JPH06107752A - Curable resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent heat resistance, weather ability and hardness, comprising an unsaturated epoxy ester resin prepared by a specific method, an ethylenically unsaturated bond-containing vinyl compound and a photosensitizer. CONSTITUTION:The objective composition comprises (A) 5-95 pts.wt. unsaturated epoxy ester resin prepared by reacting (i) a compound containing both a vinyl group and an epoxy group with (ii) at least one selected from a polybasic acid anhydride, a polybasic acid, a terminal acid-containing polymer and a carboxylic acid-containing polymer and (iii) an active hydrogen-containing compound to give a vinyl group-containing resin, epoxidizing the resin and reacting the epoxy resin with an unsaturated monocarboxylic acid in the presence of a reaction catalyst and optionally a polymerization inhibitor, a solvent or a polymerizable monomer under heating, (B) 95-5 pts.wt. ethylenically unsaturated bond- containing vinyl compound and (C) 0-10 pts.wt. photosensitizer. In order to epoxidize the vinyl group-containing resin prepared by reacting the components (i) to (iii), peracetic acid is preferably used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin composition which is cured by irradiation with radiation to give a cured product having excellent weather resistance, heat resistance and transparency.

[0002]

2. Description of the Related Art A radiation curable resin composition which is cured by irradiation with radiation such as ultraviolet rays and electron beams has been developed and put to practical use in various applications such as printing, coating and electrical insulation. Its advantages are: 1) Solvent-free and low-pollution type. 2) The curing speed is extremely fast and the productivity is high. 3) Since it cures at 100% solids, the volume change before and after curing is extremely small. 4) There is no heat loss due to the material or heat effect on the material. Etc., and has been developed for paints and adhesives for plastics, paper, wood, inorganic materials, etc.

Radiation-curable paints, inks, adhesives and the like having such characteristics exhibit excellent properties such as adhesion, water resistance and heat resistance.

[0004]

However, the epoxy resins usually used are molecular skeletons such as epibis type epoxy resin synthesized from bisphenol A and epichlorohydrin, and novolac epoxy resin synthesized from novolac phenol and epichlorohydrin. It has a benzene ring. A cured product of an unsaturated epoxy polyester resin obtained by using these epoxy resins has drawbacks such as poor weather resistance and lack of transparency due to the benzene ring.

Aliphatic epoxies, epoxidized vegetable oils and the like are used as other epoxy resins, but the heat resistance,
It has the drawback of lacking toughness.

Under the circumstances described above, as a result of investigations by the present inventors, the unsaturated epoxy ester resin obtained from the epoxy resin disclosed in Japanese Patent Application No. 04-83739 is used, so that it is excellent in heat resistance, weather resistance and hardness. It was found that a curable resin composition having the above characteristics was obtained, and the present invention was completed.

Further, it has been clarified that the characteristics of the epoxy resin can be changed by giving various combinations of (a), (b) and (c) to be used, and a wide range of characteristics can be given.

[0008]

Means for Solving the Problems That is, the present invention provides "[A] (a) a compound having at least one vinyl group and one epoxy group in one molecule, and (b) a polybasic acid. At least one selected from anhydrides, polybasic acids, acid-terminated polymers, and polymers containing carboxylic acid groups, and (c) at least one selected from compounds having one or more active hydrogens. Of the vinyl group-containing resin obtained by further reacting with the epoxy resin obtained by further epoxidizing the resin and an unsaturated monocarboxylic acid, or if necessary, a part or a large amount of the unsaturated monocarboxylic acid. Saturated part is selected from monocarboxylic acid, polycarboxylic acid, saturated polycarboxylic acid anhydride, unsaturated polycarboxylic acid, unsaturated polycarboxylic acid anhydride, and saturated alkyd having a terminal carboxyl group. 1 or more Unsaturated epoxy ester resin obtained by substituting with 5 to 95 parts by weight of [B] ethylenically unsaturated bond obtained by heating and reacting in the presence of a reaction catalyst and optionally a polymerization inhibitor, a solvent or a polymerizable monomer. A vinyl compound having a content of 95 to 5 parts by weight [C] photosensitizer 0 to 10 parts by weight.

