WO2013089149A1 - Composition d'amino-résine, et produit durci obtenu à partir de ladite composition - Google Patents

Composition d'amino-résine, et produit durci obtenu à partir de ladite composition Download PDF

Info

Publication number
WO2013089149A1
WO2013089149A1 PCT/JP2012/082238 JP2012082238W WO2013089149A1 WO 2013089149 A1 WO2013089149 A1 WO 2013089149A1 JP 2012082238 W JP2012082238 W JP 2012082238W WO 2013089149 A1 WO2013089149 A1 WO 2013089149A1
Authority
WO
WIPO (PCT)
Prior art keywords
amino resin
resin composition
polyol
weight
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2012/082238
Other languages
English (en)
Japanese (ja)
Inventor
貴文 平川
清隆 赤尾
幸夫 金子
亮一 高澤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ube Corp
Original Assignee
Ube Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ube Industries Ltd filed Critical Ube Industries Ltd
Priority to JP2013549289A priority Critical patent/JP6146314B2/ja
Publication of WO2013089149A1 publication Critical patent/WO2013089149A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/0644—Poly(1,3,5)triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C09D161/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • 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
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08J2361/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08J2361/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • 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
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to an amino resin composition containing a specific amino resin and a polyol compound, and a cured product obtained from the composition.
  • Epoxy resins, polyurethane resins, fluororesins, acrylic resins, polyimide resins, etc. are widely used as insulators due to their insulating properties.
  • resins that function as an insulator and function as an adhesive such as an epoxy resin, an acrylic resin, and a polyimide resin.
  • Patent Document 2 discloses an aminoalkyd resin obtained by co-condensation of an alkyd resin obtained from a hydroxy compound containing a polycarbonate diol and 1,6-hexanediol and an aliphatic carboxylic acid, and an amino resin, and a product obtained therefrom. A cured coating having excellent non-slip properties is described. Further, it is described that the number average molecular weight of the amino resin is 1200 to 5000.
  • Patent Document 3 describes a coating composition containing a polycarbonate diol-modified amino resin and a polyester resin or an acrylic resin. From the composition, a coating film excellent in stain resistance and hardness without impairing flexibility. It is described that can be formed.
  • JP-A-6-186402 Japanese Patent Laid-Open No. 9-157369 JP-A-6-313149
  • An object of the present invention is to provide a material capable of forming a cured product that is excellent in transparency and is transparent even after high-temperature heat treatment with little coloration / discoloration.
  • the cured product formed according to the present invention preferably has excellent strength and flexibility.
  • the present invention relates to the inventions of the following items.
  • the present invention (1) relates to an amino resin composition
  • an amino resin composition comprising (A) an amino resin having a free hydroxyl group and an alkoxyl group, and (B) a polyol compound.
  • the present invention (2) relates to the amino resin composition according to the present invention (1), wherein the amino resin (A) is an ether-modified melamine resin having a polystyrene-equivalent number average molecular weight of 2000 or less as measured by GPC.
  • the amino resin (A) is an ether-modified melamine resin having a polystyrene-equivalent number average molecular weight of 2000 or less as measured by GPC.
  • This invention (3) relates to the amino resin composition as described in this invention (1) or (2) whose said polyol compound (B) is a polycarbonate polyol.
  • the present invention (4) relates to the amino resin composition according to the present invention (3), wherein the polycarbonate polyol is obtained by reacting a polyol monomer with a carbonate ester compound or phosgene.
  • the present invention (5) relates to the amino resin composition according to the present invention (4), wherein the polyol monomer is a polyol monomer having an alicyclic structure and / or an aliphatic polyol monomer.
  • the ratio of the polyol monomer having the alicyclic structure and the aliphatic polyol monomer is from 100/0 to molar ratio. It is related with the amino resin composition as described in this invention (5) which is 0/100.
  • the present invention (8) is the amino resin according to any one of the present invention (1) to (7), wherein the amino resin (A) is an etherified alkylol melamine resin represented by the following general formula (I): Relates to the composition.
  • the amino resin (A) is an etherified alkylol melamine resin represented by the following general formula (I): Relates to the composition.
  • —X— is —R 13 —O—R 14 — or —R 14 —
  • R 1 to R 6 and R 15 to R 18 may be the same or different and each represents hydrogen or an optionally substituted alkyl group having 1 to 6 carbon atoms
  • At least one of 18 is hydrogen, but not all are hydrogen at the same time
  • R 7 to R 14 and R 19 to R 22 may be the same or different and each is an optionally substituted alkylene group having 1 to 6 carbon atoms
  • n is a number from 0 to 5, and when there are
  • the present invention (9) relates to the amino resin composition according to the present invention (8), wherein in the general formula (I), R 7 to R 14 and R 19 to R 22 are methylene groups.
  • the present invention (10) is the amino resin composition according to any one of the present inventions (5) to (9), wherein the polyol monomer having an alicyclic structure is cyclohexanedimethanol.
  • the weight ratio of the amino resin (A) to the polyol compound (B) in the amino resin composition is 80/20 to 20/80.
  • the acid catalyst (C) is dimethylolbutanoic acid or dimethylolpropionic acid, and a proportion of 0.1 to 5 parts by weight with respect to 100 parts by weight of the solid content in the amino resin composition
  • the present invention (13) relates to a cured product obtained by heating the amino resin composition according to any one of the present inventions (1) to (12).
  • the present invention (14) relates to a film obtained by heating the amino resin composition according to any one of the present inventions (1) to (12).
  • the present invention relates to an insulator obtained by heating the amino resin composition according to any one of the present inventions (1) to (12).
