JP2002105388A - Resin composition for coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition for a coating, having excellent storage stability and various coating performances such as curability at a low temperature (<=80 deg.C), appearance of coating, adhesivity to various substrates, weather resistance, etc. SOLUTION: This resin composition for a coating is characterized in that the composition comprises a coating resin (A) composed of a silane group- containing acrylic resin (P) which is copolymerized with an alkoxysilane group- containing unsaturated monomer (a), contains an alkoxysilane group at the side chain and has 500-80,000 number-average molecular weight, an epoxy group- containing acrylic resin (Q) which is copolymerized with an epoxy group- containing unsaturated monomer (b), contains an epoxy group at the side chain and has 500-80,000 number-average molecular weight, a curing agent (B) and a nonionic surfactant (C) and the amount of the epoxy group-containing unsaturated monomer (b) contained in the coating resin (A) is <5.000 ppm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for a paint and a paint containing the resin composition for a paint.

More specifically, the present invention relates to a coating resin composition for producing a coating material curable at room temperature or by heating, and a coating coated with a coating material containing the coating resin composition. The article maintains a beautiful painted appearance over a long period of time and realizes a high level of performance and functions required for the painted article.

[0003]

2. Description of the Related Art Conventionally, the performance and functions required of paints are diverse, and various paint resins have been developed and put into practical use so as to exhibit sufficient functions and performances in each field or application. ing. For example, fluororesin paint for high weather resistance and durability, inorganic paint for stain resistance and scratch resistance, zinc rich paint for metal contact prevention, low VOC (emission to the environment) Water-based emulsion paints and high-solid paints developed for the purpose of reducing organic solvents.

[0004] These coatings have received high praise in the fields in which they have been aimed and have been accepted in the market.

[0005] On the other hand, one coating material which can be applied to all fields or applications, or a curing agent is already prepared (= one-pack coating or a pot life after the curing agent is blended (the coating material is thickened). Or paint that has a sufficiently long time until it becomes gelled and becomes unusable), and paint that can be regarded as equivalent to the already prepared mixture in paint work) Paint that reduces work related to paint preparation at the painting site, and delivery and storage of paint There is a strong need for an easy-to-use one with no restrictions. Examples of these are disclosed in JP-A-60-67553 and JP-A-63-67553.
No. 108048, JP-A-2-73825, JP-A-6-128533, JP-A-8-157722
JP-A-10-60211, JP-A-11-31
No. 5,248, JP-A-2000-44867 and the like have been proposed.

[0006] However, these proposed techniques do not sufficiently satisfy the basic various performances required for paints, such as curability, appearance of the coating film, and adhesion to various kinds of objects to be coated. Is the current situation.

As an example, when one performance (design / coating appearance) required for a paint is observed, these techniques are used in low-temperature drying (winter) or high-temperature and high-humidity (seasonal season to summer). When applied, or when a thick film of about 40 μm or more is applied, blemishes (a phenomenon in which the surface of the coating film becomes a crepe pattern) occur in the coating film, and it is difficult to obtain a beautiful coating film appearance. In other words, in addition to the inadequacy in design and aesthetics, in such a case, various coating film properties, gloss, smoothness of the coating film, adhesion to the object to be coated, chemical resistance or weather resistance, etc. It is always very bad. These items related to the appearance of the coating film are closely related to the amount of the epoxy group-containing unsaturated monomer remaining unreacted in the coating resin and the total amount of the unsaturated monomer remaining unreacted. It is hard to say that meticulous consideration has been taken.

[0008]

SUMMARY OF THE INVENTION The present invention relates to a resin composition for coatings in consideration of the above points and a coating containing the resin composition for coatings.

More specifically, an object of the present invention is to obtain a beautiful coating film appearance even in a severe coating environment, and to adhere to various substrates, chemical resistance, scratch resistance, weather resistance and metal. An object of the present invention is to provide a coating resin composition for obtaining a coating excellent in various coating film performances such as anti-corrosion properties.

Another object of the present invention is to provide a paint containing the above resin composition for a paint, and a coated article coated with the paint.

[0011]

The resin composition for coatings of the present invention has a number average molecular weight of from 500 to 80,000 having a hydroxyl group in a side chain obtained by copolymerizing a hydroxyl group-containing unsaturated monomer (a).
Of a hydroxyl group-containing acrylic resin (P), an epoxy group-containing unsaturated monomer (b) copolymerized with an epoxy group-containing acrylic resin (Q) having an epoxy group in a side chain and having a number average molecular weight of 500 to 80,000. A coating resin composition containing a coating resin (A), a curing agent (B) and a nonionic surfactant (C), wherein the epoxy resin-containing unsaturated resin contained in the coating resin (A) When the amount of the monomer (b) is 5,000
It is a resin composition for coatings characterized by being less than 0 ppm.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition for coatings of the present invention comprises a hydroxyl group-containing acrylic resin having a number average molecular weight of 500 to 80,000 having a hydroxyl group in a side chain obtained by copolymerizing a hydroxyl group-containing unsaturated monomer (a). Resin (P), coating resin containing epoxy group-containing acrylic resin (Q) having an epoxy group in a side chain and having an epoxy group-containing unsaturated monomer (b) copolymerized and having an average molecular weight of 500 to 80,000. A coating resin composition containing (A), a curing agent (B) and a nonionic surfactant (C), wherein the epoxy group-containing unsaturated monomer (A) is contained in the coating resin (A). It is a resin composition for paints in which the amount of b) is less than 5,000 ppm.

