JP6588281B2 - Putty resin composition and putty using the same - Google Patents

Description

  The present invention relates to a putty resin composition that is excellent in thin film drying properties and has little shrinkage after curing, and a putty using the same, without using a styrene monomer.

  Conventionally, putty mainly composed of unsaturated polyester resin has been widely used as a covering material putty for automobiles and vehicles because it is excellent in terms of curability, drying property, polishing property, adhesiveness and the like. In addition, styrene monomers are frequently used in putty using this unsaturated polyester resin from the viewpoints of curability and physical properties. However, in recent years, from the viewpoint of environmental problems, there has been an increasing social demand to regulate the use of styrene monomers that are problematic in terms of volatility, odor, toxicity, etc., and non-styrelation of putty resin compositions is required. ing.

  As a non-styrenized putty resin composition, two or more polymerizations per molecule, which is one selected from unsaturated polyester resin, epoxy (meth) acrylate, urethane (meth) acrylate, and polyester (meth) acrylate Room temperature having a polymerizable unsaturated resin (A) having a polymerizable unsaturated double bond, a hydroxyalkyl (meth) acrylate (B), one or more cyclohexene rings and two or more allyl ether groups in one molecule A curable unsaturated resin composition containing a liquid unsaturated compound (C) has been proposed (for example, see Patent Document 1). This curable unsaturated resin composition has a relatively good putty thick film drying property, but has a problem in the thin film drying property of the putty edge part and the putty curing shrinkage property.

  Therefore, there has been a demand for a putty resin composition that is excellent in thin film drying and has little shrinkage after curing without using a styrene monomer.

JP 2003-40949 A

  The problem to be solved by the present invention is to provide a putty resin composition excellent in thin film drying property and having a small shrinkage after curing, and a putty using the same, without using a styrene monomer.

  As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition containing a specific unsaturated polyester, 2-hydroxyethyl methacrylate and diallyl phthalate prepolymer is a thin film without using a styrene monomer. The present invention has been completed by finding that it has excellent drying properties and small shrinkage after curing.

  That is, the present invention contains an air-drying impartable unsaturated polyester (A) having an alicyclic structure, a monomer (B) having a (meth) acryloyl group, and a diallyl phthalate prepolymer (C). A putty resin composition and putty are provided.

  The resin composition for putty according to the present invention is a material that takes into consideration the working environment with little impact on the environment, because it does not use a styrene monomer, has excellent thin film drying properties, and has little shrinkage after curing. Therefore, the resin composition for putty of the present invention is useful as a sealing material for repair putty for vehicles such as automobiles and trains, primers for steel furniture, joint parts of buildings, around sashes, glass fitting parts, etc. In addition, it can be used for adhesives and paints.

  The resin composition for putty of the present invention contains an air-drying impartable unsaturated polyester (A) having an alicyclic structure, a monomer (B) having a (meth) acryloyl group, and a diallyl phthalate prepolymer (C). To do.

  The unsaturated polyester (A) is obtained by reacting a polybasic acid and a polyhydric alcohol. Moreover, in order to provide the said unsaturated polyester (A) with an alicyclic structure and air-drying property, the air-drying raw material which has an alicyclic structure is used as the raw material. As air-drying raw materials having an alicyclic structure, cycloaliphatic unsaturated polybasic acids and their derivatives, dicyclopentadiene, hydroxydicyclopentadiene, dicyclopentadiene malate (monoester of dicyclopentadiene and maleic acid), etc. Is mentioned. Examples of the cycloaliphatic unsaturated polybasic acid and derivatives thereof include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, α-terpinene / maleic anhydride adduct, trans-piperylene / maleic anhydride. Examples include acid adducts. Among these, methyltetrahydrophthalic anhydride and tetrahydrophthalic anhydride are preferable because air drying property (air drying property) is particularly improved.

