JP4359575B2 - Unsaturated polyester resin composition and coating method using the same - Google Patents

Description

  The present invention relates to an unsaturated polyester resin composition excellent in curability, drying property and water resistance.

  In general, unsaturated polyester resins are relatively inexpensive compared to other resins, and are cured in a short time even at room temperature, so that workability is excellent, and various physical and chemical properties can be improved by selecting main raw materials. Therefore, it is widely used in various applications such as repair putty paints for vehicles such as automobiles, woodwork paints, molded products, and sealing materials. Unsaturated polyester resin compositions used in these applications are (1) quickly cured at normal temperature and excellent in surface drying, and (2) excellent adhesion to the substrate. Performance is required. In particular, (1) surface dryness at normal temperature is an important factor for workability.

Conventionally, styrene monomers have been used as reactive diluents for such unsaturated polyester resins from the viewpoints of curability and physical properties. However, in recent years, the use of styrene monomers is being regulated in terms of odor. Therefore, Patent Document 1 discloses an unsaturated polyester resin composition using hydroxyalkyl methacrylate as a reactive diluent instead of styrene monomer without reducing curability and physical properties. According to the composition, although the odor is low, the curability safety is excellent, and the surface drying property is excellent, the adhesion to the substrate may be insufficient.
JP 2002-332316 A

  The objective of this invention is providing the unsaturated polyester resin composition which can make surface dryness and adhesiveness with a base material compatible.

As a result of intensive studies to solve the above problems, the present inventors have found that an unsaturated polyester resin composition containing a specific polymerizable unsaturated monomer as a reactive diluent in the unsaturated polyester resin is used in the present invention. Reached. That is, the present invention
1. (I) an unsaturated polyester resin composition, (II) a polymerizable unsaturated compound containing a hydroxyl group, and (III) an unsaturated polyester resin composition containing a polymerizable unsaturated compound represented by the following formula (1):

(In the above formula (1), R ¹ represents an alkylene group having 2 to 12 carbon atoms, n represents an integer of 0 to 2, and when n is 2, each R ¹ in the repeating unit is the same. Or the total number of carbon atoms of R ¹ is 4 to 24, and R ² is a methyl group or a hydrogen atom).
2. The blending ratio of the unsaturated polyester resin (I), the polymerizable unsaturated compound (II) containing a hydroxyl group and the polymerizable unsaturated compound (III) represented by the formula (1) is the components (I) and (II). And component (I) is 25 to 85% by weight, component (II) is 5 to 65% by weight, and component (III) is 10 to 70% by weight, based on the total weight of (III). The unsaturated polyester resin composition according to item 1,
3. The unsaturated polyester resin (I), wherein the unsaturated polyester resin (I) contains 1 to 40 mol% of units derived from a cycloaliphatic unsaturated polybasic acid based on the total number of moles of all structural units. Polyester resin composition,
4). Item 4. The unsaturated polyester resin (I) according to any one of items 1 to 3, wherein the unsaturated polyester resin (I) contains 0.5 to 10 mol% of units derived from bisphenols based on the total number of moles of all structural units. Saturated polyester resin composition,
5. The unsaturated polyester according to any one of 1 to 4, wherein the unsaturated polyester resin (I) contains 5 to 50 mol% of allyl ether units of polyhydric alcohol based on the total number of moles of all structural units. Resin composition,

6). Item 1 to item 5 wherein the unsaturated polyester resin (I) contains a unit derived from a cycloaliphatic unsaturated polybasic acid, a unit derived from a bisphenol and an allyl ether unit of a polyhydric alcohol in the same molecule. 6. The unsaturated polyester resin composition according to any one of The unsaturated polyester resin (I) comprises an unsaturated polyester resin (I-1) containing a unit derived from a cycloaliphatic unsaturated polybasic acid and an allyl ether unit of a polyhydric alcohol; 1 to 6 which is a resin mixture comprising an unsaturated polyester resin (I-2) containing a unit derived from a polybasic acid other than a basic acid, a unit derived from a bisphenol, and an allyl ether unit of a polyhydric alcohol. The unsaturated polyester resin composition according to any one of the items,
8).
The unsaturated polyester resin composition according to 1, wherein the unsaturated polyester resin (I) contains an allyl ether unit, a terephthalic acid unit, and an ethylene glycol unit of a polyhydric alcohol in the same molecule,
9. Furthermore, the unsaturated polyester resin composition of any one of 1 thru | or 8 containing a rust preventive agent,
10. 10. The unsaturated polyester resin composition according to 9, wherein the rust inhibitor is at least one rust preventive pigment selected from molybdate, phosphomolybdate, metaborate, and cyanamide zinc calcium.
11. Furthermore, the unsaturated polyester resin composition of any one of 1 thru | or 10 containing the aromatic amine represented by Formula (2),