The hydroxyl group-containing acrylic resin (P) having a hydroxyl group in the side chain and having a number average molecular weight of 500 to 80,000 used in the present invention comprises a hydroxyl group-containing unsaturated monomer (a) and, if necessary, other resins. It can be produced by radical copolymerization of the unsaturated monomer (1-1). As long as it is a radical copolymerization, any polymerization method such as emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization may be used, and the polymer form to be produced may be any of liquid, dispersion, and bulk. In the present invention, solution polymerization can be recommended in terms of convenience,
It is desirable to obtain the polymer in liquid form.

As the hydroxyl group-containing unsaturated monomer (a),
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, monoacrylate of cyclohexanedimethanol,
2-hydroxyethyl methacrylate, 2-methacrylic acid 2-
Examples thereof include monopropyl methacrylates of hydroxypropyl, 4-hydroxybutyl methacrylate and cyclohexanedimethanol, and adducts thereof with lactones such as ε-caprolactone and γ-valerolactone. The hydroxyl group-containing unsaturated monomer (a) may be used alone or as a mixture of two or more.

The copolymerization of the hydroxyl group-containing unsaturated monomer (a) tends to improve the adhesion to various objects to be coated (particularly metals such as aluminum alloys and magnesium alloys) and the curability of the coating. is there.

Other unsaturated monomers (1-1) include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, methacrylic acid Ethyl, propyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate and the like, alkyl esters of (meth) acrylic acid having 1 to 18 carbon atoms, trifluoroethyl methacrylate, heptafluoropropyl methacrylate, Unsaturated monomer (c) containing a fluoroalkyl group (fluoroalkyl group has 1 to 24 carbon atoms) such as perfluorooctylethyl methacrylate, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyl Alkoxysilane group-containing unsaturated monomer having an alkoxysilane group in the molecule, such as triethoxy silane (d), glycidyl acrylate, glycidyl methacrylate, methyl glycidyl methacrylate, 3,
4-epoxycyclohexylmethyl methacrylate,
Epoxy group-containing unsaturated monomer (b) such as 3,4-epoxycyclohexylmethyl acrylate, and amide group-containing unsaturated monomer such as diacetone acrylamide, diacetone methacrylamide, N-butoxymethyl acrylamide and N-butoxymethyl methacrylamide Monomer, 2- [2
'-Hydroxy-5'-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2
'-Hydroxy-5'-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2
'-Hydroxy-5'-(methacryloyloxypropyl) phenyl] -2H-benzotriazole and other benzotriazole ultraviolet absorbing unsaturated monomers (R-UV
A) hindered amine based light stability such as 4-methacryloylamino-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine; Saturated monomer (R-HAL
S), styrene, vinyl acetate, tetrahydrofurfuryl (meth) acrylate, butadiene, vinyl compounds such as tetrafluoroethylene, trichlorofluoroethylene, dichlorofluoroethylene, monochlorofluoroethylene, butyl vinyl ether, cyclohexyl vinyl ether, and one molecule such as allyl methacrylate Examples thereof include a compound having an allyl group and an acryloyl group. The other unsaturated monomers (1-1) may be used alone or as a mixture of two or more.

Among the above compounds, the weather resistance is particularly improved,
From the viewpoint of improvement, R-UVA and R-HALS can be suitably copolymerized. As R-UVA, benzotriazole-based R-UVA and RH
As ALS, R-HALS having no hydrogen atom directly bonded to a nitrogen atom is preferable, and more preferably PK-
Those having b of 8 or more are recommended from the viewpoints of improving the storage stability of the paint, suppressing the inhibition of curability over time, preventing coloring of the coating film and improving the appearance.

It is recommended that R-UVA be copolymerized in the hydroxyl group-containing acrylic resin (P) preferably in an amount of 0.01 to 30% by weight, more preferably 0.5 to 10% by weight. When the copolymerization amount is less than 0.01% by weight, the effect of improving the weather resistance and the like is not so great, and the copolymerization amount is 30%.
If the amount is more than 10% by weight, the coating film may be colored or the alkali resistance of the coating film may be deteriorated. It is desirable that R-HALS is copolymerized in the hydroxyl group-containing acrylic resin (P) in an amount of 0.01 to 30% by weight, preferably 0.5 to 10% by weight. If the copolymerization amount is less than 0.01% by weight, the effect of improving the weather resistance and the like is not so great. May be.

As described above, the hydroxyl group-containing acrylic resin (P) having a hydroxyl group in the side chain is composed of the hydroxyl group-containing unsaturated monomer (a) and, if necessary, other unsaturated monomer (l).
-1) can be produced by radical copolymerization.

The production of the hydroxyl group-containing acrylic resin (P) is as follows.
As long as it is a radical polymerization, differences in polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization and bulk polymerization do not matter. Examples of solution polymerization include toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, isopropyl alcohol, n-butyl alcohol, diacetone alcohol, ligroin, dioxane, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether. Using organic solvents such as propylene glycol methyl ether and γ-butyrolactone to polymerize organic azo polymerization initiators such as azobisisobutyronitrile, organic peroxides such as benzoyl peroxide, and other free radical generating compounds As an initiator, under pressure or normal pressure, at -20 to 150 ° C, preferably 60 to
At 100 ° C, more preferably within + 25 ° C of the decomposition half-life temperature of the polymerization initiator to be used, the hydroxyl group-containing unsaturated monomer (a) and, if necessary, other unsaturated monomers (l
-1) can be produced by radical copolymerization. Here, in order to adjust the molecular weight, butyl mercaptan, alkylthiols such as n-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane,
Chain transfer of compounds having a mercapto group and a silane group, such as 3-mercaptopropyltriethoxysilane, and compounds (m) having a thio group and a carboxyl group in a molecule such as alpha methylstyrene dimer, thioglycolic acid, and thiopropionic acid. Agents can also be used.