Next, the present invention will be described in detail.

The compound having one epoxy group and one or more vinyl groups in one molecule used in the present invention has the general formula (IV) << i is an integer of 1 to 5, R ¹ and R ⁴ are hydrogen atoms or an alkyl group having 1 to 50 carbon atoms or a substituted phenyl group,
R ² and R ³ are a hydrogen atom or an alkyl group having 1 to 50 carbon atoms, and R ² and R ³ may be wound around a ring. 》
An example of the compound represented by is a compound as shown below.

4-vinylcyclohexene-1-oxide, 5-vinylbicyclo [2.2.1] hept-2-ene-2-oxide, limonene monoxide, trivinylcyclohexane monoxide, divinylbenzene monoxide, butadiene monooxide. Oxide and 1,2-epoxy-
Examples thereof include compounds represented by (I) such as 9-decene, compounds represented by (II) such as allyl glycidyl ether, and compounds such as glycidyl styryl ether.

Further, the following compounds can also be used.

[0013]

[Chemical 1]

[Chemical 2]

[Chemical 3]

[Chemical 4] These may be used alone or in combination of two or more.

If desired, ethylene oxide,
Propylene oxide, cyclohexene oxide, styrene oxide, monoepoxides such as α-olefin epoxide, vinyl cyclohexene dioxide, 3,4-
A diepoxide such as epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate may be used at the same time as the compound having one epoxy group and one or more vinyl groups in one molecule.

The polybasic acid anhydrides or polybasic acids (b) used in the present invention include aromatic polybasic acids and acid anhydrides thereof, and aliphatic polybasic acids and acid anhydrides thereof. Examples of aromatic polybasic acids and acid anhydrides thereof include:
Examples include phthalic anhydride, isophthalic acid, terephthalic acid and trimellitic anhydride. Examples of the aliphatic polybasic acid and its acid anhydride include tetrahydrophthalic acid, 4-methylhexahydrophthalic acid, hexahydrophthalic acid, adipic acid, maleic acid, and their acid anhydrides, fumaric acid and sebacic acid. , Dodecane diacid, and their acid anhydrides.

The acid-terminated polymer used in the present invention is an acid-terminated polymer obtained by reacting a polybasic acid with polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, polycyclohexene glycol, polyvinyl cyclohexene glycol or the like. Examples include ethers, acid-terminated polyesters, acid-terminated polybutadienes and acid-terminated polycaprolactones.

Further, an acrylic copolymer having a carboxylic acid group can be used instead of the acid terminal polymer, and it contains a polybasic acid anhydride, a polybasic acid, an acid terminal polymer, and a carboxylic acid group. These polymers may be used alone or in combination of two or more.

Next, as the compound (c) having active hydrogen used in the present invention, alcohols, phenols, carboxylic acids, amines, thiols, hydroxyl-terminated polymers, and hydroxyl groups can be used. The polymer etc. which are contained are mentioned. The alcohols are monovalent, divalent, trivalent or higher, and include, for example, methanol, ethanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butanediol, Examples include hexanediol, glycerin, butanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, diglycerol, triglycerol and the like. In addition, neopentyl glycol, neopentyl glycol ester of hydroxyhivalic acid, dipentaerythritol, 1,4-cyclohexanedimethanol, trimethylpentanediol,
1,3,5-Tris (2-hydroxyethyl) cyanuric acid, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct and the like can also be used.

Examples of the phenols are phenol, cresol, catechol, pyrogallol, hydroquinone,
Hydroquinone monomethyl ether, bisphenol A, bisphenol F, 4,4'-dihydroxybenzophenone, bisphenol S, ethylene oxide adduct of bisphenol A, propione oxide adduct of bisphenol A, phenol Resin and cresol-novolak resin.

Examples of the hydroxyl group-terminated polymer used in the present invention include polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, polycyclohexene glycol and polyvinyl cyclohexene glycol, hydroxyl group terminated polyesters, hydroxyl group terminated polybutadiene, Examples include hydroxyl-terminated polycaprolactone and polycarbonate diol.