(Wherein R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group having 1 to 5 carbon atoms, an aryl group or an alkoxy group, and R ⁵ is a hydrogen atom. , Represents an optionally substituted alkyl group having 1 to 20 carbon atoms or an aryl group).
12. A coating composition containing the unsaturated polyester resin composition according to any one of items 12.1 to 11.
13. A putty composition containing the unsaturated polyester resin composition according to any one of items 11 to 11;
14 A coating method characterized by applying the composition according to item 12 or 13 to a substrate surface and overcoating it,
About.

  According to the unsaturated polyester resin composition of the present invention, it is possible to form a coating film that is excellent in surface drying and water resistance and excellent in adhesion to a substrate surface while ensuring a good coating environment. Is possible. The unsaturated polyester resin composition of the present invention is particularly useful for repair putty for automobiles, railway vehicles, industrial equipment, woodworking, etc., and is not limited to repairing cracks and sealing joints in buildings and furniture. It is useful for various applications such as lining materials, lining materials, FRP molded products, regicon and cast products.

The present invention relates to an unsaturated polyester resin composition comprising (I) an unsaturated polyester resin, (II) a polymerizable unsaturated compound containing a hydroxyl group, and (III) a polymerizable unsaturated compound represented by the above formula (1). It is a thing.

Unsaturated polyester resin (I)
As unsaturated polyester resin (I) used for the composition of this invention, the conventionally well-known resin obtained by esterifying the component containing a polybasic acid and a polyhydric alcohol can be used without a restriction | limiting.
Examples of the polybasic acid include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride Unsaturated polybasic acid such as het anhydride, hymic anhydride; phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid, hexa Hydroisophthalic 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 2,3-naphthalenedicarboxylic anhydride, 4, '- biphenyl dicarboxylic acid and a saturated polybasic acid such as these dialkyl esters can be mentioned, and these may be used in combination one or more.

In the present invention, it is desirable to contain an unsaturated polybasic acid as a polybasic acid from the viewpoint of curability.
Moreover, it is desirable to contain cycloaliphatic unsaturated polybasic acid as unsaturated polybasic acid from the point which can improve surface dryness more.
Examples of the cycloaliphatic unsaturated polybasic acid include tetrahydrophthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and the like, and methyltetrahydrophthalic anhydride is particularly preferable.

The unit derived from the cycloaliphatic unsaturated polybasic acid is desirably contained in an amount of 1 to 40 mol%, preferably 5 to 35 mol%, based on the total number of moles of all structural units.
Examples of the polyhydric alcohol include diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3-butanediol, neopentyl glycol, 1 , 4-butanediol, 1,6-hexanediol, 1,9-nonanediol, bisphenols or adducts of bisphenols and alkylene oxide, 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, Kurohekishiru 4,4'-diol, 2,6-decalin glycol, 2,7-decalin glycol, etc. These may be used either alone or in combination.

  In the present invention, the unsaturated polyester resin (I) preferably contains a unit derived from bisphenols. Examples of the method for introducing such bisphenols include a method of using, as a polyhydric alcohol, a bisphenol or an adduct of the bisphenol and an alkylene oxide. Examples of the bisphenols include bisphenol A, bisphenol F, hydrogenated bisphenol A, and hydrogenated bisphenol F. Examples of the alkylene oxide include ethylene oxide and propylene oxide. Among these, an addition reaction product of bisphenol A and propylene oxide is preferable.

The unit derived from the bisphenols should be contained in an amount of 0.5 to 10 mol%, preferably 1 to 8 mol%, based on the total number of moles of all structural units.
Moreover, in this invention, in the manufacture of the said unsaturated polyester resin (I), you may contain the allyl ether of a polyhydric alcohol from the point which can further improve surface dryness. Examples of the allyl ether of the polyhydric alcohol 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, and 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, etc. It can, they may be used in combination one or more.