The compound (m) having a thio group and a carboxyl group may play an important role in producing a graft copolymer, as described later. That is, by using the compound (m) having a carboxyl group as a chain transfer agent, it becomes possible to introduce a carboxyl group into the polymer terminal. The terminal of the polymer can be modified into an acryloyl unsaturated double bond through an addition reaction between the carboxyl group and the epoxy group-containing unsaturated monomer (b).
Other unsaturated monomers (1-1 or 1-2 described below)
By carrying out radical copolymerization together with this, a graft copolymer can be produced.

It is recommended that the number average molecular weight measured by GPC using a standard polystyrene of a hydroxyl group-containing acrylic resin (P) is preferably 500 to 80,000, more preferably 800 to 50,000. If the number average molecular weight is less than 500, the storage stability of the coating and the weather resistance of the coating film tend to be slightly deteriorated. When the number average molecular weight exceeds 80,000, the leveling property of the coating film tends to be impaired, and the adhesion to the object to be coated tends to be slightly deteriorated.

The epoxy group-containing acrylic resin (Q) having an epoxy group in the side chain and having a number average molecular weight of 5,000 to 80,000 used in the present invention comprises a glycidyl group-containing unsaturated monomer (b) and If necessary, it can be produced by copolymerizing another unsaturated monomer (1-2). If it is a radical copolymerization, emulsion polymerization, suspension polymerization,
Any polymerization method such as bulk polymerization and solution polymerization may be used, and the form of the polymer to be produced may be any of liquid, dispersion, and bulk. In the present invention, solution polymerization can be recommended in terms of usability, and it is desirable to obtain the polymer in a liquid state.

As the epoxy group-containing unsaturated monomer (b), glycidyl acrylate, glycidyl methacrylate,
Examples thereof include those having an unsaturated double bond and an epoxy group in the molecule, such as methyl glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate. The epoxy group-containing unsaturated monomer (b) may be used alone or as a mixture of two or more. It is desirable that the epoxy group-containing unsaturated monomer (b) is copolymerized so that the epoxy equivalent of the epoxy group-containing acrylic resin (Q) becomes 450 to 30,000, preferably 650 to 22,000. When the epoxy equivalent is less than 450, the storage stability of the paint, the alkali resistance of the coating film, and the like tend to slightly deteriorate. On the other hand, when the epoxy equivalent exceeds 30,000, the adhesion to the article to be coated tends to be slightly deteriorated.

Other unsaturated monomers (1-2) include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, methacrylic acid Ethyl, propyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate and the like, alkyl esters of (meth) acrylic acid having 1 to 18 carbon atoms, trifluoroethyl methacrylate, heptafluoropropyl methacrylate, Unsaturated monomer (c) containing a fluoroalkyl group (fluoroalkyl group has 1 to 24 carbon atoms) such as perfluorooctylethyl methacrylate, acrylic acid 2-
Hydroxyethyl, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, monoacrylate of cyclohexane dimethanol, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, cyclohexane dimethanol Monomethacrylic acid esters, adducts of these with lactones such as ε-caprolactone, γ-valerolactone, etc., such as hydroxyl-containing unsaturated monomers (a), 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxy An alkoxysilane group-containing unsaturated monomer (d) such as propyltriethoxysilane, diacetone acrylamide, diacetone methacrylamide, N-butoxymethylacrylamide,
Amide group-containing unsaturated monomers such as N-butoxymethyl methacrylamide, 2- [2'-hydroxy-5 '-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5 Benzotriazole-based UV-absorbing unsaturated monomers such as '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole and 2- [2'-hydroxy-5'-(methacryloyloxypropyl) phenyl] -2H-benzotriazole Body (R-UVA), 4-methacryloylamino-
Hindered amine-based photostable unsaturated monomers (R-HALS) such as 2,2,6,6-tetramethylpiperidine and 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine ), Styrene, vinyl acetate, tetrahydrofurfuryl (meth) acrylate, butadiene,
Examples thereof include vinyl compounds such as tetrafluoroethylene, trichlorofluoroethylene, dichlorofluoroethylene, monochlorofluoroethylene, butyl vinyl ether and cyclohexyl vinyl ether, and compounds having an allyl group and an acryloyl group in one molecule such as allyl methacrylate. The other unsaturated monomer (l
-2) may be a single compound or a mixture of two or more compounds.

Among the other unsaturated monomers (1-2) described above, particularly, from the viewpoint of improving and improving the weather resistance, R-
UVA and R-HALS can be suitably copolymerized. Further, as R-UVA, benzotriazole-based R-UVA, and as R-HALS, R-HALS having no hydrogen atom directly bonded to a nitrogen atom are preferable, and more preferably PKb having 8 or more. Those are recommended from the viewpoints of improving the storage stability of the paint, suppressing the inhibition of the curability over time, preventing coloring of the coating film and improving the appearance.

It is recommended that R-UVA be copolymerized in the epoxy group-containing acrylic resin (Q) preferably in an amount of 0.01 to 30% by weight, more preferably 0.5 to 10% by weight. If the copolymerization amount is less than 0.01% by weight, the effect of improving the weather resistance and the like will not be remarkable. If the copolymerization amount exceeds 30% by weight, the coating film will be colored, May worsen. It is desirable that R-HALS is copolymerized in the silane-containing acrylic resin (Q) in an amount of 0.01 to 30% by weight, preferably 0.5 to 10% by weight. When the copolymerization amount is less than 0.01% by weight, the effect of improving the weather resistance and the like is not so great. Storage stability may deteriorate.

