JP2005255937A - Unsaturated polyester resin composition and putty coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which has a low odor and a high flash point, forms a coating film having excellent drying properties, toughness, durability and adhesiveness to a base material, and to provide a putty coating using the same composition as a binder. <P>SOLUTION: The resin composition comprises (A) 10-70 wt.% unsaturated polyester obtained by reacting (a) a polybasic acid component composed of a saturated polybasic acid and an α,β-unsaturated polybasic acid, with (b) a polyhydric alcohol component containing allyl glycidyl ether expressed by a specific chemical formula and cyclopentadiene, by a specified range of their ratio, and optionally (B) 0-35 wt.% unsaturated polyester obtained by reacting an epoxy resin with an unsaturated monobasic acid and (C) 30-90 wt.% compound expressed by a specific chemical formula. The putty coating is obtained by using the same composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a resin composition and a putty paint, and more specifically, a resin composition having extremely low odor, a high flash point, excellent dryness and toughness of a coating film, and excellent adhesion to a substrate. And a putty paint using the same.

  Conventionally, a composition containing an unsaturated polyester and a monomer copolymerizable therewith is known, and is used for, for example, fiber reinforced plastics, adhesives and the like. However, when this composition is used for a primer, a top coat, an impregnating agent, a casting material, a binder for polymer concrete, a coating material or a putty paint, various problems have occurred. For example, styrene is generally used as a monomer copolymerizable with an unsaturated polyester, but when these mixtures are cured at room temperature using an organic peroxide, the surface is cured by oxygen in the air. There was a drawback that it was obstructed and the stickiness remained forever.

  In order to eliminate this drawback, a method of adding wax such as paraffin wax, forming a wax film on the surface, and blocking oxygen is used, but this method causes problems in secondary adhesion, and as a primer There was a drawback that it could not be used. In addition, wax floating unevenness occurs due to outside air temperature, wind, and the like, and when used as a top coating agent, an impregnating agent, a casting agent, a coating material, or a binding material, there is a problem that the surface is uneven or uneven. Furthermore, when this mixture is cured, sufficient flexibility cannot be obtained, so that there is a drawback that a film is cracked with a slight strain. In addition, since monomers such as styrene are likely to volatilize, there has been a problem of harming the health and working environment of workers who handle the composition containing the monomer. Furthermore, styrene, which is frequently used as a reactive diluent (monomer), has a flash point as low as 32 ° C. Therefore, non-styrenic and high flash point of the composition components can be reduced due to the problem of storage regulations in the Fire Service Act. It is desired.

  On the other hand, putty paints are mainly used as coatings or hole filling materials for base materials such as steel plates, concrete, and wood. Especially as putty paints for repairing automobile steel plates, (1) excellent spatability workability, (2) Curing quickly at room temperature, (3) Excellent polishability, (4) Excellent adhesion to the material, (5) Excellent adhesion to the top coat. (6) Performances such as excellent moisture resistance and (7) excellent durability (cracks) are required. However, in recent years, materials used for automobile outer walls have been processed directly from iron plates treated with zinc phosphate, iron phosphate, etc. for the purpose of rust prevention, directly to the iron plate for the purpose of heavy corrosion protection. Since there has been a shift to rust-proof steel sheets, there has been a problem that if the conventional putty is used for repair, the adhesion of the coating is inhibited, and peeling, prestarring, etc. occur frequently.

  In recent years, attempts have been made to suppress volatilization using high molecular weight monomers to improve odor. For example, Patent Document 1 discloses an acrylic polymer concrete composition containing an aggregate material, a binder monomer composed of dicyclopentenyloxyalkyl acrylate or methacrylate and hydroxyalkyl methacrylate, and a polymerization catalyst. . This is used for repairing floors and roads, and the upper right column on lines 5 to 18 of the publication describes improvement of the working environment due to low volatility and low odor. Yes. Further, the lower left column on page 12 of the publication describes that the composition is surface dried (= surface cured) in 2 to 4 hours. However, when this resin composition is used as a putty paint, it is not sufficient in terms of adhesion, particularly when used for the rust-proof steel plate.

  In addition, attempts have been made to modify unsaturated polyester resin compositions for improving the adhesion of putty paints to rust-proof steel sheets. For example, in Patent Document 2, adhesion is improved by using unsaturated polyester and a part of the polyhydric alcohol component of the resin composition as an ethylene oxide of bisphenol A and / or a propylene oxide derivative of bisphenol A. However, no attempt has been made to simultaneously improve odor and increase the flash point.

JP-A-57-74316 Japanese Patent Application Laid-Open No. 64-1000066 Japanese Patent Publication No. 61-43337 JP-A-57-200331

  The present invention relates to a resin composition having a low odor and a high flash point, and excellent in drying property, toughness, durability and adhesion to a substrate, and a putty using this resin composition as a binder. A paint is provided.