Further, an acrylic copolymer having a hydroxyl group can be used instead of the hydroxyl-terminated polymer.

The carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, fatty acids of animal and vegetable oils, fumaric acid, maleic acid, adipic acid, dodecane diacid, trimellitic acid, pyromellitic acid, polyacrylic acid, phthalic acid, isophthalic acid. Acid, terephthalic acid, etc.

Further, compounds having both a hydroxyl group and a carboxylic acid, such as lactic acid, citric acid and oxycaproic acid, can also be mentioned.

The amines include monomethylamine, dimethylamine, monoethylamine, diethylamine, propylamine, monobutylamine, dibutylamine, pentylamine, hexylamine, cyclohexylamine,
Examples include octylamine, dodecylamine, 4,4'-diaminodiphenylmethane, isophoronediamine, toluenediamine, hexamethylenediamine, xylenediamine, diethylenetriamine, triethylenetetramine and ethanolamine.

As the thiols, methyl mercaptan,
Mercapto such as ethyl mercaptan, propyl mercaptan, phenyl mercaptan, mercaptopropionic acid or polyhydric alcohol ester of mercaptopropionic acid, for example, ethylene glycol dimercaptopropionic acid ester, trimethylolpropane trimercaptopropionic acid, pentaerythritol pentamercaptopropionic acid, etc. Can be given.

Further, as the compound having active hydrogen, polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate, cellulose acetate butyrate, hydroxyethyl cellulose, acrylic polyol resin, styrene allyl alcohol copolymer resin, Styrene-maleic acid copolymer resin, alkyd resin, polyester polyol resin,
Examples include polyester carboxylic acid resins, polycaprolactone polyol resins, polypropylene polyols, polytetramethylene glycol, and the like.

The compound having active hydrogen may have an unsaturated double bond in its skeleton, and specific examples thereof include allyl alcohol, acrylic acid, methacrylic acid,
There are 2-hydroxyethyl methacrylate, 3-cyclohexenemethanol, tetrahydrophthalic acid and the like.

Any compound can be used as long as it is a compound having these active hydrogens, and two or more kinds thereof may be mixed.

The resin [A] having a vinyl group used in the present invention comprises a compound (a) having one or more vinyl groups and one epoxy group in the above molecule, a polybasic acid anhydride,
Obtained by reacting at least one selected from a polybasic acid, an acid terminal polymer, and a polymer (b) containing a carboxylic acid group with at least one selected from a compound (c) having active hydrogen. To be

The starting materials (a), (b),
The charging ratio of (c) is 1 to 99 parts by weight of (a), preferably 30 to 80 parts, 99 to 1 part by weight of (b), preferably 20 to 70 parts, and 0 to 99 parts by weight of (c). Parts, preferably 0 to 30 parts.

The component (c) may not be used depending on the case. When the component (c) is not used, it is necessary to control the molecular weight while detecting the dehydration amount by controlling the reaction time, the degree of reduced pressure, the reaction temperature and the like.

When the amount of the component (a) used is relatively small, the epoxy group content in the target epoxy resin is small. The molar ratio of component (a) / component (b) is
It is 0.4 to 5.0, preferably 0.5 to 3.0.

When the proportion of component (a) is high, the proportion of hydroxyl groups at the terminals increases, and when there are hydroxyl groups and carboxyl group terminals, all terminals become hydroxyl groups as the dehydration reaction proceeds.

On the contrary, when the ratio of the component (b) is high, the ratio of the terminal being a carboxyl group is large, and in the case where the hydroxyl group end and the carboxyl group end are present, all the terminals become carboxyl groups as the dehydration reaction proceeds. . However, (a)
If the ratio of the components is unnecessarily large, part of the component (a) will remain unreacted. Further, when the ratio of the component (b) becomes unnecessarily large, the component (b) remains without reacting.

In the reaction for synthesizing the resin having a vinyl group, a catalyst for promoting the ring-opening reaction of the epoxy group with a carboxyl group and, if necessary, a catalyst for promoting the (dehydration) esterification reaction may be used in combination. Good.