The epoxy group-containing acrylic resin (Q) having an epoxy group in the side chain is the above-mentioned epoxy group-containing unsaturated monomer (b) and, if necessary, other unsaturated monomer (k-2). Can be produced by radical copolymerization of

The production of the epoxy group-containing acrylic resin (Q) is not a problem as long as it is a radical polymerization, because of differences in polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization and bulk polymerization. Examples of solution polymerization include toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, isopropyl alcohol, n-butyl alcohol, diacetone alcohol, ligroin, dioxane, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether. Using organic solvents such as propylene glycol methyl ether and γ-butyrolactone to polymerize organic azo polymerization initiators such as azobisisobutyronitrile, organic peroxides such as benzoyl peroxide, and other free radical generating compounds As an initiator, under pressure or normal pressure, at -20 to 150 ° C., preferably 60 ° C.
-100 ° C, more preferably within + 25 ° C of the decomposition half-life temperature of the polymerization initiator used, the epoxy group-containing unsaturated monomer (b) and, if necessary, other unsaturated monomers (1- It can be produced by radical copolymerization of 2). Here, in order to adjust the molecular weight, alkylthiols such as butyl mercaptan and n-dodecyl mercaptan, compounds having a mercapto group and a silane group such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane, alpha A chain transfer agent such as a compound (m) having a thio group and a carboxyl group in a molecule such as methylstyrene dimer, thioglycolic acid, and thiopropionic acid can also be used.

The compound (m) having a thio group and a carboxyl group may play an important role in producing a graft copolymer as described below. That is, by using the compound as a chain transfer agent, it becomes possible to introduce a carboxyl group into the polymer terminal. The terminal of the polymer can be modified into an acryloyl unsaturated double bond through an addition reaction between the carboxyl group and the epoxy group-containing unsaturated monomer (b). Other unsaturated monomers (1-1 or 1-)
By graft copolymerizing with 2), a graft copolymer can be produced.

The number average molecular weight measured by GPC using the standard polystyrene of the epoxy group-containing acrylic resin (Q) is 500 to 80,000, preferably 800 to 5
It is recommended that it be 000. Number average molecular weight is 5
If it is less than 00, the storage stability of the coating and the weather resistance of the coating film tend to be slightly deteriorated. When the number average molecular weight exceeds 80,000, the leveling property of the coating film is impaired, or the adhesion to the object to be coated tends to be slightly deteriorated. It is necessary that the amount of the unreacted epoxy group-containing unsaturated monomer (b) in the coating resin (A) is less than 5,000 ppm, which contains P) and the epoxy group-containing acrylic resin (Q). More preferably, the total amount of unreacted unsaturated monomers is desirably less than 10,000 ppm. The amount of the unreacted epoxy group-containing unsaturated monomer (b) is 2,000 p
pm, and the total amount of unreacted unsaturated monomers is preferably less than 8,000 ppm.

Unreacted epoxy group-containing unsaturated monomer (b)
And the total amount of unreacted unsaturated monomers can be measured by a general method for analyzing unsaturated monomers, for example, a gas chromatography method, a liquid chromatography method, a GPC method and the like. In the present invention, the measurement was performed using liquid chromatography under the conditions described below.

When the amount of the epoxy group-containing unsaturated monomer (b) exceeds 5,000 ppm in the coating resin (A), the storage stability and curability of the coating are significantly impaired,
The chemical resistance and weather resistance of the coating film tend to deteriorate. Furthermore, the epoxy group-containing unsaturated monomer (b) bleeds out on the surface of the coating film or remains forever in the coating film, and significantly reduces the appearance of the coating film (particularly, the smoothness of the coating film and the thickness). Tends to worsen.

That is, the epoxy group-containing unsaturated monomer (b) inhibits the function of exhibiting curability of the curing agent, or the epoxy group-containing unsaturated monomer (b) reacts preferentially with the curing agent. However, the original curing reaction may be delayed or not progressed at all, or in some cases, the action of accelerating the cross-linking reaction may occur, and the paint may thicken or gel. Furthermore, since the epoxy group-containing unsaturated monomer (b) remains unreacted, a relatively reactive compound having an epoxy group and an unsaturated double bond remains in the coating film, and therefore, the chemical resistance is low. Deterioration (epoxy group reacts with alkali, acid, etc. to cause coloring or destruction of coating film), weather resistance deteriorates (unsaturated double bond is activated by light energy, coloring or discoloration of coating film) Decompose). In addition, when the coating film cures and crosslinks, it partially accelerates the curing reaction or stops the reaction. Is a major cause of deterioration in smoothness and sharpness. To make matters worse, this makes it more likely that shrinkage will occur. This tendency is closely related to the total amount of the unreacted unsaturated monomers, and the total amount is 10,000.
If it exceeds 0 ppm, the synergistic effect tends to be more remarkable.