で表されるアリルグリシジルエーテルと５〜４５モル％のジシクロペンタジエンとを多塩基酸成分(a) の総モル数に対する多価アルコール成分(b) の総モル数の割合を１．０〜２．０の範囲として反応させて得られる不飽和ポリエステル１０〜３５重量％と、
必要に応じて（Ｂ）エポキシ樹脂６０〜１００当量％（対エポキシ基）に、不飽和一塩基酸を反応させて得られる不飽和エステル０〜３５重量％と
（Ｃ）一般式(II)

（式中、Ｒ¹は、炭素原子数1〜１２個のアルキレン基、または少なくとも１個の酸素原子で結合された少なくとも２個のアルキレン鎖からなり、各アルキレン鎖が少なくとも２個の炭素原子を有し、合計で４〜１２個の炭素原子を有するオキサアルキレン基を意味し、Ｒ^２は、水素またはメチル基を意味する）で表される化合物３０〜９０重量％とを含有してなる樹脂組成物とを含有してなる樹脂組成物に関する。
また本発明は、前記記載の樹脂組成物に、さらに（Ｄ）不活性な微粒子状および／または粒状の無機充填材を（Ａ）成分、（Ｂ）成分および（Ｃ）成分の総量に対して３０〜４００重量％含有させてなるパテ塗料に関する。
また本発明は、前記パテ塗料に、さらに（Ｅ）有機過酸化物を（Ａ）成分、（Ｂ）成分および（Ｃ）成分の総量に対して０．１〜１０重量％含有させてなるパテ塗料に関する。
また本発明は、前記パテ塗料に、さらに（Ｆ）芳香族アミン系促進剤を（Ａ）成分、（Ｂ）成分および（Ｃ）成分の総量に対して０．０１〜１０重量％を含有させるか、（Ｇ）多価金属塩若しくは錯体を（Ａ）成分、（Ｂ）成分および（Ｃ）成分の総量に対して０．０１〜１０重量％含有させるか、またはこれらの両方を含有させるパテ塗料に関する。 The present invention comprises (A) (a) a saturated polybasic acid and an α, β-unsaturated polybasic acid, and the use ratio thereof is 0 to 90: 100 to 10 mol% (saturated polybasic acid: α, β -Unsaturated polybasic acid), and (b) 10-50 mol% of the general polyhydric alcohol component is represented by the general formula (I)

The ratio of the total number of moles of the polyhydric alcohol component (b) to the total number of moles of the polybasic acid component (a) is 1.0 to 2 10 to 35% by weight of unsaturated polyester obtained by reacting in the range of 0.0,
If necessary, 0 to 35% by weight of an unsaturated ester obtained by reacting (B) 60 to 100 equivalent% (based on epoxy group) of an epoxy resin with an unsaturated monobasic acid, and (C) the general formula (II)

(Wherein R ¹ comprises an alkylene group having 1 to 12 carbon atoms, or at least two alkylene chains bonded by at least one oxygen atom, each alkylene chain having at least two carbon atoms) And an oxaalkylene group having 4 to 12 carbon atoms in total, and R ² represents hydrogen or a methyl group) and a resin containing 30 to 90% by weight The present invention relates to a resin composition comprising the composition.
In the present invention, the resin composition described above may further contain (D) an inert fine particle and / or granular inorganic filler with respect to the total amount of component (A), component (B) and component (C). The present invention relates to a putty paint containing 30 to 400% by weight.
In the present invention, the putty paint further comprises (E) an organic peroxide in an amount of 0.1 to 10% by weight based on the total amount of the components (A), (B) and (C). It relates to paint.
In the present invention, the putty paint further contains (F) an aromatic amine accelerator in an amount of 0.01 to 10% by weight based on the total amount of the components (A), (B) and (C). Or (G) a polyvalent metal salt or complex containing 0.01 to 10% by weight based on the total amount of component (A), component (B) and component (C), or a putty containing both of them. It relates to paint.

The unsaturated polyester resin composition of the present invention can be suitably used as a binder for automobiles and vehicle repair putty paints having excellent drying properties, polishing properties, moisture resistance, and heat cycle properties. It is also possible to use it for lining materials such as resin concrete by using fiber reinforced plastic, casting material by using glass fiber or organic fiber as secondary material, and using inorganic filler such as sand or calcium carbonate as secondary material. It is.
The putty paint of the present invention is suitable for repairing automobiles and vehicles excellent in drying property, polishing property, moisture resistance, and heat cycle property.