  As a raw material for introducing an unsaturated group into the unsaturated polyester (A), an α, β-unsaturated dibasic acid or a saturated dibasic acid is used as a polybasic acid other than the air-drying raw material having the alicyclic structure. .

  Examples of the α, β-unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride and the like. Examples of the saturated dibasic acid include phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid, hexahydroisophthalic acid. Succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2, Examples include 3-naphthalenedicarboxylic acid anhydride, 4,4′-biphenyldicarboxylic acid, and dialkyl esters of these saturated dibasic acids.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3-butanediol, neo Pentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, propylene oxide or ethylene oxide adduct of bisphenol A, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-propanediol 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cyclohexanedimethanol, paraxylene glycol, bisci Rohekishiru 4,4'-diol, 2,6-decalin glycol, 2,7-decalin glycol, and the like.

  Air-drying raw materials other than the air-drying raw material having the alicyclic structure may be used as the raw material for the unsaturated polyester (A). Examples of such raw materials include hydroxy compounds having an allyl ether group, drying oils such as linseed oil and tung oil.

  Examples of the hydroxy compound having an allyl ether group include ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, Tripropylene glycol monoallyl ether, polypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether, hexylene glycol monoallyl ether, octylene glycol monoallyl ether, trimethylolpropane Diallyl ether, glyceryl diallyl ether, pentaerythritol triallyl ether Allyl ether compound of a polyhydric alcohol such as ether can be mentioned.

  The polybasic acid, polyhydric alcohol, and the like, which are raw materials for the unsaturated polyester (A), can be used alone or in combination of two or more.

  Examples of the monomer (B) having a (meth) acryloyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, T-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic Acid tridecyl, 2-hydroxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monobutyl ether (meth) acrylate, ethylene Recall monohexyl ether (meth) acrylate, ethylene glycol mono 2-ethylhexyl ether (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monobutyl ether (meth) acrylate, diethylene glycol monohexyl ether (Meth) acrylate, diethylene glycol mono 2-ethylhexyl ether (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di ( (Meth) acrylate, tetraethyleneglycol Rudi (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl Glycol di (meth) acrylate, poly (tetramethylene glycol) di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meta ) Acrylate, 1,3-bis [(meth) acryloyloxy] -2-propanol, 2,2-bis [4- (meth) acryloxyethoxyphenyl] propane, 2,2-bis [4- (meth) acrylo Yloxydiethoxyphenyl] propane, 2,2-bis [4- (meth) acryloyloxy / polyethoxyphenyl] propane, tetraethylene glycol di (meth) acrylate, ethylene oxide modified di (meth) acrylate of bisphenol A, isocyanuric Examples thereof include ethylene oxide-modified di (meth) acrylate of acid, pentaerythritol di (meth) acrylate monostearate and the like.

  When it is necessary to further improve the performance of the surface of the cured product, such as abrasion resistance, scratch resistance, peristaltic resistance, chemical resistance, etc., a monomer having two or more (meth) acryloyl groups is added. It is preferable to use as the monomer (B), and it is more preferable to use a monomer having three or more (meth) acryloyl groups as the monomer (B). Examples of the monomer having three or more (meth) acryloyl groups include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and trimethylolpropane. Ethylene oxide-modified tri (meth) acrylate, propylene oxide-modified tri (meth) acrylate of trimethylolpropane, ethylene oxide-modified tri (meth) acrylate of isocyanuric acid, ethylene oxide of isocyanuric acid / ε-caprolactone modified tri (meth) acrylate, Examples thereof include dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Among these, 2-hydroxyethyl methacrylate is preferable in terms of odor, safety, viscosity, and curability.

  The monomer (B) can be used alone or in combination of two or more. In the present invention, “(meth) acrylic acid” refers to both or one of acrylic acid and methacrylic acid, and “(meth) acrylate” refers to both or one of acrylate and methacrylate. “) Acryloyl” refers to both or one of acryloyl and methacryloyl.