In the present invention, the hydroxyl group-containing acrylic resin (P), the epoxy group-containing acrylic resin (Q) and the epoxy group-containing acrylic resin (Q) are used in order to keep the amount of the unreacted epoxy group-containing unsaturated monomer (b) less than 5,000 ppm. In addition, in producing the graft copolymer by radical copolymerization, the polymerization temperature is used, and the polymerization initiator is used for a 10-hour decomposition half-life temperature of ± 25 ° C., preferably 10-hour decomposition half-life temperature + 5 ° C. to 10-hour decomposition half-life. It is recommended that the temperature be in the range of + 25 ° C. Further, the epoxy equivalent of the epoxy group-containing acrylic resin is adjusted to the epoxy equivalent range as described above, that is, 450 to 3
It is desirable to set it to 0000. By performing the production process under these conditions, the amount of the unreacted epoxy group-containing unsaturated monomer (b) can be suppressed to less than 5,000 ppm. In the present invention, the object can be achieved by implementing the above measures.However, if necessary, the residual amount of the unsaturated monomer is appropriately measured by inspection in the production process, and the Continue the polymerization reaction until the monomer amount is less than the desired value, or continue the polymerization step by further adding a polymerization initiator, and if necessary,
After the polymerization step, a purification step of removing the unsaturated monomer from the coating resin (A) (for example, washing with water, distillation and distillation, adsorption and removal with an adsorption tower or column, an adsorbent substance, etc.).
It is recommended to implement manufacturing methods such as incorporating

The curing agent (B) used in the present invention may be selected from the group consisting of dibutyltin dilaurate, zinc acetate, magnesium acetate, lead octylate, calcium octylate and the like.
A, IIB, IIIA, IVA, IVB, VB, VIIB, an organometallic compound containing a group VIII metal atom, an epoxy resin such as a bisphenol A type epoxy resin (reference: “1370
0 Chemical Products ”Chemical Daily (2000), p968
-P977), tri (N, N-dimethylaminomethyl)
Acidic hydroxyl group-containing compounds such as phenol, (hydrogen) polybasic acids such as tetrahydrophthalic anhydride and trimellitic acid, melamine resins, hexamethylene diisocyanate,
Polyisocyanate compounds such as toluene diisocyanate and diphenylmethane diisocyanate (and blocked polyisocyanate compounds in which the compounds are blocked with, for example, methyl alcohol), 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, phenyltriisocyanate Reactive with silane compounds having a reactive silane group such as methoxysilane and functional groups (alkoxysilane group, epoxy group, hydroxyl group, carboxyl group, etc.) of the coating resin (A) such as those obtained by condensation of the compound. Compounds having a functional group that can be used, or compounds having an effect of accelerating the crosslinking reaction of the acrylic resin for coating (A) (for example, a catalyst) can be exemplified. These compounds exemplified as the curing agent may be used alone or as a mixture of two or more.

The above compound is preferably used in an amount of 0.05 to 500 parts by weight (0.
05-500 PHR), more preferably 0.5-200 PHR.
It is recommended to incorporate PHR. Compounding amount is 0.05P
If it is less than HR, the curability and crosslinkability are insufficient, and the chemical resistance and water resistance may be deteriorated. On the other hand, when the amount exceeds 500 PHR, the coating film becomes brittle, and the adhesion to the object to be coated may be deteriorated. However, when a compound that is further reactive, for example, a compound having a functional group such as an alkoxysilane group, an epoxy group, a hydroxyl group, or a carboxyl group in the molecule, is added to the coating resin (A). Total amount of resin (A) and the compound (1)
With respect to 100 parts by weight, preferably 0.05 to 500 parts by weight (0.05 to 500 PHR), more preferably 0.5 to 500 parts by weight.
It is recommended to mix up to 200 PHR. The nonionic surfactant (C) is blended in the resin composition for a paint of the present invention. The nonionic surfactant (C) used in the present invention includes polyoxyethylene-polyoxypropylene condensate, polyoxyethylene lauryl ether, secondary alcohol ethoxylate, primary alcohol ethoxylate, nonylphenol ethoxylate ,
Octylphenol ethoxylate, oleyl alcohol ethoxylate, lauryl alcohol ethoxylate, polyethylene glycol, polyoxyethylene glycol oleate, sorbitan stearyl ester, sorbitan oleyl ester, polyoxyethylene sorbitan oleyl ester, 2-hydroxyethyl methacrylate, 4-hydroxyacrylate Examples thereof include acrylic resins in which a hydroxyl group-containing unsaturated monomer (d) such as butyl or polyethylene glycol monomethacrylate is copolymerized. Further, isopropyl alcohol, n-butyl alcohol, propylene glycol monomethyl ether,
Examples thereof include alcohols such as propylene glycol monobutyl ether, and glycol ethers. The nonionic surfactant (C) may be used alone or as a mixture of two or more.

[0038] By blending the nonionic surfactant (C), the storage stability of the paint is remarkably improved and improved. That is, during the storage of paint, highly reactive functional groups (alkoxysilane group, epoxy group, hydroxyl group, etc.)
It is considered that an action of protecting the water from the paint, approach-reaction between functional groups, and contact with the curing agent to the minimum necessary, and protecting against undesired inadvertent reactions are exhibited. In addition, when forming a coating film, it has the effect of lowering or appropriately increasing the interfacial tension of the coating material and suppressing the curing reaction of the coating material, and appropriately adjusting the viscosity. improves.

The nonionic surfactant (C) is preferably incorporated in the resin composition for coatings in an amount of preferably 20 to 50,000 ppm. More preferably, 50 to 2
It is recommended that the content be 0.00000 ppm. If the blending amount is less than 20 ppm, storage at 50 ° C or higher
In the case of storage at a relatively high temperature, sufficient storage stability may not be obtained. When the amount is more than 50,000 ppm, chemical resistance such as water resistance and alkali resistance of the coating film and recoat adhesion tend to be slightly deteriorated.

