% by weight, and a hard segment of 90 to 10% by weight, preferably 80 to 20% by weight, based on 100% by weight. preferable. This ratio can be easily controlled by the ratio of the raw material components.
  • the phosphorus content of the polyurethaneimide resin of the present invention (phosphorus atom weight% in the polyurethaneimide resin) is 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 1% by weight or more. It is preferable to improve the flame resistance.
  • the upper limit of the phosphorus content is naturally determined by the composition such as the proportion of the hard segment, but is usually 30% by weight or less, particularly 20% by weight or less.
  • the phosphorus content of the polyurethaneimide resin can be easily controlled by using a phosphorus-containing polycarbonate polyol having a known phosphorus content in advance as a raw material component.
  • a phosphorus-containing polycarbonate polyol having a known phosphorus content can be easily obtained by making the raw material components at a ratio that makes the target phosphorus content in advance and reacting them "substantially all” when producing the polycarbonate polyol. Can do. Whether or not “substantially all” transesterification has occurred can be confirmed by GPC measurement of the reaction mixture.
  • a segment having a reactive group capable of reacting with an epoxy group or an isocyanate group may be further introduced.
  • a resin composition is formed combining with an epoxy compound, an isocyanate compound, etc., a hardened
  • cured material can be suitably obtained from the said resin composition.
  • a segment having a reactive group is not limited.
  • a diol compound having a thermal reactive group such as a carboxy group or a phenolic hydroxyl group or a photoreactive group such as a methacryl group may be used as the above 1) to 3a).
  • a photoreactive group such as a methacryl group
  • it can be easily carried out by reacting with the compounds 1) to 3b).
  • diol compound having a reactive group examples include 2,2-bis (hydroxymethyl) propionic acid and 2,2-bis (hydroxymethyl) butyric acid as diol compounds having a carboxyl group. Can do.
  • diol compound having a phenolic hydroxyl group examples include 2,6-bis (hydroxymethyl) -phenol and 2,6-bis (hydroxymethyl) -p-cresol.
  • the polyurethane imide resin of the present invention is obtained by combining a resin composition with another resin component such as an epoxy compound or a polyisocyanate compound in an organic solvent, a filler component such as an inorganic filler, and a curing catalyst as necessary. It can be suitably obtained.
  • a cured film can be suitably obtained by forming a coating film on the surface of the substrate by, for example, printing this resin composition, and then drying and curing the coating film by a conventionally known method such as heating or light irradiation. .
  • This cured film preferably has various properties such as flexibility, heat resistance, low warpage, electrical insulation, printability, solder resistance, solvent resistance and mechanical strength required as an insulating protective film for flexible substrates. It is a cured film with improved combustion resistance without degrading properties.
  • the resin composition of the sample is applied to the surface of a polyimide film (UPILEX 35SGA) manufactured by Ube Industries, Ltd. to form a coating film, and heat-treated at 80 ° C. for 30 minutes and then at 120 ° C. for 60 minutes to form a 10 ⁇ m thick cured film. Formed.
  • the obtained polyimide film and cured film laminate is cut into a 5 cm ⁇ 5 cm square to form a test piece, which is placed on a horizontal surface with the cured film on the top, and from the four horizontal corners of the test piece. The height of was measured. The average value of the heights of the four corners from the horizontal plane was determined as an index of warpage.
  • the resin composition of the sample is applied to the surface of a polyimide film (UPILEX 35SGA) manufactured by Ube Industries, Ltd. to form a coating film, and heat-treated at 80 ° C. for 30 minutes and then at 120 ° C. for 60 minutes to form a 10 ⁇ m thick cured film. Formed.
  • the obtained polyimide film and cured film laminate was cut into a 2 cm long x 1 cm wide rectangle to obtain a test piece.
  • the test piece was folded so that the cured film was inward in the center in the length direction, and a 500 g weight was placed on the bent portion and allowed to stand for 1 minute. After removing the weight, the bent part of the test piece was observed with a microscope, and the case where there was no abnormality was indicated as ⁇ , and the case where cracks, whitening, etc. were observed was indicated as x.
  • Evaluation of flame resistance was performed according to the UL94 standard vertical combustion test method. That is, the test piece was held on a stand with a clamp in the vertical direction, and the upper portion was fixed with a clamp so that the lower end thereof was 12 inches (304.8 mm) in height. Absorbent cotton was placed under the sample to confirm ignition when a fireball fell. A burner adjusted to a flame of 0.75 inch (19.05 mm) at the center of the lower end of the test piece was indirect flame for 10 seconds (the portion at the bottom of the sample 1 inch (25.4 mm)), the flame was released, and the burning time of the sample was measured. Immediately after extinguishing the fire, the indirect flame was again applied for 10 seconds, and the combustion (red heat) time was measured.
