JP2007297604A - Thermosetting resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition excellent in moist heat resistance and capable of forming a transparent cured material, to provide an optical film prepared by curing the thermosetting resin composition, and to provide a laminated film prepared by applying the thermosetting resin composition on a base film and curing the same. <P>SOLUTION: The thermosetting resin composition comprises (A) a polycarboxylic acid resin, and (B) an epoxy resin and/or an oxetane resin as essential components, and the transmittance of a film of ca. 80 μm thickness obtained by curing the thermosetting resin composition is at least 90% in the whole wave length range of 380-750 nm. The optical film is obtained by curing the thermosetting resin composition, and the laminated film is obtained by applying the thermosetting resin composition on a base film, followed by curing the same. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention comprises (A) a polycarboxylic acid resin, and (B) an epoxy resin and / or an oxetane resin as essential components, which are cured to give a film having a thickness of about 80 μm. The present invention relates to a thermosetting resin composition that is 90% or more in the region, an optical film and a laminated film obtained from the thermosetting resin composition, and a liquid crystal display using the film.

The protective layer of the polarizing plate, which is the basic constituent material of liquid crystal displays, has no birefringence, high transmittance, good heat resistance and moisture absorption resistance, high mechanical strength, changes in temperature and humidity Performances such as a low shrinkage ratio, a smooth surface, high resolution, good adhesion with an adhesive, and excellent appearance are required.
Conventionally, as a protective layer of a liquid crystal display, a cellulose triacetate (TAC) film having high film uniformity, non-orientation, low birefringence, high transparency and good appearance is mainly used. However, the TAC film has insufficient properties such as moisture resistance, and particularly in a large-sized liquid crystal display, there is a problem that durability under high temperature and high humidity is low.
On the other hand, for example, Japanese Patent Application Laid-Open No. 05-212828 (Patent Document 1) uses a norbornene-based resin film, and Japanese Patent Application Laid-Open No. 2005-092112 (Patent Document 2) uses an acrylic photocurable resin composition. It has been proposed to use a cured product.
On the other hand, it is known that a cured product obtained from a thermosetting resin is generally excellent in heat resistance, but there has been almost no study on the use of this as a polarizing plate protective layer.

Japanese Patent Laid-Open No. 05-212828 Japanese Patent Laying-Open No. 2005-092112

As described above, the present invention provides a protective layer having improved durability under high temperature and high humidity than before by using a cured product obtained from a thermosetting resin excellent in heat resistance for a polarizing plate protective layer. It is aimed at.
That is, the present invention provides a thermosetting composition excellent in wet heat resistance and capable of forming a transparent cured product, providing an optical film obtained by curing the thermosetting resin composition, and the above It aims at providing the laminated | multilayer film obtained by apply | coating a thermosetting resin composition on a base film, and hardening this.

  As a result of intensive studies, the present inventors have found that a thermosetting resin composition containing (A) a polycarboxylic acid resin and (B) an epoxy resin and / or an oxetane resin as an essential component achieves the above-described problems. It was.

That is, this invention relates to the following 1-7 thermosetting resin compositions, 8-9 optical films, 10 laminated films, and 11 liquid crystal displays.
1. (A) Polycarboxylic acid resin, and (B) Epoxy resin and / or oxetane resin as essential components, cured into a film having a thickness of about 80 μm, has a light transmittance of 90 in the entire range of wavelengths of 380 to 750 nm. % Thermosetting resin composition.
2. (A) The thermosetting resin composition as described in 1 above, wherein the polycarboxylic acid resin is a carboxyl group-containing urethane resin.
3. The carboxyl group-containing urethane resin is (a) a polyisocyanate compound,
(B) a polyhydroxy compound,
(C) The thermosetting resin composition according to 2 above, which is a dihydroxy compound having a carboxyl group and, if necessary, (d) a compound using a monohydroxy compound as a raw material.
4). (C) The thermosetting resin composition according to any one of the above 1 to 3, comprising a curing catalyst.
5). The molar ratio of carboxyl group of the polycarboxylic acid resin (A) / [epoxy group and / or oxetanyl group of the epoxy resin and / or oxetane resin (B)] is 0.5 to 2, and the polycarboxylic acid resin ( A) The thermosetting resin composition according to the above 1 to 4, comprising 0.01 to 10 parts by mass of the curing catalyst (C) with respect to 100 parts by mass.
6). The thermosetting resin composition according to any one of 1 to 5, which contains an inorganic or organic filler having an average particle diameter of 1 to 100 nm determined by a dynamic light scattering method. 7). 7. The thermosetting resin composition according to any one of 1 to 6, comprising an inorganic or organic filler having the same refractive index as a cured product obtained by curing the thermosetting resin composition.
8). The optical film obtained by hardening | curing the thermosetting resin composition in any one of said 1-7.
9. 9. The optical film as described in 8 above, wherein the thickness is 200 μm or less.
10. The laminated film obtained by apply | coating the thermosetting resin composition in any one of said 1-7 on a base film, and hardening this.
11. A liquid crystal display using at least one of the optical film according to 8 or 9 or the laminated film according to 10 as a member.

  The thermosetting resin composition of the present invention can provide an optical film excellent in durability under high temperature and high humidity. The optical film obtained by curing the thermosetting resin composition of the present invention can be suitably used as a protective film for a polarizing plate, a substrate such as a retardation film, an antireflection film, a member for a liquid crystal display, and the like.

Hereinafter, the thermosetting resin composition, the optical film, the laminated film, and the liquid crystal display of the present invention will be described in detail.
The thermosetting resin composition of the present invention has (A) a polycarboxylic acid resin and (B) an epoxy resin and / or an oxetane resin as essential components, and a film cured to a thickness of about 80 μm has a light transmittance of 380 wavelengths. It is 90% or more in the whole region of ˜750 nm.

[About Polycarboxylic Acid Resin (A)]
Examples of the polycarboxylic acid resin (A) that can be used in the present invention include (a) a carboxyl group-containing urethane resin,
(B) a resin obtained by adding a monocarboxylic acid to an epoxy resin and then reacting with an acid anhydride;
(C) a copolymer of (meth) acrylic acid or a compound represented by the following general formula (2), or (d) a polyimide, a polyamideimide, a polyamide, a polyurethane and a polyester having a carboxylic acid or an acid anhydride at both ends. Can be mentioned.

(A) Carboxyl group-containing urethane resin In the present invention, the carboxyl group-containing urethane resin (a) can be used as the polycarboxylic acid resin (A). The carboxyl group-containing urethane resin (a) is, for example,
(A-1) a polyisocyanate compound,
(A-2) a polyhydroxy compound,
(A-3) a hydroxy compound containing a carboxyl group and, if necessary,
(A-4) It can be synthesized by combining raw materials of monohydroxy compounds.

(A-1) Polyisocyanate compound Examples of the polyisocyanate compound (a-1) include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, (o, m, or p) -xylene diisocyanate. Aromatic diisocyanates such as narate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3′-methylene ditolylene-4,4′-diisocyanate, 4,4′-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, 6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethyl Aliphatic diisocyanates such as xamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate And alicyclic diisocyanates such as cyclohexane-1,4-dimethylene diisocyanate and norbornene diisocyanate, and ether diisocyanates such as 2,2′-diethyl ether diisocyanate.