In the present invention, the coating resin (A) containing the hydroxyl group-containing acrylic resin (P) and the epoxy group-containing acrylic resin (Q) is made of the hydroxyl group-containing acrylic resin (P) and / or the epoxy group-containing acrylic resin (Q). ) As a branch polymer, and a graft copolymer containing a hydroxyl group-containing acrylic resin (P) and / or an epoxy group-containing acrylic resin (Q) as a trunk polymer.

The coating resin (A) of the present invention comprises a hydroxyl group-containing acrylic resin (P) and / or an epoxy group-containing acrylic resin (Q) as a branch polymer, and a hydroxyl group-containing acrylic resin (P) and / or an epoxy group-containing resin. By containing a graft copolymer having an acrylic resin (Q) as a backbone polymer, the storage stability of the coating material is dramatically improved,
Various substrates (for example, acrylonitrile-styrene-butadiene resin (ABS), polycarbonate resin (P
C), polystyrene resin (PS), nylon (NY),
Noryl resin (PPO), epoxy resin, thermoplastic or curable plastics such as old paint film, iron (alloy), aluminum (alloy), magnesium (alloy), copper (alloy), zinc (alloy), tin (alloy) ), Metals such as nickel (alloy), glass, ceramics, cement, asbestos cement, mortar, tiles, rocks, bricks, and other inorganic substances, etc.)
The coating film performance is extremely excellent, such as adhesion to coating, chemical resistance, weather resistance, gloss, smoothness, sharpness, etc., and anticorrosion of various metals and concrete. This is because the silane group-containing acrylic resin (P) and the epoxy group-containing acrylic resin (Q) were graft-copolymerized,
A microphase-separated structure is formed between both polymers (however, both polymers are tightly bound by covalent bonds, which is different from a simple mixture of the two. A separation structure is formed, and the two are likely to separate and precipitate over time, resulting in a paint having poor storage stability, whereas when the compatibility of the two is good, the effect exhibited by the present invention is obtained. Is not expected.), And characteristic functional groups such as an alkoxysilane group and an epoxy group are more likely to exhibit their characteristic functions.

That is, the alkoxysilane group has its original function (reactivity, --Si--O--
(Si-bond stability, corrosion protection of inorganic substances, good adhesion to metals and inorganic substances, water / oil repellency, stain resistance, hardness, etc.). It is considered that the original functions (reactivity, pigment dispersibility, pigment dispersion stability, anticorrosion properties of metals, adhesion to organic substances, etc.) can be more easily exhibited. Also, at the same time,
The graft copolymer acts as a surfactant having a characteristic function. From this viewpoint, during the storage of the paint, highly reactive functional groups (alkoxysilane groups, epoxy groups,
(A hydroxyl group, etc.) from an inadvertent reaction, and has the effect of dramatically improving storage stability. Further, when forming a coating film, the coating film has an effect of lowering or appropriately increasing the interfacial tension of the coating material and appropriately adjusting the viscosity, thereby improving the finish of the coating and the appearance of the coating film. Further, in the process of curing the coating film, there is an effect of promoting an appropriate curing speed and a quick crosslinked coating film formation based on the function of enhancing the function of each functional group as described above.

At this time, the branch polymer of the graft copolymer is a hydroxyl group-containing acrylic resin (P) and / or an epoxy group-containing acrylic resin (Q), and the trunk polymer is a hydroxyl group-containing acrylic resin (P) and / or an epoxy resin. It is preferable to have a group-containing acrylic resin (Q). More preferably, the branch polymer is a hydroxyl group-containing acrylic resin (P), and the trunk polymer is an epoxy group-containing acrylic resin (Q).
Is the case. At this time, the above effects become more remarkable, and the performance of the paint and the coating film is improved to the maximum.

In the present invention, when the branch polymer is a hydroxyl group-containing acrylic resin (P) and the backbone polymer is an epoxy group-containing acrylic resin (Q), the storage stability of the paint is as follows:
This is a preferred embodiment because the water repellency and oil repellency of the coating film tend to be improved.

When the branch polymer is a hydroxyl group-containing acrylic resin (P) and the trunk polymer is a hydroxyl group-containing acrylic resin (P), the coating film is densely cross-linked, and the coating film has durability, scratch resistance, and various coating properties. This is preferable since the adhesion to coatings (particularly inorganic substances) tends to be improved.

When the branch polymer is an epoxy group-containing acrylic resin (Q) and the trunk polymer is a hydroxyl group-containing acrylic resin (P), the storage stability of the coating material is particularly excellent, and the weather resistance of the coating film is excellent. This is preferable because it tends to improve.

When the branch polymer is an epoxy group-containing acrylic resin (Q) and the trunk polymer is an epoxy group-containing acrylic resin (Q), the coating can be sufficiently cured and crosslinked even at a relatively low temperature of about -20 to 50 ° C. Tends to form a dense coating film, chemical resistance,
This is preferable because the durability tends to be improved. In addition, there is a tendency that the adhesion to various kinds of objects to be coated (not limited to the objects to be coated) is extremely excellent.

The production of the graft copolymer may be performed by any method as long as the graft copolymer is formed. As an example of a method for producing a graft copolymer, when producing a hydroxyl group-containing acrylic resin (P), an unsaturated monomer having an allyl group and a methacryloyl group in one molecule such as allyl methacrylate may be used as another unsaturated monomer. A saturated monomer is copolymerized to produce a hydroxyl group-containing acrylic resin (P) having an allyl group in a polymer molecule side chain. Next, an epoxy group-containing acrylic resin (Q) is produced in the presence of the polymer to convert the epoxy group-containing unsaturated monomer (b) and the allyl group of the other unsaturated monomer (1-2). A graft copolymer having a hydroxyl group-containing acrylic resin (P) as a trunk polymer and an epoxy group-containing acrylic resin (Q) as a branch polymer is produced by utilizing the chain transfer reaction of the above.