  The diallyl phthalate prepolymer (C) is a prepolymer obtained by polymerizing diallyl orthophthalate or diallyl isophthalate. The weight average molecular weight of the diallyl phthalate prepolymer (C) is preferably in the range of 5,000 to 100,000, more preferably in the range of 10,000 to 80,000, and further in the range of 20,000 to 60,000. preferable. Examples of commercially available products include “Daiso Dup A”, “Daisoh Dup S”, “Daisoh Dup K”, and “Daisoh Isodap”, which are diallyl phthalate resins (Dup resins) manufactured by Daiso Corporation. Among these, “Dyso Dup A” is preferable in terms of compatibility. Moreover, the said diallyl phthalate prepolymer (C) can be used individually by 1 type, or can also be used together 2 or more types.

  In the putty resin composition of the present invention, the amount of the monomer (B) is preferably in the range of 10 to 100 parts by mass with respect to 100 parts by mass of the unsaturated polyester (A), and preferably 25 to 85. The range of parts by mass is more preferable, and the range of 40 to 60 parts by mass is more preferable. On the other hand, as a compounding quantity of the said diallyl phthalate prepolymer (C), the range of 5-60 mass parts is preferable with respect to 100 mass parts of said unsaturated polyester (A), and the range of 10-50 mass parts is more preferable. A range of 15 to 40 parts by mass is more preferable.

  Moreover, in the resin composition for putty of the present invention, an unsaturated monomer (A) other than the unsaturated polyester (A), the monomer (B) and the diallyl phthalate prepolymer (C), if necessary. D) may be blended. Examples of the unsaturated monomer (D) include α-methylstyrene, chlorostyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, vinyl toluene, vinyl acetate, diaryl phthalate, and triaryl cyanurate. And so on.

  The putty of this invention contains the resin composition for putty demonstrated above, and knead | mixes a filler and another additive in paste form with this. Further, a coloring agent may be blended to color the putty in a desired color. Further, a curing agent, a curing accelerator, a polymerization inhibitor and the like may be blended in order to adjust the curing rate of the putty as necessary.

  Examples of the filler include calcium carbonate, magnesium carbonate, barium sulfate, mica, talc, kaolin, clay, celite, asbestos, barlite, baryta, silica, silica sand, dolomite, limestone, gypsum, aluminum powder, hollow balloon , Alumina, glass powder, aluminum hydroxide, cryolite, zirconium oxide, antimony trioxide, titanium oxide, molybdenum dioxide and the like. These fillers include those subjected to surface treatment. Moreover, the filler to be used can be selected in consideration of workability and the strength, appearance, economy and the like of the obtained molded product, and can be used alone or in combination of two or more. Among these fillers, calcium carbonate, aluminum hydroxide, silica, and talc are preferable from the viewpoint of workability and polishing properties. The content of the filler in the putty of the present invention is preferably in the range of 30 to 80% by mass, and more preferably in the range of 40 to 70% by mass.

  Examples of the curing agent include organic peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, benzoyl peroxide, cumene hydroperoxide, and the like. These curing agents can be used alone or in combination of two or more.

  Examples of the curing accelerator include metal soaps such as cobalt naphthenate, cobalt octylate, zinc octylate, vanadium octylate, copper naphthenate, and barium naphthenate; vanadium acetyl acetate, cobalt acetyl acetate, iron acetylacetonate, and the like. Metal chelate compounds: aniline, N, N-dimethylaniline, N, N-diethylaniline, p-toluidine, N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p-toluidine 4- (N, N-dimethylamino) benzaldehyde, 4- [N, N-bis (2-hydroxyethyl) amino] benzaldehyde, 4- (N-methyl-N-hydroxyethylamino) benzaldehyde, N, N- Bis (2-hydroxypropyl) -p-toluidine, N- N, N-substituted anilines such as til-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, N, N-bis (hydroxyethyl) aniline, diethanolaniline, N, N- Examples thereof include amine compounds such as substituted-p-toluidine and 4- (N, N-substituted amino) benzaldehyde. These curing accelerators can be used alone or in combination of two or more. Of these curing accelerators, metal soaps and amine compounds are preferred.