  First, the unsaturated polyester (component (A)), which is an essential component of the resin composition of the present invention, will be described. The polybasic acid component (a) used in the present invention is composed of a saturated polybasic acid and an α, β-unsaturated polybasic acid, and the use ratio thereof is a saturated polybasic acid: α, β-unsaturated polybasic acid. = 0 to 90: 100 to 10 mol%, preferably 0 to 40: 100 to 60 mol%. If the proportion of the α, β-unsaturated polybasic acid is outside the above range, curing at room temperature will be slow, and the drying and polishing properties of the putty coating will be reduced. Examples of the saturated polybasic acid include phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, het acid, adipic acid, sebacic acid and the like. Examples of the α, β-unsaturated polybasic acid include maleic anhydride, maleic acid, fumaric acid, itaconic acid, citraconic acid and the like. Two or more of these saturated polybasic acids or α, β-unsaturated polybasic acids may be used in combination.

  As the polyhydric alcohol component (b) used in the present invention, a drying oil and an allyl compound are used as materials for imparting the drying and polishing properties of the putty coating film. In the former, unreacted components are likely to remain and are easily attacked by zinc ions. For the latter, glycerin, trimethylolpropane and pentaerythritol monoallyl ether, diallyl ether or triallyl ether and glycidyl allyl ether are generally used, but ether glycol components are unreacted components as well as oil components. And tend to be easily attacked by zinc ions. Among allyl compounds, allyl glycidyl ether is excellent in reactivity, no unreacted components remain, can be introduced into the resin skeleton more completely, and is excellent in adhesion to a zinc-treated steel sheet.

  In the present invention, the allyl glycidyl ether represented by the general formula (I) is used in an amount of 10 to 50 mol%, preferably 15 to 45 mol%, based on the component, thereby preventing formation of metal soap by zinc ions. It is possible to prevent hydrolysis by zinc hydroxide and to improve the drying and polishing properties of the putty coating film.

  If the amount of allyl glycidyl ether used is less than 10 mol% of the total polyhydric alcohol component, the drying and polishing properties of the putty coating are not sufficient, and if it exceeds 45 mol%, the drying and polishing properties are good. The hardness is not sufficient and the coating film is easily damaged during polishing.

  Examples of other polyhydric alcohol components include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol, and 1,6-hexane. Diol, trimethylolpropane, glycerin, trimethylolethane, pentaerythritol, hydrogenated bisphenol A, ethylene or propylene addition derivatives of bisphenol A, and the like are used. These may be used in combination. Furthermore, as a component of polyhydric alcohol having air-drying properties, glycerin, trimethylolpropane and pentaerythritol monoallyl ether, diallyl ether or triallyl ether, a range in which the adhesiveness of the putty coating to the electrogalvanized steel sheet is not reduced, Specifically, you may use at 2 mol% or less in the component of all the polyhydric alcohols.

  The ratio of the polybasic acid component component (a) and the polyhydric alcohol component (b) is such that the ratio of the total number of moles of the component (b) to the total number of moles of the component (a) is 1.0 to 2.0, preferably Is in the range of 1.1 to 1.8. If the total molar ratio of the polyhydric alcohol component is less than 1.0, the acid value of the unsaturated polyester is not sufficiently reduced, and the water resistance of the putty coating film tends to decrease. On the other hand, if it exceeds 2.0, the molecular weight of the unsaturated polyester is reduced, and the curability of the putty coating film is deteriorated, so that the drying property and the polishing property are lowered, and the adhesion to the electrogalvanized steel sheet is also lowered.

  The unsaturated polyester (A) used in the present invention can be obtained by a conventional method. For example, a quaternary ammonium salt (eg, tetraammonium chloride, dimethyldodecylbenzylammonium chloride, etc.) or an alkali metal salt (eg, potassium benzoate, benzoic acid) as a catalyst for ring-opening reaction of the epoxy group of allyl glycidyl ether of the polyhydric alcohol component Sodium, etc.) is used in an amount of 0.05 to 5.0% by weight with respect to allyl glycidyl ether, and after a preliminary addition reaction at 80 to 140 ° C. with a part or all of the polybasic acid component (a), the remaining And a polycondensation reaction at 150 to 220 ° C., or a part or all of the polybasic acid component (a) and the polyhydric alcohol component (b) are allyl. After prepolycondensation reaction at 150 to 220 ° C. with a polyhydric alcohol component excluding glycidyl ether, allyl glycidyl Ether was added and ring opening catalysts, obtained by polycondensation reaction at 150 to 220 ° C..

  The molecular weight of the unsaturated polyester (A) is usually 500 to 10,000, preferably 800 to 3,000, from the viewpoint of workability of the putty paint, water resistance and adhesion of the coating film, and the acid value is usually It is adjusted to 100 or less, more preferably 50 or less.