Among these diisocyanate compounds, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,6 from the viewpoint of light stability and the flexibility of the resulting film. Aliphatic diisocyanates such as 4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, methylene bis (Cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, norbornene diisocyanate, etc. Cycloaliphatic diisocyanates, ether diisocyanates such as 2,2'-diethyl ether diisocyanate are particularly preferred. These diisocyanate compounds can be used alone or in combination of two or more.
Further, as the polyisocyanate compound (a-1), a small amount of polyisocyanate having 3 or more isocyanate groups such as triphenylmethane triisocyanate in a range in which gelation does not occur, for example, in a range of less than 50 mol% of the total polyisocyanate compound. Can be used.

(A-2) Polyhydroxy compound Examples of the polyhydroxy compound (a-2) include alkylene glycol, alicyclic diol, epoxy compound addition product to bisphenol A, polycarbonate diol, polyether diol, polyester diol, and polylactone. Examples include diol compounds such as diol, polybutadiene diol, hydrogenated polybutadiene diol, polyisoprene diol, hydrogenated polyisoprene diol, both-end hydroxylated polysilicone, and hydrogenated dimer acid.

  Examples of the alkylene glycol include ethylene glycol, propylene glycol, 1,3-propanediol, tetramethylene glycol, hexamethylene glycol, 1,9-nonanediol, 1,10-decanediol, and the like.

  Examples of the alicyclic diol include 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, and the like.

  Examples of the epoxy compound adduct to bisphenol A include bisphenol A ethylene oxide 2 mol adduct, bisphenol A ethylene oxide 4 mol adduct, bisphenol A propylene oxide 2 mol adduct, bisphenol A propylene oxide 4 mol adduct, and the like. .

  Examples of the polycarbonate diol include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8- Octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol , 1,3-cyclohexanediol, tricyclohexane dimethanol, and a polycarbonate diol component consisting of pentacyclopentadecane dimethanol.

  Examples of the polyether diol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly-3-methyltetramethylene glycol, and copolymers of these polyether diols.

Examples of polyester diols include saturated aliphatic dicarboxylic acids such as succinic acid and adipic acid as unsaturated carboxylic acid components, unsaturated aliphatic dicarboxylic acids such as fumaric acid and maleic acid, and saturated alicyclic dicarboxylic acids such as hexahydrophthalic acid. , Unsaturated alicyclic dicarboxylic acids such as tetrahydrophthalic acid, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid, trifunctional or higher carboxylic acid compounds such as trimellitic acid and pyromellitic acid In addition, as the polyol component, ethylene glycol, propylene glycol, 1,3-propanediol, tetramethylene glycol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1 , 5-pentanediol, neopentyl glycol, 1,6 Fragrance-containing aroma such as hexanediol, alkylene glycol such as 3-methyl-1,5-pentanediol, cycloaliphatic alcohol such as cyclohexanediol and cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A Mention may be made of those containing a trifunctional or higher functional hydroxy compound such as ring diol, glycerin and pentaerythritol.
Among these, those containing isophthalic acid as a dicarboxylic acid component from the viewpoint of scratch resistance, and propylene glycol, 1,3-butanediol, 2-methyl-1,3-propanediol, 3 as a polyol component from the viewpoint of crystallinity, 3 It is particularly preferable to use a branched alkylene glycol such as methyl-1,5-pentanediol.

Examples of the polylactone diol include polycaprolactone diol.
Examples of polybutadiene diol include polybutadiene diol mainly having 1,4-repeating units (for example, Poly bd T-15HT (trade name: manufactured by Idemitsu Kosan Co., Ltd.)), hydroxyl group mainly having 1,2-repeating units. Polybutadiene (for example, G-1000, G-2000, G-3000 (all trade names: manufactured by Nippon Soda Co., Ltd.)).

Examples of the hydrogenated polybutadiene diol include hydrogenated polybutadiene diol mainly having 1,4-repeating units (for example, polytail H and polytail HA (both trade names: manufactured by Mitsubishi Chemical Corporation)), 1,2-repeat. Examples thereof include hydrogenated polybutadiene diol mainly having units (for example, GI-1000, GI-2000, and GI-3000 (all trade names: Nippon Soda Co., Ltd.)).
An example of polyisoprene diol is Poly IP (trade name: manufactured by Idemitsu Kosan Co., Ltd.).
An example of hydrogenated polyisoprene diol is Epol (trade name: manufactured by Idemitsu Kosan Co., Ltd.).

（式中、Ｒ¹はそれぞれ独立して炭素数２〜５０の脂肪族炭化水素基または芳香族炭化水素基を表し、これらはエーテル基を含んでいてもよく、複数個あるＲ²はそれぞれ独立して炭素数１〜１２の脂肪族炭化水素基または芳香族炭化水素基を表す。）
で示される。 The both-end hydroxylated polysilicone has, for example, the following general formula (1):

(In the formula, each R ¹ independently represents an aliphatic hydrocarbon group having 2 to 50 carbon atoms or an aromatic hydrocarbon group, which may contain an ether group, and a plurality of R ² are each independently selected. And represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group.)
Indicated by

  Examples of the hydrogenated dimer acid include Sovermol 908 (trade name: manufactured by Cognis Co., Ltd.).

Among these diol compounds listed above, it is particularly preferable to use a polyester diol when the resulting film requires scratch resistance.
Moreover, as a polyhydroxy compound (a-2), it has 3 or more hydroxyl groups, such as glycerol, a trimethylol ethane, a trimethylol propane, a pentaerythritol, in the range which does not gelatinize, for example, less than 50 mol% of all the polyisocyanate compounds. A small amount of the compound can also be used. These polyhydroxy compounds can be used alone or in combination of two or more.

(A-3) Hydroxy compound containing a carboxyl group Examples of the hydroxy compound (a-3) containing a carboxyl group include carboxyl group-containing monoalcohols such as glycolic acid and hydroxypivalic acid, dimethylolpropionic acid, and dimethylolbutane. Examples thereof include carboxyl group-containing diols such as acid, N, N-bishydroxyethylglycine, and N, N-bishydroxyethylalanine.
Since it is easy to freely control the molecular weight of the resulting urethane, the crosslinking density of the cured product, among them, dimethylolpropionic acid, dimethylolbutanoic acid, N, N-bishydroxyethylglycine, N, N-bishydroxyethyl It is preferable to mainly use a carboxyl group-containing diol such as alanine, and it is particularly preferable to mainly use dimethylolpropionic acid or dimethylolbutanoic acid from the viewpoint of solubility in a solvent. These hydroxy compounds containing a carboxyl group can be used alone or in combination of two or more.

(A-4) Monohydroxy compound The carboxyl group-containing urethane resin (a) is composed of the polyisocyanate compound (a-1), the polyhydroxy compound (a-2), and the hydroxy compound (a-3) containing a carboxyl group. Synthesis is possible with only three components, but for the purpose of imparting radical polymerizability and cationic polymerizability and eliminating the influence of the terminal isocyanate residue, the monohydroxy compound (a-4) is added and reacted. Can do.

  Examples of such monohydroxy compound (a-4) include fats such as methanol, ethanol, 1-propanol, isopropanol, n-butanol, isobutanol, and t-butanol as alcohols having no reactive groups other than hydroxyl groups. 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone or alkylene oxide addition of each of the above (meth) acrylates as a group monoalcohol, having a radically polymerizable double bond Glycerin di (meth) acrylate, trimethylol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tri (meth) ) Acrylate, allyl alcohol, allyloxy ethanol and the like. These monohydroxy compounds can be used alone or in combination of two or more.

  The carboxyl group-containing urethane resin (a) of the present invention is prepared by using a suitable solvent in the presence or absence of a known urethanization catalyst such as dibutyltin dilaurate, polyisocyanate compound (a-1), polyhydroxy It is obtained by reacting the compound (a-2), the dihydroxy compound (a-3) containing a carboxyl group, and, if necessary, the monohydroxy compound (a-4).