In the present invention, the unsaturated polyester resin (I) preferably contains 5 to 50 mol%, preferably 7 to 40 mol% of allyl ether units of polyhydric alcohol based on the total number of moles of all structural units. .
In the present invention, in particular, the unsaturated polyester resin (I) comprises a unit derived from a cycloaliphatic unsaturated polybasic acid, a unit derived from a bisphenol and an allyl ether unit of a polyhydric alcohol in the same molecule. An unsaturated polyester resin (I-1) containing a unit derived from a cycloaliphatic unsaturated polybasic acid and an allyl ether unit of a polyhydric alcohol; A resin mixture containing an unsaturated polyester resin (I-2) containing units derived from polybasic acids other than basic acids, units derived from bisphenols, and allyl ether units of polyhydric alcohols is desirable.

  The unsaturated polyester resin (I) may contain an allyl ether unit, a terephthalic acid unit, and an ethylene glycol unit of a polyhydric alcohol in the same molecule. In this case, from the viewpoint of curability of the formed coating film and surface drying properties, the allyl ether unit of the polyhydric alcohol is 5 to 50 mol%, preferably 10 to 35 mol%, based on the total number of moles of all structural units. From the viewpoint of water resistance and adhesion, the terephthalic acid unit is 1 to 30 mol%, preferably 3 to 20 mol%, preferably the ethylene glycol unit is based on the total number of moles of all structural units, based on the total number of moles of all structural units. 3 to 60 mol%, preferably 5 to 40 mol%.

  In the above unsaturated polyester resin, terephthalic acid units and ethylene glycol units should use bishydroxyethyl terephthalate as a polyhydric alcohol production raw material in particular because it is a condensation reaction under a temperature that suppresses the reaction of the allyl ether group. Thus, both constituent units can be easily introduced in one step. As bishydroxyethyl terephthalate, it is also possible to use a decomposition regenerated product of polyethylene terephthalate (PET).

  In the present invention, the unsaturated polyester resin (I) may be modified with a fatty acid as necessary. The fatty acid is preferably a dry oil fatty acid and / or a semi-dry oil fatty acid, such as fish oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid, linseed oil fatty acid, soybean oil fatty acid / sesame oil fatty acid / poppy oil fatty acid, Eno oil fatty acid, hemp seed fatty acid, grape kernel oil fatty acid, corn oil fatty acid, tall oil fatty acid, sunflower oil fatty acid, cottonseed oil fatty acid, walnut oil fatty acid, rubber seed oil fatty acid, hydienoic acid fatty acid, etc. It can be used in combination of two or more species.

  The unsaturated polyester resin (I) can be produced by a conventional method. For example, the unsaturated polyester resin (I) can be obtained by subjecting a component containing the polybasic acid and the polyhydric alcohol to a condensation reaction in a nitrogen atmosphere. The heating temperature during the condensation reaction is desirably in the range of 140 to 250 ° C, preferably 160 to 200 ° C, from the viewpoint of preventing gelation. The weight average molecular weight of the obtained unsaturated polyester resin (I) is in the range of 500 to 20,000, preferably 1,000 to 5,000, such as drying property, water resistance, and adhesion. Desirable from.

  In the present specification, the weight average molecular weight is a value obtained by converting the weight average molecular weight measured with a gel permeation chromatograph (“HLC8120GPC” manufactured by Tosoh Corporation) based on the weight average molecular weight of polystyrene. Columns are “TSKgel G-4000H × L”, “TSKgel G-3000H × L”, “TSKgel G-2500H × L”, “TSKgel G-2000H × L” (both manufactured by Tosoh Corporation, trade names) ), Mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 cc / min, detector: RI.

Polymerizable unsaturated compound containing a hydroxyl group (II)
In the present invention, the polymerizable unsaturated compound (II) containing a hydroxyl group is blended as a reactive diluent and has one hydroxyl group and one polymerizable unsaturated group in one molecule. Specifically, for example, C _{2 to} C ₈ such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and the like. Hydroxyalkyl (meth) acrylate, allyl alcohol, (meth) acrylate having a hydroxyl group such as a modified ε-caprolactone of the above C ₂ -C ₈ hydroxyalkyl (meth) acrylate; having a polyoxyethylene chain having a hydroxyl group at the molecular end (Meth) acrylate, etc. Not to be able to use. Among these, hydroxyalkyl (meth) acrylate, particularly hydroxyethyl methacrylate is preferred because of its good surface drying properties.

Polymerizable unsaturated compound (III) represented by formula (1)
In the present invention, the polymerizable unsaturated compound (III) represented by the following formula (1) is blended as a reactive diluent, and a coating film formed from the composition by the compound (III). Adhesion can be improved.