  The blending amount of the curing agent is preferably in the range of 0.1 to 6 parts by mass with respect to 100 parts by mass in total of (A) to (C). Moreover, the compounding quantity of the said hardening accelerator has the preferable range of 0.1-5 mass parts with respect to a total of 100 mass parts of said (A)-(C). In addition, a hardening accelerator may be mix | blended with resin previously or may be mix | blended at the time of use.

  Examples of the polymerization inhibitor include trihydrobenzene, toluhydroquinone, 1,4-naphthoquinone, parabenzoquinone, hydroquinone, benzoquinone, hydroquinone monomethyl ether, p-tert-butylcatechol, 2,6-di-tert-butyl- 4-methylphenol etc. are mentioned. These polymerization inhibitors can be used alone or in combination of two or more. The content of the polymerization inhibitor in the putty of the present invention is preferably in the range of 10 to 1,000 ppm.

  Examples of the colorant include inorganic pigments such as titanium white (titanium oxide) and carbon black; organic pigments such as phthalocyanine blue and quinacridone red. These colorants can be used by appropriately adjusting one or more colorants in order to color the putty in a desired color.

  In the putty of the present invention, as other various additives other than those described above, for example, viscosity modifiers such as a viscosity reducer, defoaming agents, silane coupling agents, air blocking agents such as paraffin, ultraviolet absorbers, plasticizers Further, aggregates, flame retardants, stabilizers, reinforcing materials and the like may be blended.

  A diluent may be used for the purpose of adjusting the viscosity of the putty of the present invention. Examples of the diluent include toluene, xylene, methanol, ethanol, propanol, butanol, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, and the like. These diluents can be used alone or in combination of two or more.

  The viscosity of the putty of the present invention is preferably in the range of 50 to 500 Pa · s, more preferably in the range of 100 to 200 Pa · s because it can be designed to be cured with time.

  Hereinafter, the present invention will be described in more detail with reference to examples.

(Production Example 1: Production of unsaturated polyester (1))
In a 2 L glass flask equipped with a nitrogen gas inlet tube, a reflux condenser and a stirrer, 502 g (4.74 mol) of diethylene glycol, 320 g (2.75 mol) of fumaric acid and 305 g (1.83 mol) of methyltetrahydrophthalic anhydride And heating was started under a nitrogen stream. A dehydration condensation reaction was carried out at an internal temperature of 200 ° C., and when the acid value reached 29 mg KOH / g, 0.33 g of toluhydroquinone was added and then cooled to 150 ° C. to obtain a normal temperature solid unsaturated polyester (1). .

(Production Example 2: Production of unsaturated polyester (2))
In a 2 L glass flask equipped with a nitrogen gas inlet tube, a reflux condenser, and a stirrer, 509 g (4.80 mol) of diethylene glycol, 103 g (0.48 mol) of trimethylolpropane diallyl ether and 557 g (4.80 mol) of fumaric acid were used. And heating was started under a nitrogen stream. A dehydration condensation reaction was carried out at an internal temperature of 190 ° C., and when the acid value reached 29 mg KOH / g, 0.33 g of toluhydroquinone was added and then cooled to 150 ° C. to obtain a normal temperature solid unsaturated polyester (2). .

(Production Example 3: Production of unsaturated ester compound (1))
A 2 L glass flask equipped with a nitrogen gas inlet tube, a reflux condenser, and a stirrer was charged with 973 g (3.80 mol) of pentaerythritol triallyl ether and 614 g (3.70 mol) of methyltetrahydrophthalic anhydride under a nitrogen stream. Heating was started. An esterification reaction was performed at an internal temperature of 160 ° C. for 4 hours to obtain a normal temperature liquid (viscosity: 20 Pa · s) unsaturated ester compound (1).