Although there is no restriction | limiting in particular in the reaction mode, the typical example when implementing industrially is shown below.
The organic solvent used for the reaction is not particularly limited as long as it has a low reactivity with isocyanate, such as tetrahydrofuran, toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, propylene glycol methyl ether acetate, propylene glycol. Ethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl acetate, n-butyl acetate, isoamyl acetate, ethyl lactate, Acetone, methyl ethyl ketone, cyclohexanone, N, N-dimethyl Le formamide, N, N- dimethylacetamide, N- methylpyrrolidone, .gamma.-butyrolactone, dimethyl sulfoxide, chloroform and methylene chloride. Among these, from the viewpoints of solubility of the carboxyl group-containing urethane to be formed, coatability during film formation, quick drying, etc., diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl Particularly preferred are solvents such as ether acetate, diethylene glycol ethyl ether acetate, and γ-butyrolactone.

  As a density | concentration of a reaction liquid, it is preferable that the carboxyl group-containing urethane resin density | concentration is 10-90 mass%, and it is more preferable that it is 40-80 mass%.

  Although there is no restriction | limiting in particular about the order which prepares a raw material, Generally, after preparing the polyhydroxy compound (a-2) and the dihydroxy compound (a-3) which has a carboxyl group first, and making it melt | dissolve in a solvent, it is 20-20. The polyisocyanate compound (a-1) is added dropwise at 150 ° C., more preferably 40 to 120 ° C., and then reacted at 40 to 160 ° C., more preferably 40 to 130 ° C.

  When the reaction of the polyhydroxy compound (a-2) and the dihydroxy compound (a-3) having a carboxyl group with the polyisocyanate compound (a-1) is almost completed, the monohydroxy compound (a-4) is converted to 20 to 150. C., more preferably 40 to 120.degree. C., followed by reaction with isocyanate remaining at both ends at 20 to 150.degree. C., more preferably 40 to 120.degree. C., to complete the reaction.

(B) Resin obtained by adding monocarboxylic acid to epoxy resin and then reacting with acid anhydride In the present invention, (B) epoxy resin and (b-2) monocarboxylic acid are used as (A) polycarboxylic acid resin. After reacting
(B-3) A polycarboxylic acid resin synthesized by reacting an acid anhydride can be used.

(B-1) Epoxy resin Examples of the epoxy resin (b-1) used herein include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, Novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, N-glycidyl epoxy resin, bisphenol A novolac epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenolic epoxy resin, silicone modified epoxy resin, ε-caprolactone modified epoxy resin, bisphenol S type epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, bixylenol type epoxy resin, biphenyl type epoxy resin, grease Jill methacrylate copolymers, epoxy compounds having two or more epoxy groups in one molecule such as alicyclic epoxy resins.

Among these epoxy resins, N-glycidyl type epoxy resin, silicone modified epoxy resin, ε-caprolactone modified epoxy resin, heterocyclic epoxy resin, glycidyl methacrylate copolymer, fat from the viewpoint of light stability of the resulting resin A compound containing no carbon-carbon double bond such as a cyclic epoxy resin or a compound containing no aromatic ring is particularly preferred.
These epoxy resins can be used alone or in combination of two or more.

(B-2) Monocarboxylic acid Examples of the monocarboxylic acid (b-2) to be reacted with the epoxy resin (b-1) include acetic acid, propionic acid, butanoic acid, isobutanoic acid, valeric acid, isovaleric acid, and pivalin. Acid, t-butylacetic acid, 2,2-dimethylbutanoic acid, 2-ethylbutanoic acid, n-hexanoic acid, 2-methylvaleric acid, 3-methylvaleric acid, 4-methylvaleric acid, n-heptanoic acid, 2- Saturated aliphatics such as ethylhexanoic acid, n-octanoic acid, 2-propylvaleric acid, nonanoic acid, 3,5,5-trimethylhexanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid Unsaturated fatty acids such as carboxylic acid, acrylic acid, methacrylic acid, crotonic acid, 3-butenoic acid, 3-methylcrotonic acid, tiglic acid, oleic acid, sorbic acid, cinnamic acid, Fragrances such as saturated cycloaliphatic carboxylic acids such as chlorohexanecarboxylic acid, benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, salicylic acid, o-anisic acid, m-anisic acid, p-anisic acid Hydroxycarboxylic acids such as aromatic carboxylic acids, lactic acid, glycolic acid and hydroxypivalic acid, half esters of saturated aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, corkic acid, sebacic acid and dodecanedioic acid, 1,4 A half ester of a saturated alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid, a half ester of an unsaturated alicyclic dicarboxylic acid such as tetrahydrophthalic acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, Chlorendic acid, fumaric acid, maleic acid, itaconic acid, citracone Half esters of unsaturated aliphatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalene dicarboxylic acid, half esters of aromatic dicarboxylic acids such as 2,6-naphthalene dicarboxylic acid.

Among these monocarboxylic acids, acetic acid, propionic acid, butanoic acid, isobutanoic acid, valeric acid, isovaleric acid, pivalic acid, t-butylacetic acid, 2,2-dimethylbutanoic acid, 2-ethylbutanoic acid, n-hexane Acid, 2-methylvaleric acid, 3-methylvaleric acid, 4-methylvaleric acid, n-heptanoic acid, 2-ethylhexanoic acid, n-octanoic acid, 2-propylvaleric acid, nonanoic acid, 3,5,5 -Saturated aliphatic carboxylic acids such as trimethylhexanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, saturated alicyclic carboxylic acids such as cyclohexanecarboxylic acid, lactic acid, glycolic acid, hydroxypivalic acid Hydroxycarboxylic acids such as succinic acid, glutaric acid, adipic acid, corkic acid, sebacic acid and dodecanedioic acid Half esters of phosphate, 1,4-cyclohexane half esters of saturated alicyclic dicarboxylic acids such as dicarboxylic acid, compound or carbon no aromatic ring - compound not containing carbon double bonds are particularly preferred.
These monocarboxylic acids can be used alone or in combination of two or more.

(B-3) Acid anhydride Examples of the acid anhydride (b-3) to be reacted with the reaction product of the epoxy resin (b-1) and the monocarboxylic acid (b-2) include hexahydrophthalic anhydride, methylhexa Saturated alicyclic acid anhydrides such as hydrophthalic anhydride, succinic anhydride, polyazeline acid anhydride, polydodecanedioic anhydride, glutaric anhydride, diethyl glutaric anhydride and other saturated aliphatic acid anhydrides, maleic anhydride , Itaconic anhydride, dodecenyl anhydride, chlorendic anhydride, 7,12-dimethyl-7,11-octadecadien-1,18-dicarboxylic acid partial anhydride, etc., unsaturated aliphatic acid anhydride, tetrahydrophthalic anhydride Unsaturated alicyclic acid anhydrides such as methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, Aromatic acid anhydrides such as water phthalic acid, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate) Etc.

Among these acid anhydrides, hexahydrophthalic anhydride, saturated alicyclic acid anhydrides such as methylhexahydrophthalic anhydride, succinic anhydride, polyazelaic anhydride, polydodecanedioic anhydride from the viewpoint of stability to light Acid anhydrides that do not contain an aromatic ring or a carbon-carbon double bond, such as a saturated aliphatic acid anhydride such as an acid product, glutaric anhydride, and diethyl glutaric anhydride.
These acid anhydrides can be used alone or in combination of two or more.