In the present invention, as described above, a hydroxyl group-containing acrylic resin (P) or an epoxy group-containing acrylic resin (Q) is copolymerized, and thioglycolic acid, thiopropionic acid, etc. are used as chain transfer agents. The compound (m) having a thio group and a carboxyl group in the molecule is used to introduce a carboxyl group at the polymer terminal, and then an epoxy group-containing unsaturated monomer (b) is added to the carboxyl group to effect an addition reaction. Is converted to a radical polymerizable (meth) acryloyl group (modified), and then the polymer is used as a macromonomer to obtain a graft copolymer.

That is, in the presence of the macromonomer,
Production (radical copolymerization) of hydroxyl group-containing acrylic resin (P) or epoxy group-containing acrylic resin (Q)
A method of incorporating (copolymerizing) the macromonomer into a polymer is desirable.

In carrying out an addition reaction between the carboxyl group at the polymer terminal and the epoxy group-containing unsaturated monomer (b) to produce a macromonomer, polymerization of p-methoxyphenol, hydroquinone, dilaurylthiodipropionate, etc. is carried out. It is recommended that an addition reaction catalyst such as tetrabutylammonium bromide or triethylbenzylammonium chloride be used as an inhibitor or inhibitor, in an amount of about 50 to 50,000 ppm based on the total amount of the polymer and the epoxy group-containing unsaturated monomer. In addition, the addition reaction is performed at an oxygen concentration of 6 to
It is preferable to carry out the reaction under the conditions of 20% and a reaction temperature of 20 to 130 ° C. in order to prevent gelation and runaway reaction.

The graft copolymer used in the present invention comprises:
It is desirably contained in the coating resin (A) in an amount of 0.005 to 100% by weight, preferably 0.05 to 100% by weight. If the content is less than 0.005% by weight, the coating material tends to have a macro phase separation structure, and tends to precipitate and separate over time. In addition, as described above, there are cases where excellent performances are not exhibited even in the case of paint. In particular, in terms of adhesion to various substrates (adhesion regardless of the type of substrate) and shortening of the period until the performance of the coating film is exhibited, performance and function may be slightly reduced.

When the coating resin (A) is formed of 100% of the graft copolymer, various properties of the coating material and the coating film tend to exhibit extremely excellent performance as described above.
When the coating resin (A) is formed of 100% of the graft copolymer, the silane group-containing acrylic resin (P) and the epoxy group-containing acrylic resin (Q) are preferably in a weight ratio of P / Q = 0. .01 / 99.99 to 99.99 / 0.0
1, more preferably 2/98 to 98/2, further preferably 5/95 to 95/5.
If the compounding ratio is less than 0.01 / 99.99, the low-temperature curability of the coating and the adhesion to various coated objects (particularly, inorganic substances) may be deteriorated. The compounding ratio is 99.99 / 0.
01, the storage stability of the paint,
Adhesion to various substrates (especially plastics) and top coating resistance may be slightly deteriorated.

The hydroxyl group-containing acrylic resin (P) and / or the epoxy group-containing acrylic resin (Q) are preferably further copolymerized with the fluoroalkyl group-containing unsaturated monomer (c). The fluoroalkyl group-containing unsaturated monomer (c) may be used alone or as a mixture of two or more.

More preferably, in the present invention, the coating resin (A) contains a graft copolymer comprising a hydroxyl group-containing acrylic resin (P) and an epoxy group-containing acrylic resin (Q), and is used as a copolymer as a branch polymer. It is recommended that either the hydroxyl group-containing acrylic resin (P) and / or the epoxy group-containing acrylic resin (Q) be copolymerized with the fluoroalkyl group-containing unsaturated monomer (c).

When the fluoroalkyl group-containing unsaturated monomer (c) is copolymerized, the storage stability of the paint, the pigment dispersibility, the pigment dispersion stability, the weather resistance, durability and chemical resistance of the coating film Various properties such as water resistance, warm water resistance, and stain resistance tend to be improved. This characteristic performance tends to be manifested as a more pronounced effect when copolymerized with a branch polymer. The fluoroalkyl group-containing unsaturated monomer (c)
The copolymer has a tendency to further enhance the surface active function, which is a preferable embodiment. That is, during storage of the paint, there is an effect of protecting a highly reactive functional group (such as an alkoxysilane group, an epoxy group, or a hydroxyl group) from an inadvertent reaction and dramatically improving storage stability. Further, when forming a coating film, the coating film has an effect of lowering or appropriately increasing the interfacial tension of the coating material and appropriately adjusting the viscosity, thereby improving the finish of the coating and the appearance of the coating film. Further, in the process of curing the coating film, there is an effect of promoting an appropriate curing speed and a quick crosslinked coating film formation based on the function of enhancing the function of each functional group as described above.

The fluoroalkyl group-containing unsaturated monomer (c) is added to the hydroxyl group-containing acrylic resin (P) and / or the epoxy group-containing acrylic resin (Q) in an amount of preferably 0.002 to 98% by weight, more preferably 0.005-
It is recommended to copolymerize 95% by weight. When the copolymerization amount is less than 0.002% by weight, the storage stability of the paint,
The effect of improving pigment dispersibility may not be remarkable. Further, when the copolymerization is more than 98% by weight, the microphase separation between the hydroxyl group-containing acrylic resin (P) and the epoxy group-containing acrylic resin (Q) becomes too large, and the adhesion to the coating object is increased. In some cases, or the adhesion to the top coating material may be deteriorated.