  • the cured product obtained by heating the amino resin composition of the present invention is excellent in transparency, has little coloration / discoloration even after high-temperature heating, and can maintain transparency. Moreover, according to the amino resin composition of the present invention, a cured product having excellent strength and flexibility can be formed.
  • the composition of the present invention components of the amino resin composition of the present invention (hereinafter also simply referred to as “the composition of the present invention”) and a cured product obtained from the amino resin composition will be described in order.
  • amino resin composition ⁇ Amino resin having a free hydroxyl group and an alkoxyl group>
  • the amino resin (A) which is a constituent component of the amino resin composition of the present invention has a free hydroxyl group and an alkoxyl group.
  • the amino resin (A) may be used alone or in combination of two or more.
  • the alkoxyl group is excellent in reactivity and is cured by causing a crosslinking reaction with the polyol compound (B) described later by heating.
  • the free hydroxyl group does not participate in the crosslinking reaction with the polyol compound (B).
  • the presence of free hydroxyl groups in the amino resin (A) appropriately controls the amount of crosslinking points per molecule of the amino resin.
  • the cured product formed according to the present invention preferably has excellent strength and flexibility.
  • the ratio of the alkoxyl group in the amino resin (A) to the total of the hydroxyl group and the alkoxyl group (alkoxyl group / (hydroxyl group + alkoxyl group)) is preferably 97/100 to 7 in terms of the number ratio. / 100, more preferably 62/100 to 23/100.
  • a preferred amino resin (A) satisfying such conditions includes an ether-modified melamine resin having a free hydroxyl group having a number average molecular weight of 2000 or less, preferably 200 to 1500, as measured by GPC.
  • the amino resin (A) having a number average molecular weight of a certain value or less has a limited number of cross-linking points, so that the degree of cross-linking is hardly increased and a cured product having flexibility can be obtained.
  • Examples of the preferred amino resin (A) described above include etherified alkylol melamine resins represented by the following general formula (I).
  • —X— is —R 13 —O—R 14 — or —R 14 —.
  • R 1 to R 6 and R 15 to R 18 may be the same or different and each represents hydrogen or an optionally substituted alkyl group having 1 to 6 carbon atoms; R 1 to R 6 and R 15 to R At least one of the 18 is hydrogen, but not all are hydrogen at the same time.
  • the alkyl group may have a branch.
  • Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a pentyl group, and a hexyl group.
  • a butyl group and an isobutyl group are preferred.
  • examples of the substituent in the alkyl group include a halogen atom and a hydroxyl group.
  • R 7 to R 14 and R 19 to R 22 may be the same or different and each is an optionally substituted alkylene group having 1 to 6 carbon atoms.
  • the alkylene group may have a branch.
  • Examples of the substituent in the alkylene group include a halogen atom and a hydroxyl group.
  • R 7 to R 12 and R 19 to R 22 also serve as spacers for adjusting the position of the crosslinking point.
  • These are preferably alkylene groups having 1 to 4 carbon atoms, more preferably methylene groups.
  • X consisting of R 14 , R 13 , R 14 and an oxygen atom serves to connect the melamine skeleton when n is 1 or more in the general formula (I), and —X— is —
  • R 13 —O—R 14 — —R 13 is bonded to the nitrogen atom of the adjacent melamine skeleton.
  • Preferred groups for R 13 and R 14 are the same as the preferred groups for R 7 to R 12 and R 19 to R 22 .
  • n is a number from 0 to 5, and for example, a mixture of resins in which n is an integer from 0 to 5 can be used. A mixture of each resin that is an integer of is preferred.
  • X, R 1 to R 6 and R 15 to R 18 , R 13 and R 14 are as defined above, but R 13 , R 14 and R 19 to R 22 , and R 15 to R 18 are When two or more are present, they may be the same or different.
  • the amino resin (A) described above is obtained by reacting a compound having a triazine skeleton and a free amino group such as melamine or a melamine resin with an appropriate aldehyde compound (the general formula ( R 7 to R 12 and R 19 to R 22 in I) can be changed) and the resulting alkylol compound is reacted with an alcohol compound (depending on the alcohol compound to be reacted, R 1 in the general formula (I)) -R 6 and R 15 -R 18 can be altered), and can be obtained by alkoxylation of a portion of the hydroxyl group.
  • an appropriate aldehyde compound the general formula ( R 7 to R 12 and R 19 to R 22 in I) can be changed
  • the amount of the alcohol compound used may be appropriately adjusted, and such methods are known to those skilled in the art.
  • aldehyde compound examples include formaldehyde, acetaldehyde, propionaldehyde, and n-butyraldehyde.
  • formaldehyde is preferable from the viewpoint of reactivity.
  • Examples of the alcohol compound include alcohols having 1 to 6 carbon atoms. Among these, alcohol compounds having 1 to 4 carbon atoms are preferable, and methanol, ethanol, isopropyl alcohol, isobutyl alcohol, and n-butyl alcohol are particularly preferable.
  • reaction conditions temperature, pressure, time, catalyst, etc.
  • X in the general formula (I) can be changed depending on the type of aldehyde compound used in the synthesis of the melamine resin.
  • the amino resin (A) obtained by the method described above is a dimer component having two triazine skeletons or an oligomer component having three or more triazine skeletons in one molecule, even when melamine is a starting compound. May contain various by-product components.
  • the commercial product of the melamine resin contains various compounds having different degrees of polymerization in addition to the main component, so that the amino resin (A) obtained therefrom also has a degree of polymerization. May contain a variety of different compounds.
  • the amino resin (A) used in the present invention can also be obtained as a commercial product.
  • examples thereof include Uban 2020, 2061, 122, 22R, 28-60, 2021, 20HS, 20SE60, 21R, 125, 128, 62E, 60R (manufactured by Mitsui Chemicals, Inc.), Nicarak MS-11, MS-001, MX-750, MX-706, MX-410, MX-750LM (manufactured by Sanwa Chemical Co., Ltd.), Cymel 370N, Cymel 327, Examples include Cymel 211 and Cymel 202 (Nippon Cytec Industries, Inc.).
  • These may also contain the above-mentioned by-product components, and there are products containing a solvent or the like in addition to the amino resin and the by-product components.