（式中、ｘは０〜１５の範囲の整数である）で表される化合物が用いられる。 Next, the unsaturated ester (component (B)) which is an essential component of the resin composition of the present invention will be described. The unsaturated ester used in the present invention is obtained by reacting an epoxide compound with an unsaturated monobasic acid and a polybasic acid used as necessary. The epoxy resin is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule. For example, the general formula (III)

(Wherein x is an integer in the range of 0-15) is used.

  As commercially available products of this compound, Epicoat 828, Epicoat 1001, Epicoat 1004 (above, Yuka Shell Epoxy Co., Ltd. trade name), AER-664H, AER-331, AER-337 (above, Asahi Kasei Kogyo Co., Ltd.) Name), DER330, DER660, DER664 (above, Dow Chemical Japan Co., Ltd. trade name). Moreover, the compound which substituted some hydrogen atoms of the said epoxy resin with halogen (for example, bromine) can also be used. As this type of commercial products, Epototo YDB-400, YDB-340 (above, Toto Kasei Co., Ltd. trade name), DER-542, DER-511, DER-580 (above, Dow Chemical Japan Co., Ltd. trade name) ), 1045, 1050, 1046, DX-248 (above, Yuka Shell Epoxy Co., Ltd. trade name) and the like.

（式中、Ｒ³、Ｒ⁴およびＲ⁵はそれぞれ独立に水素原子またはアルキル基を示し、ｘは０〜１５の範囲の整数である）で表される化合物を用いることもできる。 In addition, general formula (IV)

(Wherein R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom or an alkyl group, and x is an integer in the range of 0 to 15) can also be used.

  Examples of commercially available products of this compound include D.E.N.431, D.E.N.438 (above, trade name of Dow Chemical Japan Co., Ltd.), Epicoat 152, and Epicoat 154 (above, trade name of Yuka Shell Epoxy Co., Ltd.). Moreover, YDCN-702, YDPN-638 (above, Toto Kasei Co., Ltd. trade name), CY208, CY221, CY350, XB2615, CY192, CY184 (above, Nihon Ciba Geigy Co., Ltd. trade name), etc. are also used.

  These epoxy resins can be used alone or in combination of two or more. Also, in order to improve workability, epi-bis type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, etc. and low viscosity epoxy resin such as bisphenol AD type epoxy resin may be used in combination. it can.

Examples of the unsaturated monobasic acid to be reacted with the epoxide compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, tricyclo [5.2.1.0 ^2,6 ] -4-decene-8 or 9 residues. And partially esterified carboxylic acid containing an unsaturated dibasic acid residue as a constituent element can be used. Examples of partially esterified carboxylic acids include 8 or 9-hydroxytricyclodecene-4- [5.2.1.0 ^2,6 ] 1.00-1.20 moles and maleic anhydride, itaconic acid, citracone Examples thereof include unsaturated dibasic acid monoesters obtained by heating 1 mol of an unsaturated dibasic acid such as an acid at 70 to 150 ° C. in an inert gas stream. In addition, unsaturated dibasic acids such as maleic acid, fumaric acid and itaconic acid are added to tricyclodecadiene-4,8- [5.2.1.0 ^2,6 ] in the presence of a catalyst such as sulfuric acid and Lewis acid. An unsaturated dibasic acid monoester obtained by addition can also be used.

  From the viewpoint of the toughness and durability of the coating film, the epoxide compound can be reacted with a polybasic acid as necessary. Polybasic acids include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, adipic acid, azelaic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic anhydride, etc. Is mentioned. In addition, it is preferable to use a dibasic acid having 12 or more carbon atoms as the polybasic acid used as necessary. Specific examples of this dibasic acid include ULB-20 (trade name of Okamura Oil Co., Ltd.), which is a mixture of isomers of todecanedioic acid and unsaturated dibasic acid having 16 carbon atoms, saturated dibasic having 20 carbon atoms. Examples thereof include SL-20 (trade name of Okamura Oil Co., Ltd.) which is a mixture mainly composed of acid, and dimerized fatty acid (dimer acid having 36 carbon atoms) using tall oil fatty acid as a raw material. Examples of commercially available dimer acids include Versadim 216, Versadim 288 (trade name of Henkel Hakusui Co., Ltd.), Haridimer # 200 (trade name of Harima Kasei Co., Ltd.), and the like.

  The unsaturated ester of component (B) can be obtained by reacting an epoxide compound with an unsaturated monobasic acid and a polybasic acid used as necessary. The reaction temperature at this time is preferably 60 to 150 ° C, more preferably 70 to 130 ° C. The blending ratio of the epoxide compound to the unsaturated monobasic acid and the polybasic acid used as needed is such that the carboxyl group of these acid components and the epoxy group of the epoxide compound are in an equivalent ratio (carboxyl group: epoxy group). The range is preferably 0: 0.9 to 1.0: 1.2, more preferably 1.0: 0.9 to 1.0: 1.1. When the epoxy group is less than 0.9 or more than 1.2 with respect to 1 equivalent of carboxyl group, desired coating film performance such as durability, toughness, drying property and strength may not be obtained. The production of the unsaturated ester can be determined by quantifying the unsaturated monobasic acid and the carboxyl group of the polybasic acid used as necessary, and examining the acid value. The acid value is preferably 50 or less, more preferably 15 or less.