(In the above formula (1), R ¹ represents an alkylene group having 2 to 12 carbon atoms, n represents an integer of 0 to 2, and when n is 2, each R ¹ in the repeating unit is the same. Or the total number of carbon atoms of R ¹ is 4 to 24, and R ² is a methyl group or a hydrogen atom.
Specific examples of the compound (III) include dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxypropyl acrylate, dicyclopentenyloxypropyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate and the like. Can be mentioned.

Unsaturated polyester resin composition The unsaturated polyester resin composition of the present invention contains the unsaturated polyester resin (I), a polymerizable unsaturated compound (II) containing a hydroxyl group, and the polymerizable unsaturated compound (III). And
The blending ratio of the unsaturated polyester resin (I), the polymerizable unsaturated compound (II) containing a hydroxyl group and the polymerizable unsaturated compound (III) is the total weight of the components (I), (II) and (III). Based on the standard, component (I) is 25 to 85% by weight, preferably 30 to 80% by weight, component (II) is 5 to 65% by weight, preferably 7 to 57% by weight, and component (III) is 10 to 70%. It is desirable that the amount be 13% by weight, preferably 13 to 63% by weight.

When the component (I) is less than 25% by weight, the drying property and curability are insufficient. On the other hand, when the component (I) exceeds 85% by weight, the viscosity becomes high and the coating workability may be lowered. When the component (II) is less than 5% by weight, the surface drying property is insufficient. On the other hand, when the component (II) exceeds 65% by weight, the adhesion to the substrate may be lowered. If component (III) is less than 10% by weight, adhesion to the substrate is insufficient, while 70% by weight
If it exceeds 1, the surface drying property may be lowered.
The resin composition of the present invention contains the unsaturated polyester resin (I), the hydroxyl group-containing polymerizable unsaturated compound (II) and the polymerizable unsaturated compound (III) represented by the formula (1) as essential components. Further, a curing accelerator, a pigment and the like can be blended as necessary.

Examples of the curing accelerator include organic metals such as naphthenates such as cobalt naphthenate, copper naphthenate, and barium naphthenate, and octenoates such as cobalt octenoate, manganese octenoate, zinc octenoate, and vanadium octenoate. Compounds; tertiary amines; quaternary ammonium salts; and the like. These can be used alone or in combination of two or more. The amount used is 0.000 based on the total weight of the unsaturated polyester resin (I), the polymerizable unsaturated compound (II) containing a hydroxyl group and the polymerizable unsaturated compound (III) represented by the formula (1). A range of 01 to 5% by weight is suitable.

Examples of the pigment include extender pigments such as talc, mica, barium sulfate, kaolin, calcium carbonate, clay, silica, quartz, and glass; color pigments such as titanium white, bengara, carbon black, and iron black; and glass Balloons, plastic balloons and the like can also be included. These can be used alone or in combination of two or more. The amount of the pigment used is represented by the unsaturated polyester resin (I), the polymerizable unsaturated compound (II) containing a hydroxyl group, and the formula (1) from the viewpoints of polishing workability and finishability in putty applications. The amount is preferably in the range of 70 to 500 parts by weight, preferably 80 to 200 parts by weight, based on 100 parts by weight of the total amount of the polymerizable unsaturated compounds (III).

In this invention, it is desirable to mix | blend a rust preventive agent from the point of the water resistance improvement of a forming film. Examples of the rust inhibitor include phosphates such as zinc phosphate and calcium phosphate; polyphosphates such as aluminum dihydrogen triphosphate; molybdates such as zinc molybdate and calcium molybdate; aluminum phosphomolybdate and the like. Phosphomolybdate, borate, metaborate, such as barium metaborate, cyanamide, zinc, calcium, cations such as calcium, zinc, cobalt, lead, strontium, barium, etc. Modified silica, ion exchange silica by binding cations by ion exchange; rust preventive pigments such as aluminum pyrophosphate, 1- (benzothiazol-2-ylthio) succinic acid, (2-benzothiazole-2- (Ilthio) succinic acid di- (C ₁₂ -C ₁₄ alkylammonium) Benzothiazole-based compounds such as sodium salts; addition reaction products of 4-methyl-γoxo-benzenebutanoic acid and N-ethylmorpholine, addition reaction products of 4-methyl-γoxo-benzenebutanoic acid and zirconium, etc. Organic rust preventives such as ketocarboxylic acid can be used, and these can be used alone or in combination of two or more of them. The at least one rust preventive pigment selected from an acid salt type and a cyanamide zinc calcium type is particularly preferable from the viewpoint of improving the water-resistant adhesion property on the steel sheet surface.