  • the amino resin (A) used in the present invention has a free hydroxyl group and an alkoxyl group, thereby achieving an appropriate degree of crosslinking to give a cured product excellent in strength and flexibility.
  • the amino resin composition of the present invention contains a polyol compound (B).
  • the hydroxyl group of the polyol compound (B) undergoes a crosslinking reaction with the alkoxyl group of the amino resin (A) by heating to form a cured product.
  • the said polyol compound (B) may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the polyol compound (B) is not particularly limited as long as it has a plurality of hydroxyl groups, and examples thereof include a low molecular weight polyol and a high molecular weight polyol.
  • the number average molecular weight of the low molecular weight polyol can be 60 or more and less than 400, and the number average molecular weight of the high molecular weight polyol can be 400 or more and less than 8000.
  • all the number average molecular weights of a polyol compound (B) are the number average molecular weights calculated based on the hydroxyl value measured based on JISK1577.
  • a low molecular weight diol and a high molecular weight diol are preferable from the viewpoint of ease of production.
  • Low molecular weight polyol examples include ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, and 2-butyl-2-ethyl.
  • the polyol compound (B) is preferably the above high molecular weight polyol.
  • polycarbonate polyol for example, polycarbonate polyol, polyester polyol, or polyether polyol can be used. From the viewpoint of the heat resistance of the cured product obtained from the composition of the present invention, polycarbonate polyol is preferred.
  • the polycarbonate polyol is obtained by reacting one or more polyol monomers with a carbonate compound or phosgene. It is preferable to use a carbonic acid ester compound because it is easy to produce and has no byproduct of terminal chlorinated products.
  • the polyol monomer is not particularly limited, and examples thereof include an aliphatic polyol monomer, a polyol monomer having an alicyclic structure, an aromatic polyol monomer, a polyester polyol monomer, and a polyether polyol monomer.
  • the aliphatic polyol monomer is not particularly limited.
  • Use branched aliphatic diols such as 5-pentanediol and 2-methyl-1,9-nonanediol; and trifunctional or more polyhydric alcohols such as 1,1,1-trimethylolpropane and pentaerythritol. Can do.
  • the polyol monomer having an alicyclic structure is not particularly limited, and examples thereof include cyclohexanedimethanol such as 1,4-cyclohexanedimethanol and 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, and the like. Cyclopentanediol, 1,4-cycloheptanediol, 2,5-bis (hydroxymethyl) -1,4-dioxane, 2,7-norbornanediol, tetrahydrofuran dimethanol, 1,4-bis (hydroxyethoxy) cyclohexane, etc. A diol having an alicyclic structure in its main chain. Among these, cyclohexanedimethanol is preferred from the viewpoint of imparting good flexibility to a cured product obtained by curing the composition of the present invention.
  • the aromatic polyol monomer is not particularly limited, and examples thereof include 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 4,4′-naphthalenediethanol, and 3,4 4'-naphthalene diethanol is mentioned.
  • the polyester polyol monomer is not particularly limited, and examples thereof include a polyester diol of a hydroxycarboxylic acid and a diol such as a polyester diol of 6-hydroxycaproic acid and hexanediol, and a polyester diol of adipic acid and hexanediol. And polyester diols of dicarboxylic acids and diols.
  • the polyether polyol monomer is not particularly limited, and examples thereof include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
  • the cured product obtained from the composition of the present invention is used for an insulator for the polyol monomer used in the production of the polycarbonate polyol, it is preferable not to use an aromatic polyol monomer.
  • the cured product from the viewpoint of achieving high strength and heat resistance, it is preferable to use a polyol monomer having an alicyclic structure, in order to simultaneously achieve excellent flexibility in the cured product, Furthermore, it is preferable to use an aliphatic polyol monomer.
  • the ratio in the polycarbonate polyol is 100/0 in molar ratio. It is preferably ⁇ 0 / 100, more preferably 80/20 to 20/80.
  • This ratio may be achieved by using one type of polycarbonate polyol as the polyol compound (B), and as the ratio of each monomer in the polycarbonate polyol molecule, or by using a plurality of types of polycarbonate polyols. You may achieve as a ratio of the polyol monomer which has the alicyclic structure used in the whole polyol, and an aliphatic polyol monomer.
  • Examples of the latter include polycarbonate polyol X using a polyol monomer having an alicyclic structure as a polyol monomer, and polycarbonate polyol Y using an aliphatic polyol monomer as the polyol monomer, which has a molecular weight substantially the same as X. It is included in the composition of the present invention in a molar ratio.
  • Such a ratio can be adjusted to an arbitrary value by adjusting the amount of the polyol monomer used in the production of the polycarbonate polyol and the type and blending amount of the polycarbonate polyol used in the composition of the present invention. it can.
  • the carbonate ester compound that reacts with these polyol monomers is not particularly limited.
  • aliphatic carbonate ester compounds such as dimethyl carbonate and diethyl carbonate, aromatic carbonate ester compounds such as diphenyl carbonate, and ethylene carbonate.
  • the cyclic carbonate compound of the following As mentioned above, when using the hardened
  • phosgene or the like capable of producing a polycarbonate polyol can be used.
  • the aliphatic carbonic acid ester compounds are preferable, and dimethyl carbonate is particularly preferable because of easy manufacture of the polycarbonate polyol.
  • a method for producing a polycarbonate polyol from the polyol monomer and the carbonate compound for example, a carbonate compound and a polyol monomer having an excess number of moles relative to the number of moles of the carbonate compound are added to a reactor, and the temperature is increased.
  • An example is a method of reacting at 160 to 200 ° C. and a pressure of about 50 mmHg for 5 to 6 hours and further reacting at 200 to 220 ° C. for several hours at a pressure of several mmHg or less.
  • reaction it is preferable to carry out the reaction while extracting by-produced alcohol out of the system. At that time, if the carbonate compound escapes from the system by azeotroping with the by-produced alcohol, an excess amount of the carbonate compound may be added to the reaction system.