  In the reaction, it is preferable to use a polymerization inhibitor such as hydroquinone, parabenzoquinone, p-tertiary butyl catechol, hydroquinone monomethyl ether in order to prevent gelation by polymerization. In this esterification reaction, quaternary ammonium salts such as trimethylbenzylammonium chloride and pyridinium chloride, tertiary amines such as triethylamine and dimethylaniline, ferric chloride, lithium hydroxide, lithium chloride, stannic chloride. The reaction time can also be shortened using an esterification catalyst such as

  Next, the compound (component (C)) represented by the general formula (I) described above, which is an essential component of the resin composition of the present invention, will be described. Examples of the compound represented by the general formula (I) used in the present invention include dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxypropyl acrylate, dicyclopentenyloxypropyl methacrylate and the like. It is done.

  As described in Patent Document 3, these compounds are obtained by subjecting dicyclopentadiene to addition reaction of alkylene glycol or oxaalkylene glycol and the resulting alkylene glycol monodicyclopentenyl ether or oxaalkylene glycol monodicyclopentenyl ether. It can be produced by a condensation reaction with methacrylic acid or a transesterification reaction with methyl methacrylate. It is also possible to replace this methacrylic acid or methyl methacrylate with acrylic acid or methyl acrylate. Further, as described in Patent Document 4, it can also be produced by addition reaction of alkylene glycol monoacrylate or alkylene glycol monomethacrylate with dicyclopentadiene.

  The compound represented by the general formula (II) includes a monomer having a flash point of 80 ° C. or more, for example, glycidyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, 2-ethylhexyl acrylate, lauryl acrylate, and a polyethylene having a molecular weight of 300 to 200. Diacrylate or dimethacrylate of glycol or polypropylene glycol can be used in combination. Such a monomer is preferably 30% by weight or less based on the whole monomer, and a monomer having a functional group such as glycidyl methacrylate is preferably used at 5% by weight or less based on the whole monomer.

The resin composition of the present invention comprises (A) (a) a saturated polybasic acid and an α, β-unsaturated polybasic acid, and the use ratio thereof is 0 to 90: 100 to 10 mol% (saturated polybasic acid : (Α, β-unsaturated polybasic acid), and (b) in all polyhydric alcohol components, 10 to 50 mol% of allyl glycidyl ether represented by the general formula (I), It is obtained by reacting 45 mol% of dicyclopentadiene with a ratio of the total number of moles of the polyhydric alcohol component (b) to the total number of moles of the polybasic acid component (a) in the range of 1.0 to 2.0. 5 to 35% by weight of unsaturated polyester,
If necessary, (B) 0 to 35% by weight of an unsaturated ester obtained by reacting an epoxy resin with 60 to 100 equivalent% (epoxy group) of an unsaturated monobasic acid, and (C) the general formula (II) ( In the formula, R ¹ is composed of an alkylene group having 1 to 12 carbon atoms or at least two alkylene chains bonded with at least one oxygen atom, and each alkylene chain has at least two carbon atoms. And an oxaalkylene group having 4 to 12 carbon atoms in total, and R ² represents hydrogen or a methyl group). The present invention relates to a resin composition containing a product. The putty coating film obtained using this is also brittle and low in strength. The resin composition of the present invention can be suitably used as a binder for putty paints because it is excellent in low odor, dryness of coating film, toughness, durability and adhesion to steel plates, particularly rust-proof steel plates. By using 10 to 50 mol%, preferably 15 to 45 mol%, of allyl glycidyl ether represented by the above formula (I), the formation of metal soap by zinc ions and the addition of water by zinc hydroxide are prevented. It is possible to prevent decomposition and further improve the drying and polishing properties of the putty coating. If the amount of allyl glycidyl ether used is less than 10 mol% of the total polyhydric alcohol component, the drying and polishing properties of the putty coating are not sufficient, and if it exceeds 45 mol%, the drying and polishing properties are good. The hardness is not sufficient and the coating film is easily damaged during polishing.

  As described above, the putty paint of the present invention comprises (A) component, (B) component, and (C) component, and (D) inert fine particulate and / or granular inorganic filler. , (B) component and (C) component. The putty paint of the present invention can be obtained by adding (E) an organic peroxide to the putty paint. Furthermore, the putty paint of the present invention is obtained by adding (F) an aromatic amine accelerator, (G) a polyvalent metal salt or complex, or both (F) and (G) components to the putty paint. It is done.