The blending amount of the rust preventive is selected from the viewpoints of polishing workability, finish, curability, drying, spatability, heat-resistant yellowing, etc., unsaturated polyester resin (I), hydroxyl group-containing polymerizable unsaturated compound ( II) and 3 to 50% by weight, preferably 5 to 5% by weight relative to the total weight of the polymerizable unsaturated compound (III)
A range of 45% by weight is preferred.
In addition, the resin composition of the present invention may contain a curing aid accelerator and a polymerization inhibitor in order to adjust the curing rate. As the curing accelerator, for example, an aromatic amine represented by the following formula (2) is suitable.

(Wherein R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group having 1 to 5 carbon atoms, an aryl group or an alkoxy group, and R ⁵ is a hydrogen atom. Represents an optionally substituted alkyl group having 1 to 20 carbon atoms, or an aryl group.
Specific examples of the aromatic amine represented by the above formula (2) include 4-dimethylaminobenzoic acid, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, 4-dimethylamino. Isoamyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 3-dimethylaminobenzoic acid, ethyl 3-dimethylaminobenzoate, ethyl 3-dimethylaminobenzoate (n-butoxy), isoamyl 3-dimethylaminobenzoate, 2-dimethylhexyl 3-dimethylaminobenzoate, 2-dimethylaminobenzoic acid, ethyl 2-dimethylaminobenzoate, ethyl 2-dimethylaminobenzoate (n-butoxy), isoamyl 2-dimethylaminobenzoate, 2-dimethylamino Examples include 2-ethylhexyl benzoate. Among these, amines having a dimethylamino group, particularly 4-dimethylaminobenzoic acid, are preferable because of their good curability and little yellowing of the top coat film coated on the paint film containing the unsaturated polyester resin composition. Is suitable.

Further, amines other than the above, for example, 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-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, pheny N, N-substituted anilines such as limorpholine, piperidine, N, N-bis (hydroxyethyl) aniline, diethanolaniline, N, N-substituted-p-toluidine, 4- (N, N-substituted amino) benzaldehyde, etc. Amines can also be used as curing aid accelerators.

These curing aid accelerators may be used alone or in combination of two or more. The curing aid accelerator is based on the total weight of the unsaturated polyester resin (I), the polymerizable unsaturated compound (II) containing a hydroxyl group and the polymerizable unsaturated compound (III) represented by the formula (1). 0.0
It is suitable to be in the range of 1 to 2.0% by weight, preferably 0.05 to 1.5% by weight.

  Examples of the polymerization inhibitor include trihydrobenzene, trihydroquinone, 14-naphthoquinone, parabenzoquinone, hydroquinone, benzoquinone, hydroquinone monomethyl ether, p-tert-butylcatechol, 2,6-di-tert-butyl-4-methylphenol. Can be used alone or in combination of two or more.

When the polymerization inhibitor is blended, the amount used thereof is an unsaturated polyester resin (I), a polymerizable unsaturated compound containing a hydroxyl group (II), and a polymerizable unsaturated compound represented by the formula (1) ( III) based on the total weight of 0.002 to 1.5% by weight, preferably 0.01 to
It can be in the range of 1.0% by weight.
In the unsaturated polyester resin composition of the present invention, it is desirable to mix and blend a radical curing agent, for example, immediately before use. Examples of the radical curing agent include organic peroxides, and specific examples include diacyl peroxides, peroxyesters, hydroperoxides, dialkyl peroxides, ketone peroxides, peroxyketals. In addition, conventionally known ones such as alkyl peresters and percarbonates may be used, and these may be used alone or in combination of two or more. The blending amount of the radical curing agent is based on the total weight of the unsaturated polyester resin (I), the hydroxyl group-containing polymerizable unsaturated compound (II) and the polymerizable unsaturated compound (III) represented by the formula (1). 0.1 to 6% by weight, preferably 0.5
Within the range of ˜5% by weight is preferred.