  • a catalyst such as titanium tetrabutoxide may be used.
  • the polycarbonate polyol that can be produced by such a production method is preferably a polycarbonate diol having two hydroxyl groups from the viewpoint of reactivity with the amino resin (A).
  • a diol monomer such as an aliphatic diol monomer, a diol monomer having an alicyclic structure, an aromatic diol monomer, a polyester diol monomer, or a polyether diol monomer
  • the polyol monomer is used as the polyol monomer.
  • polycarbonate polyols described above include ETERNACOLL UM-90 (3/1) (number average molecular weight is 900), ETERNACOLL UM-90 (1/1) (number average molecular weight is 900).
  • ETERNACOLL UM-90 (1/3) (number average molecular weight is 900), ETERNACOLL UC-100 (number average molecular weight is 1000), ETERNACOLL UH-200 (number average molecular weight is 2000), ETERNACOLL UH-100 (number average molecular weight) 1000), ETERNACOLL PH-200 (number average molecular weight is 2000) and ETERNACOLL PH-100 (number average molecular weight is 1000) (all of which are manufactured by Ube Industries, Ltd.).
  • the fraction shown at the end of the trade name is the ratio (1,1,2) of 1,4-cyclohexanedimethanol and 1,6-hexanediol, which are diol monomers used in the production of these polycarbonate diols. 4-cyclohexanedimethanol / 1,6-hexanediol).
  • ETERNACOLLEUC-100 has only 1,4-cyclohexanedimethanol as its diol monomer
  • ETERNACOLL UH-100 and ETERNACOLL UH-200 have 1,6- Only hexanediol is used
  • ETERNACOLL PH-100 and ETERNACOLL PH-200 are 1,5-pentanediol and 1,6-hexanediol as diol monomers.
  • the polyester polyol mentioned as an example of the high molecular weight polyol is not particularly limited, but specifically, polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyhexamethylene isophthalate adipate diol, polyethylene succinate.
  • the polyether polyol mentioned as an example of the high molecular weight polyol is not particularly limited, but specifically, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, a random copolymer of ethylene oxide and propylene oxide, ethylene oxide and butylene oxide. And block copolymers. Furthermore, a polyether polyester diol having an ether bond and an ester bond may be used.
  • the blending ratio (amino resin (A) / polyol compound (B)) in the amino resin composition of the present invention of the amino resin (A) and the polyol compound (B) described above is 85/15 to 15 / 85, preferably 80/20 to 20/80, more preferably 75/25 to 25/75. With such a blending ratio, a cured product excellent in both strength and flexibility can be easily obtained from the composition of the present invention.
  • the amino resin composition of the present invention can be cured by heating, and from the viewpoint of the strength and flexibility of the cured product, it is preferable to form a cured product by heating in the presence of the acid catalyst (C).
  • the acid catalyst (C) is not particularly limited as long as it has a function of promoting the crosslinking reaction between the amino resins (A) and between the amino resin (A) and the polyol compound (B). Such an acid catalyst (C) may be used alone or in combination of two or more.
  • Examples of the acid catalyst (C) include mineral acids and organic acids.
  • Examples of the mineral acids include hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid.
  • Examples of the organic acids include carboxylic acid, hydroxycarboxylic acid, and sulfonic acid.
  • Examples of the carboxylic acid include formic acid, acetic acid, monochloroacetic acid and dichloroacetic acid; examples of the hydroxycarboxylic acid include dimethylolbutanoic acid and dimethylolpropionic acid; examples of the sulfonic acid , Benzenesulfonic acid, paratoluenesulfonic acid, dinonylnaphthalenedisulfonic acid, dinonylnaphthalenesulfonic acid and dodecylbenzenesulfonic acid.
  • a block type in which an organic sulfonic acid is blocked with an amine can also be used.
  • the acid catalyst (C) is a diacid having two or more hydroxyl groups and one or more carboxylic acids in one molecule because it reacts with the amino resin (A) and is incorporated into the molecular chain of the cured product.
  • Methylol butanoic acid and dimethylolpropionic acid are preferred.
  • the compounding amount of the acid catalyst (C) in the composition of the present invention can be 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the solid content in the composition. Part, more preferably 0.2 to 3 parts by weight. With such a blending amount, the curing time of the composition of the present invention does not become long, and it is possible to obtain a cured product that is excellent in both strength and flexibility and has very little coloring and discoloration.
  • the acid catalyst (C) described above may be added to the composition of the present invention at the time of use or may be contained in the composition of the present invention from the beginning.
  • the amino resin composition of the present invention includes a solvent, other resins, pigments, dyes, and thickeners as necessary. , UV absorbers, light stabilizers, antifoaming agents, plasticizers, surface conditioners or anti-settling agents may be included.
  • a solvent for dilution can be used, alcohols such as methanol, ethanol, isopropyl alcohol, butanol and isobutanol, aromatic hydrocarbon solvents such as toluene and xylene, ethyl acetate and acetic acid.
  • An ester solvent such as butyl, a ketone solvent such as ⁇ -butyrolactone and cyclohexanone, an aprotic solvent such as N-methylpyrrolidone, and an ester ether solvent such as cellosolve acetate, butyl cellosolve acetate and carbitol acetate It can be contained in a range that does not impair the purpose.
  • the solvents may be used singly or in combination of two or more.
  • the viscosity of the composition of the present invention can be adjusted appropriately and workability can be improved.
  • the viscosity of the composition of the present invention measured at 25 ° C. using a BROOK FIELD HADV-II + C / P type E viscometer can be 100 to 40,000 cP.
  • the said solvent since the said solvent has not so high boiling point, it can be volatilized when heat-hardening the composition of this invention.
  • other resins can be added to the amino resin composition of the present invention as long as the effects of the present invention are not impaired.
  • the other resins include polyester resins, acrylic resins, polyether resins, polycarbonate resins, polyurethane resins, epoxy resins, alkyd resins, and polyolefin resins.
  • the cured product obtained from the composition of the present invention can have desired characteristics.