  The putty paint containing an inorganic filler as the component (D) in the resin composition of the present invention can be used at various working temperatures by appropriately combining the components (E), (F) and (G). It can be radically cured. In particular, when it is necessary to eliminate surface stickiness at or near room temperature, the (G) component polyvalent metal salt and / or complex is an essential component, and the (E) component and the (F) component are combined. It is preferable to use in combination.

  As the inert fine particle and / or granular inorganic filler of component (D), talc, mica, kaolin, calcium carbonate, clay, ceramic powder, alumina, aluminum hydroxide and the like are used. The amount of the inorganic filler used is in the range of 30 to 400% by weight, preferably 100 to 300% by weight, based on the total amount of the components (A), (B) and (C). If the amount of the inorganic filler used exceeds 400% by weight, it will not be able to exhibit a sufficient effect as a binder of the resin composition, and the durability of the coating film tends to decrease. Abrasiveness tends to decrease. As the organic peroxide of component (E), benzoyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, acetylacetone peroxide, and the like can be used. The amount used is 0.1 to 10% by weight, preferably 0.5 to 3% by weight, based on the putty paint. If the amount of the organic peroxide is less than 0.1% by weight, the amount of radicals generated from the organic peroxide is insufficient, and the resin composition may not be cured sufficiently. The product exhibits the function of a plasticizer, and the cured resin tends to be soft.

  As the aromatic amine accelerator of component (F), aniline, N, N-dimethylaniline, N, N-diethylaniline, toluidine, N, N-dimethyl-p-toluidine, N, N-di (hydroxyethyl) ) Toluidine, p-dimethylaminobenzaldehyde and the like can be used in one or more combinations. The amount used is 0.01 to 10% by weight, preferably 0.1 to 1% by weight, based on the total amount of component (A), component (B) and component (C). If the amount used is less than 0.01% by weight, the accelerating effect tends to be insufficient, and if it exceeds 10% by weight, the plastic effect tends to work and the strength of the resin cured product tends to decrease.

  The polyvalent metal salt and / or complex of component (G) is generally called a desiccant (dryer), and metal salts of higher fatty acids are well known. Examples thereof include naphthenic acid and polyvalent metal salts of octenoic acid. The polyvalent metal is calcium, copper, zirconium, manganese, cobalt, lead, iron, vanadium or the like. Particularly preferred examples include cobalt octenoate and cobalt naphthenate. Examples of complexes are well known acetylacetone complexes, such as cobalt acetylacetonate and manganese acetylacetonate. This component (F) is used in an amount of 0.01 to 10% by weight, preferably 0.01 to 5% by weight, based on the total amount of the components (A), (B) and (C). It has a function of promoting the action of oxides. When the amount of the component (G) used is less than 0.01% by weight, such a promoting effect tends to be insufficient. On the other hand, when the amount exceeds 10% by weight, such a promoting effect is not further improved.

  If necessary, pigments, dyes, antioxidants, ultraviolet absorbers, fluidity modifiers, thixotropic agents, plasticizers, waxes, and the like can be added to the resin composition and putty paint of the present invention. Examples of coloring pigments include titanium white, bengara, aniline black, carbon black, cyanine blue, manganese blue, iron black, chrome yellow, chrome green, and mapico yellow.

Hereinafter, the present invention will be described in detail with reference to examples. In the following examples, parts and% mean parts by weight and% by weight, respectively.
Example 1

<Manufacture of unsaturated polyester resin composition>
In a 2 liter four-necked flask equipped with a stirrer, a gas inlet tube, a thermometer and a reflux condenser, 813.6 parts (3.39 mol) of hydrogenated bisphenol A (manufactured by Shin Nippon Chemical Co., Ltd., Rikabinol HB), propylene glycol 171.8 parts (2.26 mol), dicyclopentadiene 111.9 parts (0.85 mol), maleic anhydride 553.7 parts (5.65 mol), hydroquinone 0.2 parts and circulating xylol 40 parts The mixture was heated at 140 ° C. for 1 hour while blowing nitrogen gas, heated from 140 ° C. to 190 ° C. over 3 hours, and heated at the same temperature until the acid value of the contents in the kettle reached 70-60. The acid value reached 65.7 after heating at 190 ° C. for 1.5 hours. Next, after cooling to 120 ° C., 193.2 parts (1.70 mol) of allyl glycidyl ether (manufactured by NOF Corporation, Epiol A) and dimethyldodecylbenzylammonium chloride (manufactured by NOF Corporation, cation M2-100 as a ring-opening catalyst) ) 3.86 parts were added, and the temperature was raised from 120 ° C. to 175 ° C. in 4 hours. Sampling was carried out at the same temperature over time, and the viscosity (Gardner, 25 ° C., the same applies hereinafter) and acid value when diluted with styrene to a heating residue of 60% were measured. The acid value was 22 for 5 seconds. Next, after cooling to 155 ° C, increasing the amount of nitrogen gas injected, measuring the viscosity and acid value when diluted to 60% with styrene while removing the xylol in the kettle, after heating at 160 ° C for 2 hours The unsaturated polyester (I) was obtained with the end point at which the viscosity was 6.3 seconds and the acid value was 15.2. Resin composition (I) dissolved in 400 parts of dicyclopentenyloxyethyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., FA-512M) obtained by adding 0.1 part of hydroquinone to unsaturated polyester (I) 600 produced by the above method Got.
Example 2