In the present invention, a polymerizable unsaturated compound other than the polymerizable unsaturated compound (II) containing a hydroxyl group and the polymerizable unsaturated compound (III) represented by the formula (1) is blended as a reactive diluent. You can also. Examples of the polymerizable unsaturated compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl ( (Meth) acrylate, adamantyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol (meth) acrylate, tricyclodecane dimethanol Di (meth) acrylate, 1,9
Nonanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2,2-bis (4- (3-methacryloxy-2-hydroxypropoxy) -phenyl) (Meth) acrylic acid esters of mono- or polyhydric alcohols such as propane, di (methacryloxyethyl) trimethylhexamethylenediurethane, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane; acrylic acid, Methacrylic acid, crotonic acid, itaconic acid, etc .; ethylene glycol dimaleate, propylene glycol diitaconate, etc .; 4- (meth) acryloyloxymethoxycarbonylphthalic acid, 4- (meth) acryloyloxyethoxycarbonylphthalic acid, etc. Aroma containing meth) acryloyloxyl group Polycarboxylic acids and acid anhydrides thereof; allyl compounds such as diallyl phthalate, diallyl isophthalate and triallyl phthalate; epoxy (meth) acrylates such as addition reaction products of (meth) acrylic acid and glycidyl ether of bisphenol A; polyester (Meth) acrylate; polydimethylsilicon di (meth) acrylate; urethane (meth) acrylate and the like can be mentioned, and these can be used alone or in combination of two or more.

In addition, aromatic vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, vinyltoluene, t-butylstyrene, divinylbenzene and the like can be used as long as they do not affect the composition of the present invention.
In the unsaturated polyester resin composition of the present invention, for example, an organic solvent, an ultraviolet stabilizer, an ultraviolet absorber, a low shrinkage agent, an anti-aging agent, a plasticizer, an aggregate, a flame retardant, a stabilizer, if necessary. Viscosity modifiers such as reinforcing materials, viscosity reducers, pigment dispersants, modifying resins, thixotropic agents, thixotropic agents, antifoaming agents, leveling agents, silane coupling agents, paraffinic air blocking agents, aldehyde scavengers Etc. can be blended.

The unsaturated polyester resin composition of the present invention can be used as a coating composition and / or a putty composition, and can be applied by a conventionally known method. The applied coating film can be cured to the inside of the coating film by normal temperature or forced drying.
The method of the present invention is a coating method characterized in that a coating composition containing the unsaturated polyester resin composition or a putty composition containing the unsaturated polyester resin composition is applied to a substrate surface and overcoated. is there.

Examples of substrate surfaces include metal surfaces such as iron, zinc, and aluminum, chemically treated surfaces, plastics, wood, etc., and old paint surfaces painted on them. It is appropriate to perform sanding around the damaged part as necessary.
Further, a top coat may be applied to the coating film by the coating composition or the putty composition, and as the top coating, acrylic lacquer, acrylic melamine resin-based paint, urethane curable paint, acrylic urethane resin-based paint, acid -Commonly used organic solvent-based paints such as epoxy curable paints, fluororesin paints, alkyd resin paints, alkyd resin melamine resin paints, polyester melamine resin paints, water paints, powders, etc. are not particularly limited. Can be used.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. In the examples below, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.
Production of unsaturated polyester resin Production Example 1
Add 1 mol of fumaric acid 2 mol (232 g), methyltetrahydrophthalic anhydride 1.8 mol (299 g), and 1 to 4 mol of bisphenol A and propylene oxide to a 2 L glass flask equipped with a temperature controller, reflux condenser and stirrer. Product 0.4 mol (184 g), diethylene glycol 3.2 mol (339 g), pentaerythritol triallyl ether
4 mol (102 g), trimethylolpropane diallyl ether 0.8 mol (171 g) and parabenzoquinone 0.7 g were charged, the temperature was raised to 180 ° C. to conduct a dehydration condensation reaction, and when the acid value reached 35 mgKOH / g. Heating was stopped and cooled to 100 ° C. to obtain an unsaturated polyester resin (E-1). The weight average molecular weight of the resin was 3000.

Production Example 2
Using the same apparatus as in Production Example 1, fumaric acid 2 mol (232 g), methyltetrahydrophthalic anhydride 1.8 mol (299 g), diethylene glycol 3.6 mol (382 g), pentaerythritol triallyl ether 0.4 mol ( 102 g), 0.8 mol (171 g) of trimethylolpropane diallyl ether and 0.7 g of parabenzoquinone were added, the temperature was raised to 180 ° C., a dehydration condensation reaction was performed, and the heating was stopped when the acid value reached 35 mgKOH / g. And it cooled to 100 degreeC and obtained unsaturated polyester resin (E-2). The weight average molecular weight of the resin was 2500.