  • Coloring pigments can be added to the amino resin composition of the present invention. These may be used alone or in combination of two or more.
  • color pigment examples include titanium oxide, zinc white, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, selenium pigment, and perylene pigment.
  • extender pigment examples include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica and alumina white.
  • Examples of the bright pigment include aluminum, copper, zinc, brass, nickel, aluminum oxide, mica, aluminum oxide coated with titanium oxide and iron oxide, and mica coated with titanium oxide and iron oxide. be able to.
  • a dye can be added to the amino resin composition of the present invention.
  • the dyes may be used alone or in combination of two or more.
  • the dye examples include nitroso dye, nitro dye, azo dye, stilbene dye, diphenylmethane dye, triarylmethane dye, xanthene dye, acridine dye, quinoline dye, methine dye, polymethine dye, thiazole dye, indamine dye, indophenol
  • examples include dyes, azine dyes, oxazine dyes, thiazine dyes, sulfur dyes, aminoketone dyes, oxyketone dyes, anthraquinone dyes, indigoid dyes, and phthalocyanine dyes.
  • the amino resin (A) and the polyol compound (B) preferably undergo a crosslinking reaction in the presence of the acid catalyst (C) to obtain a cured product.
  • the cured product there are a rigid site derived from the amino resin (A) and a relatively flexible site derived from the polyol compound (B), and the cured product as a whole has excellent strength, heat resistance and flexibility. Sex is achieved.
  • the polyol compound (B) is preferably a specific polycarbonate polyol. In the polycarbonate polyol, there are a part that contributes to the strength of the cured product and a part that contributes to flexibility. It contributes to high strength, heat resistance and flexibility.
  • the cured product of the present invention maintains excellent transparency and heat resistance, which are the original characteristics of the amino resin (A), and therefore hardly undergoes coloring or discoloration due to heating. Therefore, when the composition of the present invention is colored by adding a pigment or dye, the resulting cured product can be colored in various colors, and the cured product is very discolored even when exposed to heat. Hateful.
  • the amino resin composition of the present invention which is preferably the cured product
  • the content of the component having an aromatic ring structure or the like is small, so the cured product is insulating. Therefore, such a cured product is suitable for insulator applications.
  • the insulator of the present invention is excellent in transparency and heat resistance as described above, it is difficult to be colored or discolored by heating. Therefore, if this is used as various insulator materials in electronic equipment, Variations in the color design of the insulator material that has only been colored in a dark color can be greatly increased.
  • the insulator is also suitable for applications such as an insulator used as a component of a flexible display.
  • the cured product of the present invention suitable for such an insulator use is generally obtained by applying the composition of the present invention on a substrate and heating at 60 to 200 ° C. for 10 to 180 minutes. The heating may be performed in a plurality of stages.
  • the material of the substrate includes metals, plastics, inorganic materials, and wood.
  • examples of the application method include casting, bell coating, spray coating, roll coating, shower coating, and immersion coating.
  • the cured product of the present invention obtained by the coating and heating method described above has an elastic modulus of usually 5 to 3000 MPa, a strength at break of usually 3 to 200 MPa, and an elongation at break of usually 5 to 200%.
  • the thickness is usually 10 to 150 ⁇ m.
  • the color difference ⁇ E * after the cured product is heat-treated at 230 ° C. for 4 hours is usually 3 or less, and the yellowness YI is usually 5 or less.
  • the amino resin composition was cast on a glass plate and heated in an oven at 60 ° C. ⁇ 10 min, 80 ° C. ⁇ 10 min, 100 ° C. ⁇ 10 min, 150 ° C. ⁇ 40 min to obtain a cured film having an average film thickness of 15 ⁇ m.
  • the average film thickness was obtained by using a digital micrometer ⁇ -mate M-30 (manufactured by Sony Magnescale Co., Ltd.) to determine the difference between the thickness of the combined glass plate and the formed cured film and the thickness of the glass plate alone. The points were measured and averaged. The same applies hereinafter.
  • the tensile properties (elastic modulus, strength at break and elongation at break) and heat resistance of the cured product film were measured.
  • a color difference ⁇ E * and yellowness YI after the cured film was heat-treated at 230 ° C. for 1 hour, 2 hours, and 4 hours with a color meter ZE6000 manufactured by Nippon Denshoku Industries Co., Ltd. were measured.
  • the above measurement results are shown in Table 1 below.
  • the viscosity of the obtained amino resin composition is also shown in Table 1. The viscosity was measured at 25 ° C. using a BROOK FIELD HADV-II + C / P type E viscometer. The same applies hereinafter.
  • Example 2 91 parts by weight of amino resin Uban 2020 (manufactured by Mitsui Chemicals) (of which 68 parts by weight of amino resin (solid content)), 32 parts by weight of polycarbonate diol ETERNACOLL UM-90 (3/1), 0.4 parts by weight of DMBA, An amino resin composition was prepared by mixing 20.3 parts by weight of ⁇ -butyrolactone as a diluent solvent.
  • the amino resin composition was cast on a glass plate and heated in an oven at 60 ° C. ⁇ 10 min, 80 ° C. ⁇ 10 min, 100 ° C. ⁇ 10 min, 150 ° C. ⁇ 40 min to obtain a cured film having an average film thickness of 14 ⁇ m.
  • the tensile properties and heat resistance of the cured product film were measured in the same manner as in Example 1. The above measurement results are shown in Table 1 below. Moreover, the viscosity of the obtained amino resin composition is also shown in Table 1.
  • Example 3 Amino resin Uban 2020 (manufactured by Mitsui Chemicals) 81 parts by weight (of which amino resin (solid content) is 61 parts by weight), polycarbonate diol ETERNACOLL UM-90 (3/1) 39 parts by weight, DMBA 0.3 parts by weight, An amino resin composition was prepared by mixing 33.6 parts by weight of ⁇ -butyrolactone as a diluent solvent.
  • the amino resin composition was cast on a glass plate and heated in an oven at 60 ° C. ⁇ 10 min, 80 ° C. ⁇ 10 min, 100 ° C. ⁇ 10 min, 150 ° C. ⁇ 40 min to obtain a cured film having an average film thickness of 12 ⁇ m.