Next, in a 1 liter four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a condenser, Episbis type epoxy resin Ep-828 (trade name of Yuka Shell Epoxy Co., Ltd., epoxy equivalent 185), 550 parts, allyl Add 50 parts of glycidyl ether, 293 parts of methacrylic acid, 0.2 part of hydroquinone and 2 parts of dimethyldodecylbenzylammonium chloride and heat at 100 ° C. for 10 hours while blowing oxygen to obtain an unsaturated ester (I) having an acid value of 10. It was. 600 parts of the unsaturated polyester (I) and unsaturated ester (I) produced by the above method were mixed at a ratio of 50:50 to prepare 600 parts, and dicyclopentenyloxyethyl methacrylate (Hitachi Chemical Co., Ltd.) to which 0.1 part of hydroquinone was added. The resin composition (II) was obtained by dissolving in 400 parts of FA-512M manufactured by Kogyo Co., Ltd.
Comparative Example 1

Using the same apparatus as in Example 1, 813.6 parts (3.39 mol) of hydrogenated bisphenol A (manufactured by Shin Nippon Rika Co., Ltd., Rikabinol HB), 171.8 parts (2.26 mol) of propylene glycol, anhydrous 553.7 parts (5.65 mol) of maleic acid, 0.2 part of hydroquinone and 40 parts of xylol for circulation were added and the temperature was raised to 190 ° C. in the same manner as in Example 1. After heating for 2 hours, the acid value was 68.7. It was. Next, the mixture was cooled to 120 ° C., Epiol A, 145.9 parts (1.28 mol) and cation M2-100, 2.92 parts were added, the temperature was raised to 175 ° C. in the same manner as in Example 1, and the viscosity was similarly changed. And the acid value was measured. After a temperature increase of 175 ° C., the viscosity was 3.3 seconds and the acid value was 15.6 after 6 hours. Then, the mixture was cooled to 155 ° C., and the viscosity and acid value were measured in the same manner as in Example 1 while removing the xylol in the kettle. After heating at 155 ° C. for 1.6 hours, the viscosity was 6.8 seconds and the acid value The end point was reached when 11.7 was indicated, and unsaturated polyester (II) was obtained. Resin composition dissolved in 400 parts of dicyclopentenyloxyethyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., FA-512M) obtained by adding 0.1 part of hydroquinone to 600 parts of this unsaturated polyester (II) as in Example 1. (III) was obtained.
Comparative Example 2

As in Example 2, 600 parts of this unsaturated polyester (II) and unsaturated ester (I) were mixed at a ratio of 50:50 to prepare dicyclopentenyloxyethyl methacrylate (0.1 part of hydroquinone). It was dissolved in 400 parts of Hitachi Chemical Co., Ltd. (FA-512M) to obtain a resin composition (IV).
Comparative Example 3

  600 parts of unsaturated ester (I) obtained in Example 1 was dissolved in 400 parts of styrene to which 0.1 part of hydroquinone was added to obtain a resin composition (V). This resin composition (V) had a viscosity of 6.7 seconds and an acid value of 18.1.

<Test example>
Characteristics of resin compositions (I) to (V) obtained in Examples 1 and 2 and Comparative Examples 1 to 3 (low odor) and characteristics of putty coating films prepared using these resin compositions (drying) Properties, abrasiveness, adhesion and moisture resistance) were examined as follows.

1. Characteristics of resin composition (1) Odor sensitivity (low odor)
An odor sensor having an intake pipe and an exhaust pipe is attached to a sealed container having an internal volume of 20 liters, and 5 g of the resin compositions (I) to (V) produced in each of the examples and comparative examples are left at the bottom of the container, The odor sensitivity value after 90 minutes was measured. As a sensor, a new Cosmos Electric Co., Ltd. Naoi sensor XP329 type was used. The odor sensitivity value of the sensor indicates a strong odor as the value increases.

2. Putty coating characteristics (1) Putty paint formulation The materials shown in Table 1 were collected in 300 ml round cans and stirred with a high-speed dissolver for 15 minutes to uniformly disperse them.