Example 1
55 parts by mass of unsaturated polyester (1) obtained in Production Example 1, 30 parts by mass of 2-hydroxyethyl methacrylate and 15 parts by mass of diallyl orthophthalate prepolymer (“Daiso Dup A” manufactured by Daiso Corporation) are dissolved by heating. A putty resin composition (1) was obtained.

(Example 2)
55 parts by mass of the unsaturated polyester (1) obtained in Production Example 1, 30 parts by mass of phenoxyethyl methacrylate and 15 parts by mass of diallyl orthophthalate prepolymer (“Daiso Dup A” manufactured by Daiso Corporation) are dissolved by heating and used for putty. A resin composition (2) was obtained.

(Example 3)
Heat 55 parts by weight of unsaturated polyester (1) obtained in Production Example 1, 30 parts by weight of 1,3-butylene glycol dimethacrylate and 15 parts by weight of diallyl orthophthalate prepolymer ("Daiso Dup A" manufactured by Daiso Corporation). It was made to melt | dissolve and the resin composition for putty (3) was obtained.

(Comparative Example 1)
70 parts by mass of unsaturated polyester (1) obtained in Production Example 1 and 30 parts by mass of 2-hydroxyethyl methacrylate were dissolved by heating to obtain a resin composition for putty (R1).

(Comparative Example 2)
55 parts by mass of unsaturated polyester (1) obtained in Production Example 1, 30 parts by mass of 2-hydroxyethyl methacrylate, and 15 parts by mass of dicyclopentenyloxyethyl methacrylate were dissolved by heating to obtain a putty resin composition (R2). It was.

(Comparative Example 3)
55 parts by mass of unsaturated polyester (1) obtained in Production Example 1, 30 parts by mass of phenoxyethyl methacrylate, and 15 parts by mass of dicyclopentenyloxyethyl methacrylate were heated and dissolved to obtain a resin composition for putty (R3).

(Comparative Example 4)
55 parts by mass of the unsaturated polyester (1) obtained in Production Example 1, 30 parts by mass of 1,3-butylene glycol dimethacrylate and 15 parts by mass of dicyclopentenyloxyethyl methacrylate were dissolved by heating to obtain a resin composition for putty (R4 )

(Comparative Example 5)
55 parts by mass of the unsaturated polyester (1) obtained in Production Example 1 and 35 parts by mass of 2-hydroxyethyl methacrylate and 15 parts by mass of the unsaturated ester compound (1) obtained in Production Example 3 were dissolved by heating, for putty. A resin composition (R5) was obtained.

(Comparative Example 6)
55 parts by mass of unsaturated polyester (2) obtained in Production Example 2, 30 parts by mass of 2-hydroxyethyl methacrylate and 15 parts by mass of diallyl orthophthalate prepolymer (“Daiso Dup A” manufactured by Daiso Corporation) are dissolved by heating. A putty resin composition (R6) was obtained.

  The following evaluations were performed using the putty resin compositions (1) to (3) and (R1) to (R6) obtained in Examples 1 to 3 and Comparative Examples 1 to 6, respectively. In addition, since the resin composition for putty (R6) obtained in Comparative Example 6 was separated in the evaluation of storage stability, the subsequent evaluation was not performed.

[Evaluation of storage stability]
The putty resin composition was allowed to stand at 25 ° C. for 24 hours, the presence or absence of separation was visually confirmed, and the stability of the resin composition was evaluated according to the following evaluation.
○: No separation.
X: There is separation.