As the catalyst for promoting the ring-opening reaction of an epoxy group with a carboxyl group which can be used in the present invention, a tertiary amine such as dimethylbenzylamine, triethylamine, tetramethylethylenediamine and tri-n-octylamine, tetramethylammonium chloride. , Quaternary ammonium salts such as tetramethylammonium bromide and tetrabutylammonium bromide, alkylureas such as tetramethylurea, and alkylguanidines such as tetramethylguanidine.

The catalyst for promoting the ring-opening reaction that can be used in the present invention may be used alone or in combination of two or more kinds. This catalyst is 0.1 to 5.0 relative to the epoxy compound.
%, Preferably 0.5 to 3.0% by weight. The ring-opening reaction is 50 to 200 ° C, preferably
It is carried out at 100 to 180 ° C.

Examples of the catalyst for promoting the (dehydration) esterification reaction that can be used in the present invention include Sn compounds such as tin octylate and dibutyltin laurate, and Ti compounds such as tetrabutyl titanate.

The catalyst for promoting the (dehydration) esterification reaction used in the present invention may be used alone or in combination of two or more kinds. This catalyst is 0-100 with respect to the reaction system.
It is recommended to use 0 ppm, preferably 50 to 500 ppm.

This (dehydration) esterification reaction is 180 to 2
Perform at 40 ° C.

The epoxy group ring-opening reaction with a carboxyl group and the (dehydration) esterification reaction may be carried out sequentially, but after the raw materials and the catalyst have been charged all at once, the reaction temperature is raised stepwise in accordance with the progress of the reaction. Method is preferred. If necessary, after the component (c) and the catalyst are charged at once,
The components (a) and (b) may be dropped.

The resin having an epoxy group used in the present invention is synthesized by reacting the resin having a cyclic olefin or vinyl group thus synthesized with an epoxidizing agent. Examples of the agent include peracids and hydroperoxides.

Examples of peracids include formic acid, peracetic acid, perbenzoic acid and trifluoroperacetic acid. Of these, peracetic acid is industrially produced in large quantities and is available at low cost.
It is also a preferred epoxidizing agent because of its high stability.

Hydroperoxides include hydrogen peroxide, tertiary butyl hydroperoxide, cumene peroxide and the like.

In the epoxidation, a catalyst can be used if necessary.

For example, in the case of peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst.

In the case of hydroperoxides,
A mixture of tungstic acid and caustic soda with hydrogen peroxide,
Alternatively, a catalytic effect can be obtained by using an organic acid in combination with hydrogen peroxide or molybdenum hexacarbonyl in combination with tertiary butyl hydroperoxide.

The epoxidation reaction is carried out by adjusting the presence or absence of the solvent and the reaction temperature according to the physical properties of the equipment and raw materials.

The reaction temperature range that can be used depends on the reactivity of the epoxidizing agent used.

With respect to peracetic acid which is a preferable epoxidizing agent, 0 to 70 ° C. is preferable.

The reaction is slow below 0 ° C, and peracetic acid is decomposed at 70 ° C.

In the tertiary butyl hydroperoxide / molybdenum dioxide diacetylacetonate system, which is an example of hydroperoxide, it is 2 for the same reason.
0 degreeC-150 degreeC is preferable.

The solvent can be used for the purpose of decreasing the viscosity of the raw material and stabilizing it by diluting the epoxidizing agent.
In the case of peracetic acid, aromatic compounds, ethers, esters and the like can be used.

The charged molar ratio of the epoxidizing agent to the unsaturated bond can be changed according to the purpose such as how much unsaturated bond is desired to remain.

When a compound having a large number of epoxy groups is intended, the epoxidizing agent is preferably added in an equimolar amount or more with respect to the unsaturated group.

However, it is usually disadvantageous in excess of 2 times the molar amount in view of economical efficiency and side reactions, and in the case of peracetic acid, 1 to 1.5 times the molar amount is preferable.

The composition of interest can be removed from the reaction crude liquid by chemical engineering means such as concentration.