（式中、Ｒ³は置換されていてもよいアルキレン基、シクロアルキレン基もしくはアリーレン基を表し、Ｒ⁴は水素原子またはメチル基を表し、ｐ及びｑはそれぞれ１〜３の整数を表し、ｐ＋ｑ≦４である。）
で示される化合物と、後述するモノマーとの共重合体を用いることができる。 (C) Copolymer of (meth) acrylic acid or a compound represented by the following formula (2) In the present invention, (meth) acrylic acid or the following general formula (2) is used as the polycarboxylic acid resin (A).

(Wherein R ³ represents an optionally substituted alkylene group, cycloalkylene group or arylene group, R ⁴ represents a hydrogen atom or a methyl group, p and q each represents an integer of 1 to 3, p + q ≦ 4.)
The copolymer of the compound shown by and the monomer mentioned later can be used.

  In this application, (meth) acrylic acid refers to acrylic acid and methacrylic acid. These can be synthesized by known methods, and commercially available products can also be used.

  Specific examples of the compound represented by the general formula (2) include succinic acid, itaconic acid, dodecenyl succinic acid, phthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, endomethylene. Tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, ethylene glycol bistrimellitate, glutaric acid, mono (2-hydroxyethyl (meth) acrylate of diethyl glutaric acid ), Trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, ethylene glycol bistrimellitate, bis (2-hydroxyethyl (meth) acrylate) of glycerol tristrimerate, Mellitic acid, benzophenonetetracarboxylic acid, and ethylene glycol bistrimellitate tris (2-hydroxyethyl (meth) acrylate) and the like.

  Examples of monomers copolymerized with (meth) acrylic acid and the compound represented by the general formula (2) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) Butyl acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, Examples include tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, styrene, vinyltoluene and the like.

(D) Polyimide, polyamideimide, polyamide, polyurethane and polyester having carboxylic acid or acid anhydride at both ends In the present invention, (d-1) polyimide having carboxylic acid at both ends as polycarboxylic acid resin (A),
(D-2) polyimide having an acid anhydride at both ends,
(D-3) polyamideimide having carboxylic acid at both ends,
(D-4) polyamideimide having acid anhydrides at both ends,
(D-5) polyamide having carboxylic acid at both ends,
(D-6) polyamide having acid anhydrides at both ends,
(D-7) polyurethane having carboxylic acid at both ends,
(D-8) polyurethane having acid anhydrides at both ends;
(D-9) Polyester having a carboxylic acid at both ends or (d-10) Polyester having an acid anhydride at both ends can be used.

(D-1) Polyimide having carboxylic acid at both ends Polyimide (d-1) having carboxylic acid at both ends can be synthesized, for example, by the methods shown in the following synthesis methods (i) and (ii).

  As synthesis method (i), (1) tetracarboxylic dianhydride and (2) diisocyanate were reacted so that the molar ratio was (1) / (2)> 1, and then (3) monohydroxy The method of making a compound or a mono secondary amine compound react is mentioned.

  Examples of tetracarboxylic dianhydrides (1) that can be used here include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride. , Aromatic tetracarboxylic anhydrides such as thiophene-2,3,4,5-tetracarboxylic dianhydride, diphenylsulfone tetracarboxylic dianhydride, and aliphatic tetracarboxylic such as butanetetracarboxylic dianhydride Acid anhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, 1,2,3,4-cyclobutane Saturated alicyclic tetracarboxylic acids such as tetracarboxylic dianhydride and bis {exo-bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride} sulfone Water, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, bicyclo- (2,2,2)- Unsaturated cycloaliphatic tetracarboxylic anhydrides such as oct (7) -ene-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride And saturated heterocyclic tetracarboxylic acid anhydrides such as tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride.

  Of these tetracarboxylic acid anhydrides, aliphatic tetracarboxylic acid anhydrides such as butanetetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic acid Anhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis {exo-bicyclo [2.2.1] heptane -2,3-dicarboxylic acid anhydride} saturated alicyclic tetracarboxylic acid anhydride such as sulfone, and saturated heterocyclic tetracarboxylic acid anhydride such as tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride. A tetracarboxylic anhydride that does not contain an aromatic ring or a carbon-carbon double bond is particularly preferred.

Examples of the diisocyanate (2) include those exemplified as those that can be used for the synthesis of the carboxyl group-containing urethane resin (a). Coloring of the resulting polyimide, coloring of the cured product, and stability to light 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1 , 9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1, - dimethylene diisocyanate, cycloaliphatic diisocyanates such as cyclohexane-1,4-diisocyanate, ether-based diisocyanates such as 2,2'-diethyl ether diisocyanate are particularly preferred.
These diisocyanates can be used alone or in combination of two or more.

  Examples of the monohydroxy compound (3) include aliphatic monoalcohols such as methanol, ethanol, 1-propanol, isopropanol, n-butanol, isobutanol, and t-butanol as radicals having no reactive groups other than hydroxyl groups, radicals As those having a polymerizable double bond, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone or alkylene oxide adduct of each (meth) acrylate, glycerin di ( (Meth) acrylate, trimethylol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tri (meth) acrylate Allyl alcohol, allyloxy ethanol and the like.

  Of these monohydroxy compounds, aliphatic monoalcohols such as methanol, ethanol, 1-propanol, isopropanol, n-butanol, isobutanol, and t-butanol are particularly preferred from the viewpoint of coloring of the cured product and light stability.

Examples of the mono secondary amine compound (3) include saturated aliphatic secondary amines such as diethylamine and diisopropylamine, saturated alicyclic secondary amines such as cyclohexylamine, saturated cyclic amines such as piperidine, and imidazole. And aromatic secondary amines such as unsaturated cyclic amines and N-methylaniline.
Among these mono-secondary amine compounds, saturated aliphatic secondary amines such as diethylamine and diisopropylamine, saturated alicyclic secondary amines such as cyclohexylamine, piperidine, etc. The saturated cyclic amine is particularly preferred.
When the obtained polyimide is combined with an epoxy resin or an oxetane resin to form a thermosetting composition, it is preferable to use a monohydroxy compound rather than a monosecondary amine compound from the viewpoint of storage stability.

  As synthesis method (ii), (1) tetracarboxylic dianhydride and (2) diisocyanate are reacted so that the molar ratio is (1) / (2) <1, and then (3) Examples thereof include a method of adding a monohydroxycarboxylic acid or an amino acid.

As tetracarboxylic dianhydride (1) and diisocyanate (2) that can be used here, those exemplified in the synthesis method (i) can be used, respectively, from the viewpoint of coloring of the cured product and stability to light. Particularly preferred are those which do not contain an aromatic ring or a carbon-carbon double bond.
Examples of the monohydroxycarboxylic acid (3) include glycolic acid and hydroxypivalic acid, and examples of amino acids include glycine and alanine.
Among these, when the obtained polyimide is used in combination with an epoxy resin or an oxetane resin, it is preferable to use a monohydroxycarboxylic acid rather than an amino acid from the viewpoint of storage stability.

(D-2) Polyimide having acid anhydride groups at both ends Polyimide having acid anhydride groups at both ends is composed of (1) tetracarboxylic dianhydride and (2) diisocyanate in a molar ratio of (1) / (2) It is obtained by a synthesis method in which reaction is performed so that> 1.
Examples of tetracarboxylic dianhydride (1) and diisocyanate (2) that can be used here are exemplified in the description of the synthesis of polyimide (d-1) having carboxylic acid at both ends. It is particularly preferable to use those which do not contain an aromatic ring or a carbon-carbon double bond from the viewpoint of coloring of the resulting polyimide, coloring of the cured product, and stability to light.