Production Example 3
Using the same apparatus as in Production Example 1, fumaric acid 3.8 mol (441 g), bisphenol A and propylene oxide 1 to 4 mol adduct 0.4 mol (184 g), diethylene glycol 3.2 mol (339 g), penta Charge 0.4 mol (102 g) of erythritol triallyl ether, 0.8 mol (171 g) of trimethylolpropane diallyl ether, and 0.7 g of parabenzoquinone, raise the temperature to 180 ° C., conduct a dehydration condensation reaction, and the acid value is 35 mgKOH When it became / g, the heating was stopped, and the mixture was cooled to 100 ° C. to obtain an unsaturated polyester resin (E-3). The weight average molecular weight of the resin was 2800.

Production Example 4
Using the same apparatus as in Production Example 1, fumaric acid 2 mol (232 g), neopentyl glycol 0.6 mol (76 g), bishydroxyethyl terephthalate 0.3 mol (76 g), trimethylolpropane 0.7 mol (96 g) ), 1.1 mol (282 g) of pentaerythritol triallyl ether and 0.4 g of parabenzoquinone were added, the temperature was raised to 180 ° C., a dehydration condensation reaction was carried out, and the heating was stopped when the acid value reached 35 mgKOH / g. The mixture was cooled to 100 ° C. to obtain an unsaturated polyester resin (E-4) solution. The unsaturated polyester resin (E-4) had a weight average molecular weight of 3000.

Production Example 5
Using the same apparatus as in Production Example 1, 1.1 mol (128 g) of fumaric acid, 0.9 mol (133 g) of phthalic anhydride, 1.1 mol (117 g) of diethylene glycol, 1.1 mol of pentaerythritol triallyl ether ( 282 g) and 0.4 g of parabenzoquinone, heated to 180 ° C. and subjected to a dehydration condensation reaction. When the acid value reached 35 mgKOH / g, the heating was stopped, the temperature was lowered to 100 ° C., and an unsaturated polyester resin ( E-5) A solution was obtained. The unsaturated polyester resin (E-5) had a weight average molecular weight of 3000.

Production of unsaturated polyester resin composition Examples 1-21 and Comparative Examples 1-2
Each composition was blended so as to have the blended composition shown in Table 1 below, and stirred uniformly to obtain each unsaturated polyester resin composition. In addition, the quantity of each unsaturated polyester resin in a table | surface is a solid content display.

Examples 22-78 and Comparative Examples 3-4
Production of Putty Composition In 100 parts of each unsaturated polyester resin composition (T-1) to (T-23) obtained in Examples 1 to 21 and Comparative Examples 1 and 2, 5% Nikkanaphthex cobalt was added. "T" (trade name, manufactured by Nippon Kagaku Sangyo Co., Ltd., cobalt naphthenate) or "Nikka Octix Cobalt 12% T" (trade name, manufactured by Nippon Kagaku Sangyo Co., Ltd., cobalt octenoate), hydroquinone, "CR-95" (product Name, manufactured by Ishihara Sangyo Co., Ltd., titanium oxide), “Crown Talc DR” (trade name, manufactured by Matsumura Sangyo Co., Ltd., talc) and “BUSAN 11-M1” (trade name, manufactured by Sakai Chemical Co., Ltd., barium metaborate) or “LF” 300 ml of “Bousei ZK-S2” (trade name, manufactured by Kikuchi Color Co., Ltd., cyanamide zinc calcium) blended in the composition ratio shown in Table 2 was collected, and a high-speed kneader “TK Hibisumi” Box fmodel.1 "is 20 minutes mixing and dispersing in (Tokushu Kika Kogyo Co., Ltd.), to obtain each putty composition.

Preparation of the test coating plate “SPCC-SB” (manufactured by Nippon Test Panel Co., Ltd., mild steel plate) was lightly polished with water-resistant paper # 180, and this was used as the substrate surface. 2% each of “LUC common curing agent” (trade name, main component: cyclohexanone peroxide, manufactured by Kansai Paint Co., Ltd.) was added to each putty composition obtained above, and each substrate surface was mixed uniformly. It was applied to the top with a spatula and then applied to a thickness of 2 mm.

Evaluation test Each putty composition obtained above was tested according to the following evaluation methods and standards. The results are shown in Table 2.
(* 1) Dryability: Each test coating plate was allowed to stand at room temperature (20 ° C.) for 30 minutes, and then the surface tack and internal curing of each test coating plate were examined by finger touch. (○: good, x: tack on the surface, poor curing inside).
(* 2) Pot life: Gelation time at room temperature (20 ° C.) after blending the curing agent. The higher the value, the better.