[Evaluation of thin film drying]
100 parts by weight of putty resin composition, 0.5 parts by weight of 6% by weight cobalt naphthenate (“Co-NAPHTHENATE 6%” manufactured by DIC Corporation) and 1 part by weight of methyl ethyl ketone peroxide (“PARMEC N” manufactured by NOF Corporation) Was uniformly stirred, and the obtained liquid was coated on a glass plate at 25 ° C. with a 50 μm applicator. After coating, the time (thin film drying time) until the tackiness of the coating film surface disappeared was measured, and the thin film drying property was evaluated according to the following criteria.
○: The thin film drying time is less than 2 hours.
Δ: The thin film drying time is 2 hours or more and less than 5 hours.
X: Thin film drying time is 5 hours or more.

[Preparation of putty for evaluation]
100 parts by weight of a putty resin composition, 3 parts by weight of a cobalt-based curing accelerator (“Accelerator RP-138” manufactured by DIC Material Co., Ltd.), 150 parts by weight of talc (“Talc SW” manufactured by Nippon Talc Co., Ltd.) and a white pigment ( 5 parts by mass of titanium oxide) was stirred for 15 minutes with a high-speed dissolver. Next, 1.5 parts by mass of a curing agent (“Cyclopaste Yellow” manufactured by Kayaku Akzo Corporation, cyclohexanone peroxide) was added and stirred to obtain an evaluation putty.

[Evaluation of curing shrinkage]
The evaluation putty obtained above is 3.2 mm thick on a tin plate (made by Nippon Test Panel Co., Ltd., size 70 mm × 150 mm × 0.3 mm) whose surface is polished with water-resistant paper # 100. After coating, the evaluation putty was cured by leaving it at 25 ° C. for 24 hours. Next, after placing the cured film of the putty for evaluation of the tinplate obtained on the horizontal plate with the upper side facing up, one side of the long side of the tinplate was pressed against the horizontal plate on the opposite side of the tinplate The height (warp height) floating from the horizontal plate was measured, and the curing shrinkage was evaluated according to the following criteria. In addition, it can be said that shrinkage | contraction after hardening is so small that curvature height is small.
○: The warp height is less than 1 mm.
(Triangle | delta): Warpage height is 1 mm or more and less than 10 mm.
X: Warpage height is 10 mm or more.

  Table 1 shows the composition and evaluation results of the putty resin composition prepared above.

  From the evaluation results shown in Table 1, it was confirmed that the resin composition for Example 1 which is the putty resin composition of the present invention was excellent in storage stability. Moreover, it was confirmed that the putty using this putty resin composition had high thin film drying properties and small shrinkage after curing.

  On the other hand, Comparative Examples 1 to 4 are examples in which diallyl phthalate prepolymer was not used, and Comparative Example 5 was an example in which an unsaturated ester compound was used instead of diallyl phthalate prepolymer. It was as long as 5 to 8 hours, and it was confirmed that the film was poor in dryness. Moreover, the curvature height of the tin plate was as large as 10 to 15 mm, and it was confirmed that the shrinkage after curing was large.

  Furthermore, although the comparative example 6 is an example using the unsaturated polyester which does not have an alicyclic structure, it was confirmed that the storage stability of the resin composition for putty is inferior and there is no practicality.

Claims (5)

An air-drying imparted unsaturated polyester having an alicyclic structure (A), a monomer (B) having a (meth) acryloyl group, and a diallyl phthalate prepolymer (C), a putty resin composition, A putty resin composition, wherein the diallyl phthalate prepolymer (C) is a diallyl orthophthalate prepolymer having a weight average molecular weight in the range of 5,000 to 100,000 . The monomer (B) 10 to 100 with respect to 100 parts by mass of the unsaturated polyester (A)
2 parts by mass, containing 5 to 60 parts by mass of the diallyl phthalate prepolymer (C).
The resin composition for putty described. The putty resin composition according to claim 1 or 2, wherein the monomer (B) is 2-hydroxyethyl methacrylate. The putty resin composition according to any one of claims 1 to 3, wherein the unsaturated polyester (A) uses methyltetrahydrophthalic anhydride and / or tetrahydrophthalic anhydride as a raw material. A putty comprising the resin composition for putty according to any one of claims 1 to 4 .