  • the tensile properties and heat resistance of the cured product film were measured in the same manner as in Example 1. The above measurement results are shown in Table 1 below. Moreover, the viscosity of the obtained amino resin composition is also shown in Table 1.
  • Example 4 Amino resin Euban 2020 (manufactured by Mitsui Chemicals) 68 parts by weight (of which 51 parts by weight of amino resin (solid content)), polycarbonate diol ETERNACOLL UM-90 (3/1) 49 parts by weight, DMBA 0.4 parts by weight, An amino resin composition was prepared by mixing 36.8 parts by weight of ⁇ -butyrolactone as a diluent solvent.
  • the amino resin composition was cast on a glass plate and heated in an oven at 60 ° C. ⁇ 10 min, 80 ° C. ⁇ 10 min, 100 ° C. ⁇ 10 min, 150 ° C. ⁇ 40 min to obtain a cured film having an average film thickness of 12 ⁇ m.
  • the tensile properties and heat resistance of the cured product film were measured in the same manner as in Example 1. The above measurement results are shown in Table 1 below. Moreover, the viscosity of the obtained amino resin composition is also shown in Table 1.
  • Example 5 45 parts by weight of amino resin Euban 2020 (manufactured by Mitsui Chemicals) (of which 34 parts by weight of amino resin (solid content)), 66 parts by weight of polycarbonate diol ETERNACOLL UM-90 (3/1), 0.4 parts by weight of DMBA, An amino resin composition was prepared by mixing 21.8 parts by weight of ⁇ -butyrolactone as a diluent solvent.
  • the amino resin composition was cast on a glass plate and heated in an oven at 60 ° C. ⁇ 10 min, 80 ° C. ⁇ 10 min, 100 ° C. ⁇ 10 min, 150 ° C. ⁇ 40 min to obtain a cured film having an average film thickness of 15 ⁇ m.
  • the tensile properties and heat resistance of the cured product film were measured in the same manner as in Example 1. The above measurement results are shown in Table 1 below. Moreover, the viscosity of the obtained amino resin composition is also shown in Table 1.
  • Example 6 Amino resin Uban 2020 (manufactured by Mitsui Chemicals) 81 parts by weight (of which 61 parts by weight of amino resin (solid content)), 39 parts by weight of polycarbonate diol ETERNACOLL UM-90 (1/1), 0.4 parts by weight of DMBA, An amino resin composition was prepared by mixing 4.5 parts by weight of ⁇ -butyrolactone as a diluent solvent.
  • the amino resin composition was cast on a glass plate and heated in an oven at 60 ° C. ⁇ 10 min, 80 ° C. ⁇ 10 min, 100 ° C. ⁇ 10 min, 150 ° C. ⁇ 40 min to obtain a cured film having an average film thickness of 16 ⁇ m.
  • the tensile properties and heat resistance of the cured product film were measured in the same manner as in Example 1. The above measurement results are shown in Table 1 below. Moreover, the viscosity of the obtained amino resin composition is also shown in Table 1.
  • Example 7 Amino resin Euban 2020 (manufactured by Mitsui Chemicals, Inc.) 68 parts by weight (of which 51 parts by weight of amino resin (solid content)), polycarbonate diol ETERNACOLL UM-90 (1/1) 49 parts by weight, DMBA 0.4 parts by weight, An amino resin composition was prepared by mixing 8.0 parts by weight of ⁇ -butyrolactone as a diluent solvent.
  • the amino resin composition was cast on a glass plate and heated in an oven at 60 ° C. ⁇ 10 min, 80 ° C. ⁇ 10 min, 100 ° C. ⁇ 10 min, 150 ° C. ⁇ 40 min to obtain a cured film having an average film thickness of 17 ⁇ m.
  • the tensile properties and heat resistance of the cured product film were measured in the same manner as in Example 1. The above measurement results are shown in Table 1 below. Moreover, the viscosity of the obtained amino resin composition is also shown in Table 1.
  • Example 8 Amino resin Uban 2020 (manufactured by Mitsui Chemicals) 47 parts by weight (of which amino resin (solid content) is 35 parts by weight), polycarbonate diol ETERNACOLL UM-90 (1/3) 65 parts by weight, DMBA 0.5 part by weight, An amino resin composition was prepared by mixing 13.4 parts by weight of ⁇ -butyrolactone as a diluent solvent.
  • the amino resin composition was cast on a glass plate and heated in an oven at 60 ° C. ⁇ 10 min, 80 ° C. ⁇ 10 min, 100 ° C. ⁇ 10 min, 150 ° C. ⁇ 40 min to obtain a cured film having an average film thickness of 15 ⁇ m.
  • the tensile properties and heat resistance of the cured product film were measured in the same manner as in Example 1. The above measurement results are shown in Table 1 below. Moreover, the viscosity of the obtained amino resin composition is also shown in Table 1.
  • Example 9 65 parts by weight of amino resin Euban 2020 (Mitsui Chemicals Co., Ltd.) (of which 48.5 parts by weight of amino resin (solid content)), 51.5 parts by weight of polycarbonate diol ETERNACOLL UC-100, 0.4 parts by weight of DMBA, diluted An amino resin composition was prepared by mixing 37.6 parts by weight of ⁇ -butyrolactone as a solvent.
  • the amino resin composition was cast on a glass plate and heated in an oven at 60 ° C. ⁇ 10 min, 80 ° C. ⁇ 10 min, 100 ° C. ⁇ 10 min, 150 ° C. ⁇ 40 min to obtain a cured film having an average film thickness of 13 ⁇ m.
  • Example 10 Amino resin Uban 2020 (manufactured by Mitsui Chemicals, Inc.) 65 parts by weight (of which 48.5 parts by weight of amino resin (solid content)), polycarbonate diol ETERNACOLL UC-100 38.6 parts by weight and ETERNACOLL UH-100 12.9
  • An amino resin composition was prepared by mixing 4 parts by weight of DMBA, 0.4 part by weight of DMBA, and 37.7 parts by weight of ⁇ -butyrolactone as a diluent solvent.
  • the amino resin composition was cast on a glass plate and heated in an oven at 60 ° C. ⁇ 10 min, 80 ° C. ⁇ 10 min, 100 ° C. ⁇ 10 min, 150 ° C. ⁇ 40 min to obtain a cured film having an average film thickness of 16 ⁇ m.
  • Example 11 Amino resin Uban 2020 (Mitsui Chemicals Co., Ltd.) 65 parts by weight (of which amino resin (solid content) is 48.5 parts by weight), polycarbonate diol ETERNACOLL UH-100 51.5 parts by weight, DMBA 0.4 parts by weight are mixed Thus, an amino resin composition was prepared.
  • the amino resin composition was cast on a glass plate and heated in an oven at 60 ° C. ⁇ 10 min, 80 ° C. ⁇ 10 min, 100 ° C. ⁇ 10 min, 150 ° C. ⁇ 40 min to obtain a cured film having an average film thickness of 19 ⁇ m.
  • Table 1 shows the viscosity of the obtained amino resin composition.
  • Table 1 shows the viscosity of the obtained amino resin composition.
  • Example 12 Amino resin Uban 2020 (manufactured by Mitsui Chemicals) 64 parts by weight (of which 48 parts by weight of amino resin (solid content)) and polycarbonate diol PH-100 (manufactured by Ube Industries, Ltd., 1,5-pentanediol and 1 , 6-hexanediol and dimethyl carbonate as raw materials, polycarbonate diol having a number average molecular weight of 1000. 1,5-pentanediol: 1,6-hexanediol molar ratio 45:55) 52 parts by weight, DMBA 0. An amino resin composition was prepared by mixing 4 parts by weight.