  Moreover, the polyimide (d-1) which has carboxylic acid at both ends, and the polyimide (d-2) which has an acid anhydride at both ends use a diamine instead of diisocyanate in the synthesis method in addition to the synthesis method, respectively. It is also possible to synthesize via a polyamic acid.

  Examples of diamines that can be used here include ethylene diamine, tetramethylene diamine, hexamethylene diamine, aliphatic diamines such as N, N′-dimethyl and diethyl diamines, m-xylylenediamine, and p-xylylenediamine. Amines, and xylylenediamines such as N, N′-dimethyl, diethyl, diphenyl, and dibenzyl, piperazine, 2,5-dimethylpiperazine, 1,3-di (4-piperidyl) propane, etc. Piperazines, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylmethane, 3,4'-diaminodiphenyl meta 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenyldifluoromethane, 4,4′-diaminodiphenyldifluoromethane, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4, 4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfide, 2,2-bis (3-aminophenyl) propane, 2,2-bis (3,4'-diaminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis (3,4'-diaminophenyl) hexafluoropropane, 2,2-bis (4-amino) Phenyl) hexafluoropropane, 1,3-bis (3-aminophenyl) benzene, 1,4-bis (4-aminophenyl) Nyl) benzene, 3,3 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 3,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 4,4 ′ -[1,4-phenylenebis (1-methylethylidene)] bisaniline, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Propane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (3- Aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl Sulfurone, bis [4- (4-aminophenoxy) phenyl] sulfone, 9,9-bis (4-aminophenyl) fluorene and its N, N′-dimethyl, diethyl, diphenyl, dibenzyl and other aromatics Examples include diamines.

  Among these diamines, ethylene diamine, tetramethylene diamine, hexamethylene diamine and N, N′-dimethyl, diethyl, and diphenyl of these diamines from the viewpoint of coloring of the resulting polyimide, coloring of the cured product, and stability to light. And xylylenediamine such as dibenzyl and piperazine such as piperazine, 2,5-dimethylpiperazine, and 1,3-di (4-piperidyl) propane.

(D-3) Polyamideimide having carboxylic acid at both ends Polyamideimide (d-3) having carboxylic acid at both ends can be synthesized, for example, by the methods shown in the following synthesis methods (i) and (ii). it can.

  As the synthesis method (i), the molar ratio of (1) tetracarboxylic dianhydride, (2) trimellitic anhydride, and (3) diisocyanate is ((1) + (2)) / (3) <1 And a method of adding (1) tetracarboxylic dianhydride, (4) monohydroxy compound or mono secondary amino compound in this order.

  Examples of (1) tetracarboxylic dianhydride, (3) diisocyanate, (4) monohydroxy compound or mono secondary amino compound that can be used here are polyimides having carboxylic acids at both ends (d- What was illustrated in description about the synthesis | combination of 1) can be used, and the thing which does not contain an aromatic ring or a carbon-carbon double bond from points, such as coloring of the obtained polyamidoimide, coloring of hardened | cured material, stability to light, etc. It is particularly preferable to use it.

  As synthesis method (ii), (1) tetracarboxylic dianhydride, (2) trimellitic anhydride, and (3) diisocyanate have a molar ratio of ((1) + (2)) / (3) <4> After making it react so that it may become (1), the method of adding monohydroxycarboxylic acid or an amino acid, or dicarboxylic acid is mentioned.

  Examples of tetracarboxylic dianhydrides (1), diisocyanates (3), monohydroxy carboxylic acids or amino acids (4) that can be used here are the synthesis of polyimides (d-1) having carboxylic acids at both ends. What is illustrated in the description of can be used, and it is particularly preferable to use those which do not contain an aromatic ring or a carbon-carbon double bond from the viewpoint of coloring of the obtained polyimide, coloring of a cured product, and stability to light.

  Examples of the dicarboxylic acid compound (4) that can be used here include saturated aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, corkic acid, sebacic acid, and dodecanedioic acid, and 1,4-cyclohexanedicarboxylic acid. Saturated alicyclic dicarboxylic acid such as acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, unsaturated alicyclic dicarboxylic acid such as methylendomethylenetetrahydrophthalic acid, chlorendic acid, fumaric acid, maleic acid, Examples thereof include unsaturated aliphatic dicarboxylic acids such as itaconic acid and citraconic acid, and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid.

  Among these dicarboxylic acid compounds, saturated aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, corkic acid, sebacic acid and dodecanedioic acid, 1,4- Saturated alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid are particularly preferred.

(D-4) Polyamideimide having acid anhydrides at both ends Polyamideimide having acid anhydrides at both ends includes (1) tetracarboxylic dianhydride, (2) trimellitic anhydride, and (3) diisocyanate. Can be obtained by adding (1) tetracarboxylic dianhydride after the reaction so that the molar ratio is ((1) + (2)) / (3) <1.

  As tetracarboxylic dianhydride (1) and diisocyanate (3) that can be used here, those exemplified in the description of the synthesis of polyimide (d-1) having carboxylic acid at both ends can be used. From the viewpoint of coloring of the polyimide obtained, coloring of the cured product, and stability to light, it is particularly preferable to use a material that does not contain an aromatic ring or a carbon-carbon double bond.

(D-5) Polyamide having carboxylic acid at both ends Polyamide having carboxylic acid at both ends is, for example, (1) dicarboxylic acid and (2) diamine molar ratio (1) / (2)> 1 It is obtained by making it react.

  Examples of the dicarboxylic acid (1) that can be used here include those exemplified in the description of the synthesis of the polyamideimide (d-3) having carboxylic acid at both ends, and diamine ( As an example of 2), what was illustrated in description about the synthesis | combination of the polyimide (The other synthesis methods of (d-1) and (d-2)) which have a carboxylic acid or an acid anhydride at both the said each ends, respectively. From the viewpoints of coloring of the resulting polyamide, coloring of the cured product, and stability to light, it is particularly preferable to use one that does not contain an aromatic ring or a carbon-carbon double bond.

(D-6) Polyamide having acid anhydrides at both ends Polyamide having acid anhydrides at both ends is, for example, (1) dicarboxylic acid and (2) diamine in a molar ratio of (1) / (2) < It is obtained by reacting with (3) tetracarboxylic dianhydride after reacting to be 1.

  Examples of the dicarboxylic acid (1) that can be used here include those exemplified for the polyamideimide (d-3) having carboxylic acid at both ends, and examples of the diamine (2). , And those exemplified in the description of the synthesis of the polyimide having carboxylic acid or acid anhydride at both ends (other synthesis methods of (d-1) and (d-2)), respectively. Examples of tetracarboxylic dianhydride (3) include those exemplified for polyimide (d-1) having carboxylic acid at both ends. From the viewpoint of coloring of the obtained polyamide, coloring of the cured product, and stability to light, it is particularly preferable to use one that does not contain an aromatic ring or a carbon-carbon double bond.

(D-7) Polyurethane having carboxylic acid at both ends Polyurethane (d-7) having carboxylic acid at both ends can be synthesized, for example, by the methods shown in the following synthesis methods (i) and (ii).

  As the synthesis method (i), (1) a polyisocyanate compound and (2) a polyhydroxy compound are reacted so that the molar ratio is (1) / (2)> 1, then (3) monohydroxy The method of adding carboxylic acid or an amino acid is mentioned.

  Examples of the polyisocyanate compound (1) and polyhydroxy compound (2) that can be used here are the polyisocyanate compound (a-1) and polyhydroxy compound in the description of the carboxyl group-containing urethane resin (a). What was illustrated as a compound (a-2) can be used, and in order to prevent the gelatinization during reaction, it is preferable to use a diisocyanate compound and a diol compound among these.