(2) Adjusting the test plate An iron plate (SPCC-SB, manufactured by Nippon Test Panel Industry Co., Ltd.) and an electrogalvanized plate (manufactured by Nippon Steel Corp., silver zinc) were used as the test plate. 150 was lightly polished.
(3) Preparation of test piece 2% of 55% methyl ethyl ketone peroxide was added to each of the coating materials prepared in (1), and put on each test plate prepared in (2) to a thickness of 2 mm.
(4) Measurement of coating film performance The coating film performance shown below was tested for putty paints obtained using the resin compositions of Examples 1 to 4 and Comparative Examples 1 to 3, and the results are shown in Table 2.
i) Dryability: After putting on an iron plate, the surface was lightly polished with a finger using water-resistant paper # 150 every time at room temperature (20 ° C.), and the time (min) at which polishing was possible was measured.
ii) Abrasiveness: putty on an iron plate, left at room temperature (20 ° C) for 4 hours, then polished with fingers using water-resistant paper # 150, and compared the ease of polishing, and evaluated as follows did.
○: Even when lightly polished, the putty coating is often shaved.
Δ: The putty coating is scraped, but the polishing feels somewhat heavy.
X: Polishing is heavy and the putty coating cannot be shaved well.
iii) Adhesiveness: putty on each test plate, left at room temperature (20 ° C.) for 16 hours, then baked in a 120 ° C. drier for 60 minutes, cooled to room temperature, and bent at 90 ° angle from the center. The putty adhesion of the bent part was examined and evaluated as follows.
○: Putty is attached.
Δ: 50% putty is attached.
X: Adherence of putty is not observed.
iv) Moisture resistance: putty on each of the above test plates, left at room temperature (20 ° C.) for 16 hours, then polished the surface in order of water-resistant paper # 240, # 150 and # 400 to smooth the surface . A commercially available acrylic urethane paint (made by Isamu Paint, high art) is spray-coated on the polished putty coating (film thickness 40 μm), left at room temperature (20 ° C.) for 30 minutes, and then dried at 60 ° C. for 60 minutes. I let you. After cooling, the sample was placed in a pre-staring box (RH 99%, temperature 50 ° C.) for 72 hours, and the state of the coating film surface (pre-star, foam having a diameter of about 2 mm) and putty adhesion when bent to a 90 ° angle were examined. Prestar was evaluated as follows, and putty adhesion was performed in the same manner as in iii).
○: No occurrence of blister.
(Triangle | delta): The blister has generate | occur | produced in 20% of the coating films.
X: Blister is generated on the entire surface.
The above results are summarized in Table 2.

From the results of Table 2, the resin composition of the present invention has low odor, and the putty coating using the resin composition has a drying property, an abrasive property, an adhesion property, a moisture resistance and a heat cycle resistance. I found it excellent.

Claims (4)

(A) (a) It consists of a saturated polybasic acid and an α, β-unsaturated polybasic acid, and its use ratio is 0-90: 100-10 mol% (saturated polybasic acid: α, β-unsaturated polybasic acid). 10 to 50 mol% of the polybasic acid component which is a basic acid) and (b) the total polyhydric alcohol component is represented by the general formula (I)

The ratio of the total number of moles of the polyhydric alcohol component (b) to the total number of moles of the polybasic acid component (a) is from 1.0 to 2 10 to 70% by weight of unsaturated polyester obtained by reacting in the range of 0.0,
If necessary, 0 to 35% by weight of an unsaturated ester obtained by reacting (B) 60 to 100 equivalent% (based on epoxy group) of an epoxy resin with an unsaturated monobasic acid, and (C) the general formula (II)

(Wherein R ¹ comprises an alkylene group having 1 to 12 carbon atoms, or at least two alkylene chains bonded by at least one oxygen atom, each alkylene chain having at least two carbon atoms) An oxaalkylene group having a total of 4 to 12 carbon atoms, and R ² represents a hydrogen or methyl group). Saturated polyester resin composition. The resin composition according to claim 1, further comprising (D) an inert fine particle and / or granular inorganic filler in an amount of 30 to 400 with respect to the total amount of the component (A), the component (B), and the component (C). Putty paint made to contain by weight. The putty paint according to claim 2, further comprising (E) an organic peroxide in an amount of 0.1 to 10% by weight based on the total amount of the components (A), (B) and (C). . Whether the putty paint according to claim 3 further contains (F) an aromatic amine accelerator in an amount of 0.01 to 10% by weight based on the total amount of the component (A), the component (B) and the component (C). (G) 0.01 to 10% by weight of a polyvalent metal salt or complex with respect to the total amount of the component (A), the component (B) and the component (C), or a putty paint containing both of them .