  • the amino resin composition was cast on a glass plate and heated in an oven at 60 ° C. ⁇ 10 min, 80 ° C. ⁇ 10 min, 100 ° C. ⁇ 10 min, 150 ° C. ⁇ 40 min to obtain a cured film having an average film thickness of 13 ⁇ m.
  • the tensile properties and heat resistance of the cured product film were measured in the same manner as in Example 1. The above measurement results are shown in Table 1 below. Moreover, the viscosity of the obtained amino resin composition is also shown in Table 1.
  • Example 13 Amino resin NIKALAC MX-706 ((Ltd.) Sanwa Chemical Co., in the general formula (I), -X- is -R 13 -O-R 14 - or -R 14 - a and (R 13 and R 14 are methylene R 1 to R 6 and R 15 to R 18 are hydrogen or a methyl group, and at least one of R 1 to R 6 and R 15 to R 18 is hydrogen, and R 7 to R 12 And R 19 to R 22 are methylene groups, n is a melamine resin having 0 to 3, and the number average molecular weight in terms of standard polystyrene measured by GPC is 590) 57.1 parts by weight (of which amino resin ( 40 parts by weight of solid content), 60 parts by weight of polycarbonate diol PH-100 (manufactured by Ube Industries) and 0.4 part by weight of DMBA were mixed to prepare an amino resin composition.
  • the amino resin composition was cast on a glass plate and heated in an oven at 60 ° C. ⁇ 10 min, 80 ° C. ⁇ 10 min, 100 ° C. ⁇ 10 min, 150 ° C. ⁇ 40 min to obtain a cured film having an average film thickness of 18 ⁇ m.
  • the tensile properties and heat resistance of the cured product film were measured in the same manner as in Example 1. The above measurement results are shown in Table 1 below. Moreover, the viscosity of the obtained amino resin composition is also shown in Table 1.
  • Example 14 Amino resin Nicalac MX-410 (manufactured by Sanwa Chemical Co., Ltd., in the general formula (I), —X— is —R 13 —O—R 14 — or —R 14 — (R 13 and R 14 are methylene) R 1 to R 6 and R 15 to R 18 are hydrogen or a methyl or n-butyl group, and at least one of R 1 to R 6 and R 15 to R 18 is hydrogen, 7 to R 12 and R 19 to R 22 are methylene groups, n is a melamine resin having 0 to 3, and the number average molecular weight in terms of standard polystyrene measured by GPC is 656) 60 parts by weight (of which amino Resin (solid content is 42 parts by weight) and polycarbonate diol PH-200 (manufactured by Ube Industries, Ltd., 1,5-pentanediol, 1,6-hexanediol and dimethyl carbonate as a raw material) Polycarbonate di
  • 1,5-pentanediol 1,6-hexanediol molar ratio 45:55
  • DMBA 0.4 parts by weight
  • ⁇ -butyrolactone 15.5 parts by weight as a diluent solvent
  • the amino resin composition was cast on a glass plate and heated in an oven at 60 ° C. ⁇ 10 min, 80 ° C. ⁇ 10 min, 100 ° C. ⁇ 10 min, 150 ° C. ⁇ 40 min to obtain a cured film having an average film thickness of 14 ⁇ m.
  • the tensile properties and heat resistance of the cured product film were measured in the same manner as in Example 1. The above measurement results are shown in Table 1 below. Moreover, the viscosity of the obtained amino resin composition is also shown in Table 1.
  • Example 15 Amino resin Cymel 370N (Nippon Cytec Industries, Ltd., in the general formula (I), -X- is -R 13 -O-R 14 - or -R 14 - a and (R 13 and R 14 is a methylene group), R 1 to R 6 and R 15 to R 18 are hydrogen or a methyl group, and at least one of R 1 to R 6 and R 15 to R 18 is hydrogen, and R 7 to R 12 and R 19 to R 22 is a methylene group, n is a melamine resin of 0 to 3, and the number average molecular weight in terms of standard polystyrene measured by GPC is 527) 45.5 parts by weight (of which the amino resin (solid content) is 40 Parts by weight), 60 parts by weight of polycarbonate diol PH-200 (manufactured by Ube Industries) and 0.2 part by weight of DMBA were mixed to prepare an amino resin composition.
  • the amino resin composition was cast on a glass plate and heated in an oven at 60 ° C. ⁇ 10 min, 80 ° C. ⁇ 10 min, 100 ° C. ⁇ 10 min, 150 ° C. ⁇ 40 min to obtain a cured film having an average film thickness of 17 ⁇ m.
  • the tensile properties and heat resistance of the cured product film were measured in the same manner as in Example 1. The above measurement results are shown in Table 1 below. Moreover, the viscosity of the obtained amino resin composition is also shown in Table 1.
  • Example 16 Amino resin composition by mixing 28 parts by weight of amino resin Uban 2020 (Mitsui Chemicals Co., Ltd.) (21 parts by weight of amino resin (solid content)) and 79 parts by weight of polycarbonate diol ETERNACOLL UM-90 (1/3) A product was prepared.
  • the amino resin composition is cast on a glass plate and heated in an oven at 60 ° C. ⁇ 10 min, 80 ° C. ⁇ 10 min, 100 ° C. ⁇ 10 min, 150 ° C. ⁇ 40 min, 230 ° C. ⁇ 60 min to obtain a cured product having an average film thickness of 22 ⁇ m. A film was obtained.
  • Table 1 shows the viscosity of the amino resin composition obtained.
  • the cured product obtained from the amino resin composition of the present invention is excellent in transparency, and hardly colored even when heated at a high temperature for a long time, and is extremely excellent in heat resistance.
  • the tensile properties (strength) of the resulting cured product are excellent when the blending amount of the amino resin (A) and the ratio of the diol monomer having an alicyclic structure in the diol monomer component constituting the polycarbonate diol are high. .
  • Examples 1 to 15 indicate that the use of the acid catalyst (C) is preferable from the viewpoint of the strength of the cured product, and the heat resistance is also improved. Further, it can be seen from the comparative example that when a melamine resin having no free hydroxyl group is used as the amino resin, a cured product having sufficient strength and heat resistance cannot be obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un matériau apte à former un produit durci transparent qui est excellent en termes de transparence, de robustesse et de flexibilité, et qui ne se décolore pas ni ne devient coloré même après avoir été soumis à un traitement thermique à température élevée. L'invention porte également sur une composition d'amino-résine contenant les éléments suivants : une amino-résine (A) possédant un groupe hydroxyle libre et un groupe alkoxyle ; et un composé polyol (B).
PCT/JP2012/082238 2011-12-16 2012-12-12 Composition d'amino-résine, et produit durci obtenu à partir de ladite composition Ceased WO2013089149A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2013549289A JP6146314B2 (ja) 2011-12-16 2012-12-12 アミノ樹脂組成物及びそれから得られる硬化物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-276112 2011-12-16
JP2011276112 2011-12-16