The epoxy resin used in the present invention can be used as a mixture with other epoxy resins as long as the characteristics of the composition are not impaired. Here, the other epoxy resin may be any as long as it is generally used,
Examples include epibis-type epoxies, bisphenol F epoxies, novolac epoxies, cycloaliphatic epoxies and epoxy diluents such as styrene oxide and butylglycidyl ether.

As the unsaturated monocarboxylic acid to be reacted with these epoxy resins, acrylic acid, methacrylic acid, crotonic acid, etc. are generally used. In addition, a saturated monocarboxylic acid, a saturated polycarboxylic acid, a saturated polycarboxylic acid anhydride, an unsaturated polycarboxylic acid, or an unsaturated group which replaces a part or most of the unsaturated carboxylic acid as the component [A]. Examples of the polycarboxylic acid anhydride include acetic acid, benzoic acid, maleic anhydride, phthalic acid, phthalic anhydride, succinic acid, adipic acid, hexahydrophthalic anhydride, and pyromellitic dianhydride. You may use 1 type or 2 or more types.

The saturated or unsaturated alkyd having a carboxyl group at the terminal is an alkyd having a terminal carboxyl group obtained by a dehydration condensation reaction between a polyhydric alcohol and a polycarboxylic acid.

The reaction molar ratio of the carboxylic acid and the epoxy compound is possible if the total of the carboxyl groups of the carboxylic acid is 0.1 mol or more per 1 mol of the epoxy group, but it is in the range preferable from the viewpoint of curability and performance. Is 0.2 to 2 mol.

Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, methoxyhydroquinone and the like.

The composition of interest can be removed from the crude reaction liquid by chemical engineering means such as concentration.

As the polymerizable monomer, methyl methacrylate
, Hydroxylethyl acrylate, styrene, vinyltoluene, ethylene glycol diacrylate and the like.

Examples of the solvent include benzene and ethyl alcohol.
, Ethyl acetate, toluene, ethyl cellosolve and the like are used alone or in combination.

In the presence of these, the epoxy compound and the carboxylic acid are reacted by heating, and the reaction temperature is generally 50.
It is carried out at ˜130 ° C., preferably 80˜120 ° C.

In the curable resin composition of the present invention, the unsaturated epoxy ester resin thus obtained is used in an amount of 5 to 5.
To 95 parts by weight, preferably 20 to 80 parts by weight, 95 to 5 parts by weight, preferably 80 to 20 parts by weight of a vinyl compound having an ethylenically unsaturated bond is added. In the curable resin composition of the present invention, when the unsaturated epoxy ester resin is small, heat resistance and mechanical strength cannot be sufficiently imparted, and when it is too large, the viscosity becomes high and handling becomes difficult.

The vinyl compound having an ethylenically unsaturated bond used in the present invention is represented by an acrylic acid ester or methacrylic acid ester compound represented by the general formula (1), styrene, N-vinylpyrrolidone and the like. It is a low-viscosity compound having a radical-polymerizable double bond.

[0069] Typical acrylic acid or methacrylic acid esters are as follows. 2-hydroxyethyl acrylate
, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, tetrahydrofurfuryl alcohol acrylate, phenoxyethyl acrylate, etc. (Meth) acrylic acid ester, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate
For example, a bifunctional (meth) acrylic acid ester such as a trifunctional (meth) acrylic acid ester, a trifunctional (meth) acrylic acid ester such as a trimethylolpropane triacrylate, a pentaerythritol triacrylate, or the like is used.

These vinyl compounds having an ethylenically unsaturated bond are used alone or in a mixture of two or more.

The term "radiation" used in the present invention means that
It refers to any radiation source that produces free radicals and induces addition polymerization of vinyl bonds. Suitable as actinic radiation is 200 to 7
000 angstrom wavelength, 2000-40
Those of 00 angstrom are preferable. A type of actinic radiation useful here is ultraviolet light. Other forms of actinic radiation are sunlight, artificial arc light sources such as carbon arc lamps, and steam lamps. A suitable radiation curable resin composition may contain an effective amount of a photosensitizer when photocuring. Usually this amount is about 0.01 of the resin composition.
10 to 10% by weight, preferably about 0.1 to 5% by weight.
Examples of the photosensitizer include benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether.
Ter, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyldisulfide and the like.