  • n 5 was set as one set, and two sets were tested (10 points in total). The following items were confirmed as criteria for UL94V-0. Those that satisfy all of these items are acceptable. (1) Does not continue to burn for more than 10 seconds after the first flame contact (2) Burning time after flame contact of 5 points x 2 times (10 times in total) within 50 seconds (3) 12 inches down by fireball dripping (4) Red hot burning time after the second flame contact is within 30 seconds (5) Does not burn up to the clamp part
  • Example 1 [Production of polyurethane imide (1)] A 300 mL glass reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube was charged with 37.50 g of the phosphorus-containing polycarbonate diol obtained in Reference Example 1, 13.20 g of Coronate T-80, and 50.69 g of ⁇ -butyrolactone. The reaction was stirred at 80 ° C. for 2 hours. To this reaction mixture, 7.36 g of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and 7.36 g of ⁇ -butyrolactone were added, and the temperature was raised to 160 ° C., followed by stirring for 4 hours. It was.
  • Example 2 [Production of polyurethane imide (2)] A 300 mL glass reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube was charged with 37.50 g of the phosphorus-containing polycarbonate diol obtained in Reference Example 1, 13.21 g of Coronate T-80, and 50.69 g of ⁇ -butyrolactone. The reaction was stirred at 80 ° C. for 2 hours. To this reaction mixture, 4.80 g of trimellitic anhydride and 4.80 g of ⁇ -butyrolactone were added, and the temperature was raised to 160 ° C., followed by stirring for 4 hours for reaction.
  • Table 1 shows the results of mechanical properties, electrical insulation, and oxygen index of polyurethaneimide (2) measured in the same manner as in Example 1.
  • Example 3 [Production of polyurethane imide (3)] In a 300 mL glass reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 37.50 g of the phosphorus-containing polycarbonate diol obtained in Reference Example 1 and 10.40 g of the alcoholic hydroxyl group-terminated imide oligomer solution obtained in Reference Example 2 , 2,2-bis (hydroxymethyl) propionic acid 0.86 g, coronate T-80 10.35 g and ⁇ -butyrolactone 48.86 g were stirred at 60 ° C. for 2 hours, heated to 80 ° C., and heated to 80 ° C. The mixture was reacted at a temperature of 4 hours with stirring.
  • Table 1 shows the results of mechanical properties, electrical insulation and oxygen index of polyurethaneimide (3) measured in the same manner as in Example 1.
  • Table 1 shows the results of mechanical properties, electrical insulating properties, and oxygen index of polyurethaneimide (4) containing no phosphorus atom, measured in the same manner as in Example 1.
  • Example 4 [Production of Polyurethaneimide Resin Composition Containing Phosphorus Atom]
  • 5 parts by weight of epoxy resin 828EL and 0.5 part of curing catalyst 2E4MZ were added to 100 parts by weight of polyurethaneimide solids, and the mixture was uniformly stirred and mixed. Further, 7 parts by weight of Aerosil R972 as a filler was added and mixed, and then kneaded using three rolls to obtain a polyurethaneimide resin composition.
  • the polyurethane imide resin and the composition thereof of the present invention have excellent bendability, low warpage, and electrical insulation (volume resistance, surface resistance), while having an oxygen index and flame retardancy. As can be seen from the measurement results of the property (UL94V-0), it is clear that the flame resistance is improved.
  • various properties such as flexibility, heat resistance, low warpage, electrical insulation, printability, solder resistance, solvent resistance, and mechanical strength required as an insulating protective film of a flexible substrate are provided. It is possible to provide a polyurethaneimide resin, a resin composition thereof, and a cured film having improved flame resistance without lowering. As a result, since the flame resistance of the flexible substrate is improved, the safety of electronic devices such as a flat panel display, a mobile phone, and a personal computer using the flexible substrate can be greatly improved.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention porte sur une résine de polyuréthane-imide plus difficilement inflammable que dans la technique précédente. L'invention porte également sur une composition de résine de la résine de polyuréthane-imide et sur un film durci. De façon spécifique, l'invention porte sur une résine de polyuréthane-imide contenant un segment mou composé d'un polycarbonate polyol et un segment dur à liaison imide. Le polycarbonate polyol contient une unité structurale (I) représentée par la formule suivante : -OCOO- et une unité structurale (II) représentée par un résidu A (un résidu n-valent obtenu par retrait de n groupes hydroxyles alcooliques d'un composé du phosphore présentant au moins n groupes hydroxyles alcooliques, où n est un entier de pas moins de 2, mais présentant un groupe hydroxyle alcoolique à une extrémité.
PCT/JP2008/073792 2007-12-28 2008-12-26 Résine de polyuréthane-imide difficilement inflammable, composition de résine de celle-ci et film durci Ceased WO2009084656A1 (fr)