  Examples of the monohydroxycarboxylic acid and amino acid (3) that can be used here include those exemplified in the description of the synthesis of the polyimide (d-1) having carboxylic acid at both ends.

  As synthesis method (ii), (1) diisocyanate and (2) diol are reacted so that the molar ratio is (1) / (2) <1, and then (3) acid anhydride is added. The method of letting it be mentioned.

  Examples of the diisocyanate (1) that can be used here include those exemplified in the description of the method for synthesizing a polyimide having a carboxylic acid at both ends (d-1). Examples of the diol (2) In the description of the carboxyl group-containing urethane resin (a), those exemplified as the polyhydroxy compound (a-2) can be used. Examples of the acid anhydride include those exemplified as the acid anhydride (b-3) in the description of the synthesis of the resin (b) reacted with the acid anhydride after adding a monocarboxylic acid to the epoxy resin. Is mentioned.

(D-8) Polyurethane having acid anhydrides at both ends Polyurethane (d-8) having acid anhydrides at both ends can be synthesized, for example, by the method shown in the following synthesis methods (i) and (ii). it can.

As synthesis method (i), (1) polyisocyanate and (2) polyhydroxy compound are reacted so that the molar ratio of isocyanate group / hydroxyl group is> 1, and (3) tetracarboxylic dianhydride. The method of making this react is mentioned.

  Examples of the polyisocyanate (1) and the polyhydroxy compound (2) that can be used here are the polyisocyanate compound (a-1) and the polyhydroxy compound in the description of the carboxyl group-containing urethane resin (a), respectively. What was illustrated as (a-2) can be used. Among these, for the purpose of preventing gelation during the reaction, it is preferable to use a diisocyanate compound and a diol compound. For the purpose of coloring the cured product and stability to light, an aromatic ring and a carbon-carbon double bond are included. It is particularly preferable to use those not present.

  Moreover, as an example of tetracarboxylic dianhydride (3), what was illustrated in description of the synthesis | combination (d-1) of the polyimide which has carboxylic acid in the said both terminal can be used, and coloring and light of hardened | cured material can be used. It is particularly preferable to use a material that does not contain an aromatic ring or a carbon-carbon double bond from the viewpoint of stability to the above.

  As synthesis method (ii), (1) polyisocyanate compound and (2) polyhydroxy compound were reacted so that the molar ratio of isocyanate group / hydroxyl group was <1, and then (3) tetracarboxylic dianhydride The method of adding a thing is mentioned.

  Examples of the polyisocyanate compound (1) and polyhydroxy compound (2) that can be used here are the polyisocyanate compound (a-1) and polyhydroxy compound in the description of the carboxyl group-containing urethane resin (a), respectively. What was illustrated as a compound (a-2) can be used, and it is preferable to use a diisocyanate compound and a diol compound especially in order to prevent gelatinization during reaction.

  Moreover, as an example of tetracarboxylic dianhydride (3), what was illustrated in the description about the synthesis | combination (d-1) of the polyimide which has carboxylic acid in the both said terminal can be used, coloring of hardened | cured material or In view of stability to light, it is particularly preferable to use a material that does not contain an aromatic ring or a carbon-carbon double bond.

(D-9) Polyester having carboxylic acid at both ends Polyester (d-9) having carboxylic acid at both ends can be synthesized, for example, by the methods shown in the following synthesis methods (i) to (iii).

  Examples of the synthesis method (i) include a method in which (1) a polycarboxylic acid and (2) a polyhydroxy compound are reacted so that the molar ratio of carboxyl group / hydroxyl group is> 1.

  Examples of the polycarboxylic acid (1) that can be used here include those exemplified in the description of the synthesis (d-3) of the polyamideimide having carboxylic acids at both ends. As an example of the compound (2), those exemplified as the polyhydroxy compound (a-2) in the description of the carboxyl group-containing urethane resin (a) can be used. Among these, it is preferable to use a dicarboxylic acid and a diol compound in order to prevent gelation during the reaction.

  As the synthesis method (ii), the ester exchange reaction of (1) dicarboxylic acid diester and (2) polyhydroxy compound was carried out so that the molar ratio of ester bond / hydroxyl group was> 1, and then (3) mono The method of performing transesterification with hydroxycarboxylic acid is mentioned.

  Examples of diester (1) of dicarboxylic acid that can be used here include dimethyl ester and diethyl ester of dicarboxylic acid exemplified in the description of synthesis (d-3) of polyamideimide having carboxylic acid at both ends. , Diallyl ester and the like can be used.

Moreover, as an example of a polyhydroxy compound (2), what was illustrated as a polyhydroxy compound (a-2) in description of the said carboxyl group-containing urethane resin (a) can be used, Especially, it is gelatinized during reaction. In order to prevent this, it is preferable to use a diol compound.
As an example of monohydroxy carboxylic acid (3), what was illustrated in the description about the synthesis | combination of the polyimide (d-1) which has carboxylic acid in the said both terminal can be used.

  As the synthesis method (iii), the transesterification reaction of (1) dicarboxylic acid diester and (2) polyhydroxy compound was carried out so that the molar ratio was ester bond / hydroxyl group <1, and then (3) acid anhydride The method of adding is mentioned.

Examples of the dicarboxylic acid diester (1) that can be used here include dimethyl ester, diethyl ester of dicarboxylic acid exemplified in the description of the synthesis of polyamideimide (d-3) having carboxylic acid at both ends. Diallyl esters and the like can be used.
Moreover, as an example of a polyhydroxy compound (2), what was illustrated as a polyhydroxy compound (a-2) in description of the said carboxyl group-containing urethane resin (a) can be used. In order to prevent this, it is preferable to use a diol compound.
Examples of the acid anhydride (3) include those exemplified in the description of the synthesis of the resin (b-3) obtained by adding a monocarboxylic acid to the epoxy resin and then reacting with the acid anhydride. .

(D-10) Polyester having an acid anhydride at both ends Polyester (d-10) having an acid anhydride at both ends is, for example, (1) a dicarboxylic acid or dicarboxylic acid diester, and (2) a polyhydroxy compound. The reaction is carried out so that the molar ratio of carboxyl group / hydroxyl group is <1, and then (3) tetracarboxylic dianhydride is added.

  Examples of the dicarboxylic acid or dicarboxylic acid diester (1) that can be used here include those exemplified in the description of the synthesis of the polyamideimide (d-3) having carboxylic acid at both ends. Moreover, as an example of a polyhydroxy compound (2), what was illustrated as a polyhydroxy compound (a-2) in description of the said carboxyl group-containing urethane resin (a) can be used.

  Moreover, as an example of tetracarboxylic dianhydride (3), what was illustrated in the description about the synthesis | combination of the polyimide (d-1) which has carboxylic acid in the said both terminal can be used.

Among the polycarboxylic acid resins (a) to (d) described above, it is particularly preferable to use the carboxyl group-containing urethane resin (a) from the viewpoints of flexibility of the cured film, crosslinking density, transparency, and the like.
The number average molecular weight of the polycarboxylic acid resin is preferably 500 to 100,000, and more preferably 2000 to 30,000.
When the number average molecular weight is less than 500, the flexibility and strength of the cured film may be impaired. When the number average molecular weight exceeds 100,000, the viscosity becomes too high, and the production of the cured film becomes difficult.
Here, the number average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography.