These photosensitizers may also contain a synergist to enhance the conversion of the absorbed light energy into polymerization initiating free radicals, for example tertiary amines.

When the curable resin composition is cured by electron beam irradiation, it is not always necessary to add a sensitizer.
The resin composition of the present invention may further contain a thermal polymerization inhibitor, a surfactant, an ultraviolet absorber, a thixotropic agent, a dye, a pigment and the like as other additives, if necessary. Furthermore, a thermoplastic resin, a thermosetting resin, etc. can also be blended. The composition of the present invention can be cured by applying it as a thin film on a substrate. As a method for forming the thin film, spraying, brushing, roll coating or the like is used. The curing is preferably carried out under an inert gas atmosphere, but the curing can also be carried out under an air atmosphere.

The curable resin composition according to the present invention is an ink,
Various coating fields such as plastic coating, paper printing, film coating, furniture coating, FRP, lining, and also in the electronics field, insulating varnish, insulating sheet, laminated board, printed circuit board, resist ink, semiconductor encapsulation. It can be applied to many industrial fields such as anti-static agents. Hereinafter, the present invention will be described in detail with reference to examples.

Claims (11)

[Claims] 1. [A] (a) a compound having one or more vinyl groups and one epoxy group in one molecule, (b) a polybasic acid anhydride, a polybasic acid, an acid terminal polymer, And a resin having a vinyl group obtained by reacting at least one selected from polymers having a carboxylic acid group and (c) at least one selected from compounds having one or more active hydrogens. An epoxy resin obtained by further epoxidizing the fat and an unsaturated monocarboxylic acid, or if necessary, part or most of the unsaturated monocarboxylic acid is a saturated monocarboxylic acid, a polyvalent carboxylic acid, One or more selected from saturated polycarboxylic anhydrides, unsaturated polycarboxylic acids, unsaturated polycarboxylic anhydrides, and saturated alkyds having a terminal carboxyl group may be substituted with one or more reaction catalysts and Heavy as needed Unsaturated epoxy ester resin obtained by heating and reacting in the presence of a polymerization inhibitor, a solvent or a polymerizable monomer 5 to 95 parts by weight [B] a vinyl compound having an ethylenically unsaturated bond 95 to 5 parts by weight [C ] The photosensitizer 0-10 weight part, The curable resin composition characterized by the above-mentioned. 2. The curable resin composition according to claim 1, wherein the compound having one or more vinyl groups and one epoxy group in one molecule is 4-vinylcyclohexene-1-oxide. 3. The compound having one or more vinyl groups and one epoxy group in one molecule is 5-vinylbicyclo [2.2.1] hept-2-ene-2-oxide. 1. The curable resin composition of 1. 4. The curable resin composition according to claim 1, wherein the compound having one or more vinyl groups and one epoxy group in one molecule is limonene monoxide. 5. A compound having at least one vinyl group and one epoxy group in one molecule is represented by the following general formula (I): The curable resin composition according to claim 1, which is a compound represented by << n is an integer of 0 to 30 >>. 6. A compound having one or more vinyl groups and one epoxy group in one molecule is represented by the following general formula (II): The curable resin composition according to claim 1, which is a compound represented by << n1 and n2 are integers from 0 to 30 >>. 7. A compound having at least one vinyl group and one epoxy group in one molecule is represented by the following general formula (III): The curable resin composition according to claim 1, which is a compound represented by <Ph is a substituted phenyl group and n is an integer of 0 to 30>. 8. A compound having one or more active hydrogens,
The curable resin composition according to claim 1, which is an alcohol, a hydroxyl group-terminated polymer, or a polymer containing a hydroxyl group. 9. The curable resin composition according to claim 1, wherein the acid-terminated polymer is an acid-terminated polyester. 10. The curable resin composition according to claim 8, wherein the hydroxyl-terminated polymer is a hydroxyl-terminated polyester. 11. The curable resin composition according to claim 8, wherein the hydroxyl group terminated polymer is a hydroxyl group terminated polyether.