Publications (1)

Publication Number Publication Date
WO2013089149A1 true WO2013089149A1 (fr) 2013-06-20

Family

ID=48612592

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/082238 Ceased WO2013089149A1 (fr) 2011-12-16 2012-12-12 Composition d'amino-résine, et produit durci obtenu à partir de ladite composition

Country Status (3)

Country Link
JP (1) JP6146314B2 (fr)
TW (1) TW201331246A (fr)
WO (1) WO2013089149A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013209656A (ja) * 2008-11-20 2013-10-10 Chuo Rika Kogyo Corp ポリウレタン−（メタ）アクリル系重合体複合樹脂水性分散液、水性コーティング剤および積層体

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61115967A (ja) * 1984-11-12 1986-06-03 Dainippon Toryo Co Ltd 塗料用樹脂組成物
JPS61254653A (ja) * 1985-05-07 1986-11-12 Dainippon Ink & Chem Inc 硬化性樹脂組成物
JPH04277568A (ja) * 1991-03-04 1992-10-02 Kansai Paint Co Ltd 発水化処理組成物と発水化処理法
JPH059434A (ja) * 1991-06-28 1993-01-19 Asahi Chem Ind Co Ltd 塗料用樹脂及び塗料組成物
JPH05125345A (ja) * 1991-11-08 1993-05-21 Ube Ind Ltd 接着性組成物
JPH05230318A (ja) * 1992-02-24 1993-09-07 Kanegafuchi Chem Ind Co Ltd 熱硬化性樹脂組成物
JPH1088010A (ja) * 1996-09-17 1998-04-07 Nippon Paint Co Ltd 硬化性樹脂組成物
JPH10251613A (ja) * 1997-03-12 1998-09-22 Japan Crown Cork Co Ltd ポリエステルフィルム貼り合わせ金属板用接着剤、ポリエステルフィルム貼り合わせ金属板並びにキャップ
JP2005139343A (ja) * 2003-11-07 2005-06-02 Nippon Yushi Basf Coatings Kk 熱硬化性塗料組成物、塗装仕上げ方法及び塗装物品
JP2008144063A (ja) * 2006-12-12 2008-06-26 Nippon Paint Co Ltd 水性硬化性樹脂組成物および水性塗料組成物

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6433131B1 (en) * 2000-02-29 2002-08-13 Shell Oil Company High gloss acrylic coatings with improved impact resistance cured with melamine
JP2008056760A (ja) * 2006-08-30 2008-03-13 Inoac Corp 医療用コーティング剤、ゴム成形品および表面改質方法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61115967A (ja) * 1984-11-12 1986-06-03 Dainippon Toryo Co Ltd 塗料用樹脂組成物
JPS61254653A (ja) * 1985-05-07 1986-11-12 Dainippon Ink & Chem Inc 硬化性樹脂組成物
JPH04277568A (ja) * 1991-03-04 1992-10-02 Kansai Paint Co Ltd 発水化処理組成物と発水化処理法
JPH059434A (ja) * 1991-06-28 1993-01-19 Asahi Chem Ind Co Ltd 塗料用樹脂及び塗料組成物
JPH05125345A (ja) * 1991-11-08 1993-05-21 Ube Ind Ltd 接着性組成物
JPH05230318A (ja) * 1992-02-24 1993-09-07 Kanegafuchi Chem Ind Co Ltd 熱硬化性樹脂組成物
JPH1088010A (ja) * 1996-09-17 1998-04-07 Nippon Paint Co Ltd 硬化性樹脂組成物
JPH10251613A (ja) * 1997-03-12 1998-09-22 Japan Crown Cork Co Ltd ポリエステルフィルム貼り合わせ金属板用接着剤、ポリエステルフィルム貼り合わせ金属板並びにキャップ
JP2005139343A (ja) * 2003-11-07 2005-06-02 Nippon Yushi Basf Coatings Kk 熱硬化性塗料組成物、塗装仕上げ方法及び塗装物品
JP2008144063A (ja) * 2006-12-12 2008-06-26 Nippon Paint Co Ltd 水性硬化性樹脂組成物および水性塗料組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013209656A (ja) * 2008-11-20 2013-10-10 Chuo Rika Kogyo Corp ポリウレタン−（メタ）アクリル系重合体複合樹脂水性分散液、水性コーティング剤および積層体

Also Published As

Publication number Publication date
TW201331246A (zh) 2013-08-01
JPWO2013089149A1 (ja) 2015-04-27
JP6146314B2 (ja) 2017-06-14

Similar Documents

Publication Publication Date Title
KR102670942B1 (ko) 내열성 및 용제 용해성이 우수한 폴리에스테르 수지 및 이를 함유하는 코팅 조성물
TWI588176B (zh) 聚酯樹脂組成物及其製備方法
Noordover et al. Chemistry, functionality, and coating performance of biobased copolycarbonates from 1, 4: 3, 6‐dianhydrohexitols
CN104334608A (zh) 聚酯树脂及用于制备该聚酯树脂的方法
KR20130090748A (ko) 폴리에스테르계 수지, 폴리에스테르계 수지의 제조방법, 및 폴리에스테르계 수지 수성액
CN111511798A (zh) 聚酯树脂以及聚酯树脂的制备方法
KR101488316B1 (ko) 스크래치 자가복원 도료 조성물
US20190309161A1 (en) Polyester resin, preparation method therefor, and copolymer polyester film manufacturing method using same
KR101783122B1 (ko) 카르복실 폴리에스터 수지 및 이를 포함하는 분체도료 조성물
JP6146314B2 (ja) アミノ樹脂組成物及びそれから得られる硬化物
CN112513135B (zh) 聚酯树脂及其制备方法
JP2018505936A (ja) 高弾性ポリエステル変性ウレタン樹脂及びこれを含むクリアコート組成物
JP5560530B2 (ja) 共重合ポリエステル樹脂
US20160075819A1 (en) Novel polycarboxylic acid anhydride and use thereof
TWI798299B (zh) 抗化學性抗污性熱塑性聚胺甲酸酯組成物及提高物件的抗化學性和防沾污性之方法
JP2013181080A (ja) 樹脂組成物
CN107001784A (zh) 膜
JP5527575B2 (ja) プラスチック用非水系コーティング剤組成物
KR102556372B1 (ko) 폴리에스테르계 수지 및 이를 포함하는 광학 부재
JP3601717B2 (ja) ポリエステル樹脂組成物
KR101940784B1 (ko) 공중합 폴리에스테르 필름 및 이의 제조 방법
JP2018058939A (ja) ポリエステル樹脂組成物
KR101883819B1 (ko) 폴리에스테르 수지 및 이의 제조방법
CN115948104B (zh) 涂料组合物
CN102549040A (zh) 丙烯酸改性氨基甲酸酯脲树脂组合物及使用其得到的成形品

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12858213

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2013549289

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12858213

Country of ref document: EP

Kind code of ref document: A1