[Epoxy resin and / or oxetane resin (B)]
(B-1) Epoxy Resin Examples of the epoxy resin that can be used as the component (B) in the present invention include bisphenol A such as Epicoat 828, 1002, and 1004 (all trade names: manufactured by Japan Epoxy Resin Co., Ltd.). Type epoxy resin, Epicoat 806, 807, 4005P (all trade names: manufactured by Japan Epoxy Resins Co., Ltd.), YDF-170 (trade name: manufactured by Toto Kasei Co., Ltd.), etc. 154 (all trade names: manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-201 (trade name: manufactured by Nippon Kayaku Co., Ltd.), DEN-438 (trade name: manufactured by Dow Chemical Company), etc. O-Cresol such as resin, EOCN-125S, 103S, 104S (all trade names: Nippon Kayaku Co., Ltd.) Novolak type epoxy resin, biphenyl type epoxy resin such as Epicoat YX-4000, YL-6640 (all trade names: manufactured by Japan Epoxy Resin Co., Ltd.), Epicoat 1031S (trade name: manufactured by Japan Epoxy Resins Co., Ltd.), Araldite 0163 (trade name: manufactured by Ciba Specialty Chemicals Co., Ltd.), Denacol EX-611, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-421, EX-411, EX -321 (all trade names: manufactured by Nagase Kasei Co., Ltd.), etc., Epicoat 604 (trade name: manufactured by Japan Epoxy Resin Co., Ltd.), YH-434 (trade name: manufactured by Toto Kasei Co., Ltd.) ), TETRAD-X, TETRAD-C (all trade names: manufactured by Mitsubishi Gas Chemical Co., Ltd.), GAN (trade names: Heterochemicals), amine type epoxy resins such as ELM-120 (trade name: manufactured by Sumitomo Chemical Co., Ltd.), Araldite PT810 (trade name: manufactured by Ciba Specialty Chemicals Co., Ltd.), etc. Containing epoxy resin, Epicoat YX8000, YX8034, YL6753, YL7040, RXE21 (all trade names: manufactured by Japan Epoxy Resin Co., Ltd.), Santo Tote ST-3000, ST-4000D (all trade names: manufactured by Toto Kasei Co., Ltd.) , ERL4234, 4299, 4221, 4206 (all trade names: manufactured by UCC), Celoxide 2021P, Celoxide 3000, EHPE3150 (all trade names: manufactured by Daicel Chemical Industries, Ltd.) and the like. It is done. These epoxy resins can be used alone or in combination of two or more.

(B-2) Oxetane Resin Examples of oxetane resins that can be used as the component (B) in the present invention include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, di [1- And polyoxetane compounds such as ethyl (3-oxetanyl)] methyl ether, phenol novolac oxetane, terephthalate bisoxetane, and biphenylylene bisoxetane.

[Curing catalyst (C)]
The thermosetting resin composition of the present invention preferably contains a curing catalyst (curing accelerator) as the component (C).
In the present invention, examples of the curing catalyst (C) that can be used when an epoxy resin is included as the component (B) include benzyldimethylamine (BDMA), imidazole, 2-methylimidazole, 2-undecylimidazole, and 2-ethyl. -4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-phenylimidazole, 2-heptadecylimidazole 2-phenyl-4,5-dihydroxyimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-undecylimidazole, melamine, acetoguanamine, benzoguanamine, 2,4-diamino-6 -[2'-methyl] Louisimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6 -[2'-Ethyl-4'-imidazolyl- (1 ')]-ethyl-s-triazine, 1,8-diazabicyclo [5.4.0] undecene-7, 1,5-diazabicyclo [4.3. 0] Amine compounds such as nonene-5 and salts thereof, phosphine compounds such as triphenylphosphine and tris- (2,6-dimethoxyphenyl) phosphine and salts thereof, organometallic salts, quaternary phosphonium halides, dimethyl Examples include urea. These curing accelerators can be used alone or in combination of two or more.

  Examples of the curing catalyst (C) that can be used when an oxetane resin is included as the component (B) in the present invention include tetraethylammonium bromide, tetrabutylammonium bromide, tetraethylphosphonium bromide, tetrabutylphosphonium bromide, and tetraphenylphosphonium bromide. , Onium salts such as triphenylbenzylphosphonium chloride, amines such as triethylamine, tributylamine, 1,8-diazabicyclo [5.4.0] undecene-7, 1,5-diazabicyclo [4.3.0] nonene-5 , Crown ether complexes, triphenylphosphine and the like. These can be used alone or in combination of two or more.

  The blending ratio of the polycarboxylic acid resin (A), the oxetane resin (B) and the curing catalyst (C) in the thermosetting resin composition of the present invention is the carboxyl group of the polycarboxylic acid resin (A) / [epoxy resin. And / or the oxetane resin (B) epoxy group and / or oxetanyl group] in a molar ratio of 0.5 to 2, more preferably 0.6 to 1.9, and a polycarboxylic acid resin. (A) The curing catalyst (C) is blended in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass.

[Other additives]
In addition, the thermosetting resin composition of the present invention may contain additives such as inorganic or organic fillers, surfactants, mold release agents, antifoaming agents and the like as long as transparency is not impaired.

[Inorganic or organic filler]
The addition of an inorganic or organic filler is effective in that the refractive index of the film can be adjusted and the water absorption rate and hardness can be improved.
Examples of the inorganic filler that can be used in the present invention include silica, glass powder, quartz powder, zirconia, and smectite. Among these, zirconia is preferable because it has many smaller particle diameters than other fillers, and the effect of filler addition can be obtained without degrading the performance of the film.
Examples of the organic filler include epoxy resin powder, melamine resin powder, urea resin powder, guanamine resin powder, polyester resin powder, and silicone powder.

In order to maintain the transparency of the film prepared from the thermosetting resin composition of the present invention, these fillers have an average particle diameter of 1 to 100 nm or are obtained by curing the resin composition of the present invention. It is preferable that the cured product and the filler have the same refractive index. Here, the particle diameter is determined by a dynamic light scattering method, and the average particle diameter is the central value of the particle diameter distribution. When the average particle diameter exceeds 100 nm and the cured product of the resin composition of the present invention and the filler have different refractive indexes, the transparency of the film may be impaired. An average particle diameter of 1 to 10 nm is preferable from the viewpoint of balance between transparency and ease of blending.
Moreover, it is preferable that these fillers do not have absorption in visible region. This is because when the filler having absorption in the visible light region is used in the resin composition of the present invention, the obtained cured product may be colored, and in that case, it becomes unsuitable as an optical film.

[Surfactant]
Surfactants that can be used in the present invention include an anionic surfactant having a sodium naphthalene sulfonate group, a sodium benzene sulfonate group, a nonionic surfactant having a polyalkyleneoxy group, and a tetraalkylammonium group. And cationic surfactants.

[Release agent]
Examples of the release agent that can be used in the present invention include stearic acid, butyl stearate, zinc stearate, stearamide, fluorine compounds, silicon compounds and the like.

[Defoamer]
Examples of antifoaming agents that can be used in the present invention include KS-602A, KS-66, KS-603, KS-608, FA600 (all trade names: Shin-Etsu Chemical Co., Ltd.) )), BYK-A530 (trade name: manufactured by Big Chemie Japan Co., Ltd.) and the like as non-silicone antifoaming agents, BYK-051, BYK-052, BYK-053, BYK-055, BYK-057, BYK-354, BYK-355 (both trade names: manufactured by Big Chemie Japan Co., Ltd.) and the like can be mentioned.