Preparation of painted plate After the test coated plate was allowed to dry at room temperature (20 ° C) for 6 hours, the coated surface was lightly polished with a # 400 water-resistant paper, and "Letane PG80 White Base" (product) Name, acrylic urethane resin-based top coat, manufactured by Kansai Paint Co., Ltd.) was spray-coated to a dry film thickness of 50 μm and dried at 60 ° C. for 30 minutes to obtain each coated plate.

Each coated plate obtained above was tested according to the following evaluation methods and standards. The results are shown in Table 2.
(* 3) Adhesion 1: Each coated plate was immersed in warm water at 40 ° C. for 10 days, then bent at a 90 ° angle from the center, and the state of the coating film at the bent portion was observed (◯: good, × : The coating film is peeled off).
(* 4) Adhesion 2: Each coated plate was immersed in warm water of 80 ° C. for 1 day, then bent at a 90 ° angle from the center, and the state of the coating film at the bent portion was observed (◯: Good, Δ : Part of the coating film is peeled off, ×: The coating film is peeled off).

Claims (13)

(I) an unsaturated polyester resin, (II) a polymerizable unsaturated compound containing a hydroxyl group, and (III) the following formula (1):

(In the above formula (1), R ¹ represents an alkylene group having 2 to 12 carbon atoms, n represents an integer of 0 to 2, and when n is 2, each R ¹ in the repeating unit is the same. The total number of carbon atoms of R ¹ is 4 to 24, and R ² is a methyl group or a hydrogen atom.) The composition of the unsaturated polyester resin (I), the polymerizable unsaturated compound (II) containing a hydroxyl group and the polymerizable unsaturated compound (III) represented by the formula (I) is a component ( Based on the total weight of I), (II) and (III), component (I) is 25 to 85% by weight, component (II) is 5 to 65% by weight, and component (III) is 10 to 70% by weight. , and the said hydroxyl-containing polymerizable unsaturated compound (II) is 2-hydroxyethyl methacrylate, heavy Sex unsaturated compound (III) is an unsaturated polyester resin composition, which is a dicyclopentenyloxyethyl methacrylate.   The unsaturated polyester resin according to claim 1, wherein the unsaturated polyester resin (I) contains 1 to 40 mol% of units derived from a cycloaliphatic unsaturated polybasic acid based on the total number of moles of all structural units. Composition.   The unsaturated polyester resin composition according to claim 1 or 2, wherein the unsaturated polyester resin (I) contains 0.5 to 10 mol% of units derived from bisphenols based on the total number of moles of all structural units. .   The unsaturated polyester resin according to any one of claims 1 to 3, wherein the unsaturated polyester resin (I) contains 5 to 50 mol% of allyl ether units of polyhydric alcohol based on the total number of moles of all structural units. Resin composition. The unsaturated polyester resin (I) contains a unit derived from a cycloaliphatic unsaturated polybasic acid, a unit derived from a bisphenol and an allyl ether unit of a polyhydric alcohol in the same molecule. The unsaturated polyester resin composition according to any one of the above. The unsaturated polyester resin (I) comprises an unsaturated polyester resin (I-1) containing a unit derived from a cycloaliphatic unsaturated polybasic acid and an allyl ether unit of a polyhydric alcohol; A resin mixture comprising an unsaturated polyester resin (I-2) containing a unit derived from a polybasic acid other than a basic acid, a unit derived from a bisphenol, and an allyl ether unit of a polyhydric alcohol. 6. The unsaturated polyester resin composition according to any one of 5 above.   The unsaturated polyester resin composition according to claim 1, wherein the unsaturated polyester resin (I) contains an allyl ether unit, a terephthalic acid unit, and an ethylene glycol unit of a polyhydric alcohol in the same molecule.   Furthermore, the unsaturated polyester resin composition of any one of Claim 1 thru | or 7 containing a rust preventive agent.   The unsaturated polyester resin composition according to claim 8, wherein the rust inhibitor is at least one rust preventive pigment selected from molybdate, phosphomolybdate, metaborate, and cyanamide zinc calcium. Furthermore, the unsaturated polyester resin composition of any one of Claim 1 thru | or 9 containing the aromatic amine represented by Formula (2).

(Wherein R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group having 1 to 5 carbon atoms, an aryl group or an alkoxy group, and R ⁵ is a hydrogen atom. Represents an optionally substituted alkyl group having 1 to 20 carbon atoms, or an aryl group.)   The coating composition containing the unsaturated polyester resin composition of any one of Claim 1 thru | or 10.   The putty composition containing the unsaturated polyester resin composition of any one of Claim 1 thru | or 10.   A coating method comprising applying the composition according to claim 11 or 12 to a substrate surface and top-coating.