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CN118271901A (zh) * 2024-05-06 2024-07-02 厦门欧化实业有限公司 一种醇溶环保印刷油墨及其制备方法
CN119798635A (zh) * 2025-01-02 2025-04-11 万华化学集团股份有限公司 一种聚碳酸酯嵌段多元醇的制备方法和应用

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JPH03190983A (ja) * 1989-12-19 1991-08-20 Nippon Polyurethane Ind Co Ltd 磁気記録媒体用ポリウレタン樹脂バインダー
JPH0472318A (ja) * 1990-07-11 1992-03-06 Toyobo Co Ltd ポリウレタン系樹脂の製造方法
JPH09194559A (ja) * 1996-01-17 1997-07-29 Sanyo Chem Ind Ltd 難燃性ポリウレタンの製造法
JP2001302795A (ja) * 2000-04-25 2001-10-31 Hitachi Chem Co Ltd ポリアミドイミド樹脂組成物及び被膜形成材
WO2009005147A1 (fr) * 2007-07-04 2009-01-08 Ube Industries, Ltd. Polycarbonate polyol contenant du phosphore, son procédé de production, et polycarbonate polyuréthane contenant du phosphore

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US4556698A (en) * 1984-12-03 1985-12-03 Fmc Corporation Flame retardant thermoplastic polycarbonate polymers
KR101271989B1 (ko) * 2005-03-28 2013-06-05 우베 고산 가부시키가이샤 폴리이미드 수지 및 경화성 수지 조성물

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Publication number Priority date Publication date Assignee Title
JPH03190983A (ja) * 1989-12-19 1991-08-20 Nippon Polyurethane Ind Co Ltd 磁気記録媒体用ポリウレタン樹脂バインダー
JPH0472318A (ja) * 1990-07-11 1992-03-06 Toyobo Co Ltd ポリウレタン系樹脂の製造方法
JPH09194559A (ja) * 1996-01-17 1997-07-29 Sanyo Chem Ind Ltd 難燃性ポリウレタンの製造法
JP2001302795A (ja) * 2000-04-25 2001-10-31 Hitachi Chem Co Ltd ポリアミドイミド樹脂組成物及び被膜形成材
WO2009005147A1 (fr) * 2007-07-04 2009-01-08 Ube Industries, Ltd. Polycarbonate polyol contenant du phosphore, son procédé de production, et polycarbonate polyuréthane contenant du phosphore

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118271901A (zh) * 2024-05-06 2024-07-02 厦门欧化实业有限公司 一种醇溶环保印刷油墨及其制备方法
CN119798635A (zh) * 2025-01-02 2025-04-11 万华化学集团股份有限公司 一种聚碳酸酯嵌段多元醇的制备方法和应用

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