[Preparation of Thermosetting Resin Composition of the Present Invention]
Although there is no particular limitation on the mixing method and mixing order when preparing the thermosetting resin composition of the present invention, for example, using equipment such as a three-one motor, a high shear mixer, a planetary mixer, a bead mill, a three roll mill, (A) Polycarboxylic acid resin, (B) epoxy resin and / or oxetane resin, and (C) curing catalyst and other additives as necessary can be charged in a lump or sequentially added and mixed. In order to prevent a curing reaction during mixing, the temperature at the time of mixing is 60 ° C. or lower, more preferably 40 ° C. or lower.

[Hardened product of thermosetting resin composition of the present invention]
The film produced by curing the thermosetting resin composition of the present invention can be used as an optical film or the like. The optical film has a thickness of 200 μm or less and can be appropriately set depending on the application. Moreover, the thermosetting resin composition of this invention can be used also as a laminated | multilayer film obtained by apply | coating on a base film and hardening this. The film production methods such as the coating method and the curing method may be generally performed methods. Moreover, these films are suitable as base materials, such as a protective film of a polarizing plate, retardation film, an antireflection film, and members, such as a liquid crystal display. The thickness of the film is particularly preferably 20 to 100 μm.

  The present invention will be described below with reference to synthesis examples and examples, but the present invention is not limited to these examples.

により求めた。 Synthesis Example 1: Synthesis of carboxyl group-containing urethane resin (1) In a reaction vessel equipped with a stirrer and a thermometer, norbornene diisocyanate (NBDI) (trade name: Cosmonate, manufactured by Mitsui Takeda Chemical Co., Ltd.) 98 g, polyester diol ( Kuraray Co., Ltd., trade name: Kuraray polyol P-530) 122 g, dimethylol butanoic acid (manufactured by Nippon Kasei Co., Ltd., trade name: DMBA) 34 g, propylene glycol methyl ether acetate (manufactured by Daicel Chemical Co., Ltd.) as a solvent ) 251 g was charged and reacted at 100 ° C. for 5 hours, and then 3.6 g of isobutanol (manufactured by Junsei Chemical Co., Ltd.) was added and reacted for another 2 hours. The compound thus synthesized is referred to as carboxyl group-containing urethane resin (1). The number average molecular weight of this carboxyl group-containing urethane resin (1) was 6073, and the solid content acid value, that is, the acid value of the resin was 50. In addition, the value of acid value is according to the method of JIS K 0070

Determined by

Synthesis Example 2: Synthesis of carboxyl group-containing urethane resin (2) 56 g of hydrogenated diphenylmethane diisocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Desmodur W) in a reaction vessel equipped with a stirrer and a thermometer, polycarbonate diol (Kuraray Co., Ltd., trade name: Kuraray polyol C-1015N) 74 g, dimethylol butanoic acid (manufactured by Nippon Kasei Co., Ltd., trade name: DMBA) 20 g, diethylene glycol dimethyl ether (manufactured by Junsei Chemical Co., Ltd.) 98 g as a solvent Then, 0.28 g of dibutyltin (IV) dilaurate was charged as a catalyst and reacted at 90 ° C. for 4 hours, followed by addition of 1.6 g of isobutanol (manufactured by Junsei Chemical Co., Ltd.) and further at 100 ° C. for 2.5 hours. Reacted. The compound thus synthesized is referred to as carboxyl group-containing urethane resin (2). The number average molecular weight of this carboxyl group-containing urethane resin (2) was 5479, and the solid content acid value, that is, the acid value of the resin was 50. The value of the acid value was determined by the same method as that described in Synthesis Example 1.

Examples 1, 2 and 3: Preparation of thermosetting resin composition Carboxyl group-containing urethane resins (1) and (2) obtained in Synthesis Examples 1 and 2, epoxy resin (manufactured by Daicel Chemical Industries, Ltd., product) Name: Celoxide 2021P, epoxy equivalent: 130), curing catalyst, and filler are put in a container with the composition shown in Table 1 below, and after stirring and mixing with a high shear mixer at 2000 rpm for 10 minutes, a hybrid mixer (Keyence Corporation) Manufactured, apparatus name: HM-300) for 10 minutes. In the formulations of Example 1 and Example 2 shown in Table 1, the molar ratio of the carboxyl group of the polycarboxylic acid resin (A) / the epoxy group of the epoxy resin (B) is approximately 1.

Example 4: Production of film The thermosetting resin composition obtained in Examples 1, 2 and 3 was applied to a PET film (25 μm) with a bar coater, and 8
Heated at 0 ° C. for 15 minutes and at 120 ° C. for 3 hours.

Example 5 and Comparative Example 1: Evaluation of Film The film obtained in Example 4 and a commercially available cellulose triacetate (TAC) film as a comparative example were evaluated by the following methods. The results are shown in Table 2.
-180 degree bend | fold: The obtained film was bend | folded 180 degree by hand fold, and the thing without whitening and a crack was set as (circle).
Pencil hardness: The resin film on the PET film was measured according to JIS K 5400.
-Transparency: The light transmittance at a wavelength of 380 to 750 nm of the obtained film was measured. A film having 90% or more in the entire region was marked with ◯, and a film having a region of 90% or less was marked with ×. In addition, the thickness of the film used for this measurement was prescribed | regulated in the range of about 80 micrometers, ie, 80 +/- 10micrometer. The actual thickness is as shown in Table 2.
-Water absorption rate: Measured according to method B described in JIS K 7209 (measured water absorption after immersion in boiling water).

以上の通り、本発明によれば、耐久性、特に高温高湿下での耐久性に優れた光学フィルムを得ることができる。特に実施例１の硬化物は鉛筆硬度も高く優れていた。

As described above, according to the present invention, it is possible to obtain an optical film excellent in durability, particularly durability under high temperature and high humidity. In particular, the cured product of Example 1 was excellent in pencil hardness.

Claims (11)

(A) Polycarboxylic acid resin, and (B) Epoxy resin and / or oxetane resin as essential components, cured into a film having a thickness of about 80 μm, has a light transmittance of 90 in the entire range of wavelengths of 380 to 750 nm. % Thermosetting resin composition.   The thermosetting resin composition according to claim 1, wherein (A) the polycarboxylic acid resin is a carboxyl group-containing urethane resin. The carboxyl group-containing urethane resin is (a) a polyisocyanate compound,
(B) a polyhydroxy compound,
The thermosetting resin composition according to claim 2, which is (c) a dihydroxy compound having a carboxyl group and, if necessary, (d) a compound using a monohydroxy compound as a raw material.   (C) The thermosetting resin composition in any one of Claims 1-3 containing a curing catalyst.   The molar ratio of carboxyl group of the polycarboxylic acid resin (A) / [epoxy group and / or oxetanyl group of the epoxy resin and / or oxetane resin (B)] is 0.5 to 2, and the polycarboxylic acid resin ( A) The thermosetting resin composition in any one of Claims 1-4 containing 0.01-10 mass parts of curing catalysts (C) with respect to 100 mass parts.   The thermosetting resin composition according to any one of claims 1 to 5, comprising an inorganic or organic filler having an average particle diameter determined by a dynamic light scattering method of 1 to 100 nm.   The thermosetting resin composition in any one of Claims 1-6 containing the inorganic or organic filler which has the same refractive index as the hardened | cured material formed by hardening the said thermosetting resin composition.   The optical film obtained by hardening | curing the thermosetting resin composition in any one of Claims 1-7.   The optical film according to claim 8, wherein the thickness is 200 μm or less.   The laminated film obtained by apply | coating the thermosetting resin composition in any one of Claims 1-7 on a base film, and hardening this.   A liquid crystal display using at least one of the optical film according to claim 8 or 9 or the laminated film according to claim 10 as a member.