In the present invention, the epoxy group-containing acrylic resin (Q) is preferably further copolymerized with the alkoxysilane group-containing unsaturated monomer (d). The alkoxysilane group-containing unsaturated monomer (d) may be used alone or as a mixture of two or more.

More preferably, the coating resin (A) contains a graft copolymer comprising a hydroxyl group-containing acrylic resin (P) and an epoxy group-containing acrylic resin (Q), and the epoxy resin to be copolymerized as a backbone polymer. It is recommended that the alkoxysilane group-containing unsaturated monomer (d) is copolymerized with the group-containing acrylic resin (Q).

Copolymerization of the alkoxysilane group-containing unsaturated monomer (d) tends to further improve the curability of the coating material and the adhesion to various objects to be coated, which is a preferred embodiment.

The alkoxysilane group-containing unsaturated monomer (d) is added to the epoxy group-containing acrylic resin (Q) in an amount of 0.02 to 98% by weight, preferably 0.1 to 98% by weight of all monomers constituting the acrylic resin. Desirably, the copolymerization is carried out at 2 to 85% by weight. When the copolymerization amount is less than 0.02% by weight,
The low-temperature curability of the paint may be slightly deteriorated, and the adhesion to inorganic substances such as glass tends to be slightly deteriorated. Further, when the copolymerization amount is more than 98% by weight, the wettability of the coating material to the object to be coated tends to decrease, and the coating repels and a good coating appearance may not be obtained. .

In the present invention, it is desirable that, in addition to the epoxy group-containing acrylic resin (Q), the alkoxysilane group-containing unsaturated monomer (d) is further copolymerized with the hydroxyl group-containing acrylic resin (P). The alkoxysilane group-containing unsaturated monomer (d) may be used alone or as a mixture of two or more.

More preferably, the coating resin (A) contains a graft copolymer comprising a hydroxyl group-containing acrylic resin (P) and an epoxy group-containing acrylic resin (Q), and the hydroxyl group copolymerized as a backbone polymer. Containing acrylic resin (P) and epoxy group containing acrylic resin (Q)
It is recommended that an alkoxysilane group-containing unsaturated monomer (d) be copolymerized with the above.

In addition to the epoxy group-containing acrylic resin (Q), the hydroxyl group-containing acrylic resin (P) is also copolymerized with the alkoxysilane group-containing unsaturated monomer (d), so that the curability of the paint is higher than that described above. This is a preferred embodiment because the adhesiveness to various coated objects tends to be further improved.

The alkoxysilane group-containing unsaturated monomer (d) is added to the hydroxyl group-containing acrylic resin (P) and the epoxy group-containing acrylic resin (Q) by 0.02 to 2.0% of all monomers constituting the acrylic resin. 98% by weight, preferably 0.1%
It is desirable that the copolymer be copolymerized in an amount of 2 to 85% by weight. If the copolymerization amount is less than 0.02% by weight, the low-temperature curability of the coating material may be slightly deteriorated, and the adhesion to inorganic substances such as glass tends to be slightly deteriorated. Further, when the copolymerization amount is more than 98% by weight, the wettability of the coating material to the object to be coated tends to decrease, and the coating repels and a good coating appearance may not be obtained. .

The hydroxyl group-containing acrylic resin (P) and the epoxy group-containing acrylic resin (Q) have a weight ratio of P / Q = 0.0
1 / 99.99 to 99.99 / 0.01, preferably 2
/ 98-98 / 2, more preferably 5 / 95-95 / 5
Is recommended. The mixing ratio is 0.01 / 9
When it is less than 9.99, the low-temperature curability of the coating and the adhesion to various objects (particularly inorganic substances) may be slightly deteriorated. If the amount is more than 99.99 / 0.01, the storage stability of the coating and the adhesion to various substrates (especially plastics) may be slightly deteriorated.

In the present invention, the curing agent (B) may contain at least one of an organometallic compound (e), a polyisocyanate compound (f), a melamine resin (g), and a reactive silane compound (h). desirable. When these compounds are blended, the curability of the paint, the appearance of the paint film (gloss, smoothness, etc.), water resistance, chemical resistance, weather resistance, and the like tend to be improved, which is a preferred embodiment.

The above compound to be mixed with the curing agent is preferably contained in the curing agent (B) in an amount of at least 0.5% by weight or more.
More preferably, it is recommended to contain 3% by weight or more. If it is less than 0.5% by weight, the curability is insufficient,
Chemical resistance, water resistance, etc. may deteriorate.

As the organometallic compound (e), dibutyltin dilaurate, dibutyltin dioxide,
IIA, IIB, IIIA, IV such as zinc acetate, magnesium acetate, lead octylate, calcium octylate, zirconium chelate compound, titanium chelate compound, aluminum chelate compound, titania sol, alumina sol, etc.
Organometallic compounds containing Group A, IVB, VB, VIIB, and VIII metal atoms are exemplified. The organometallic compound (e) is
They may be used alone or as a mixture of two or more.

Among the organometallic compounds (e), organotin compounds such as dibutyltin dilaurate and organic metal chelate compounds such as zirconium chelate compounds, titanium chelate compounds and aluminum chelate compounds can be preferably used. When these compounds are blended, the performance of the coating such as low-temperature curability at about -20 to 100 ° C., chemical resistance and water resistance of the coating film tends to be improved.

Among the above compounds, the aluminum chelate compound (i) can be preferably used. Examples of the aluminum chelate compound (i) include aluminum ethyl acetoacetate diisopropylate, aluminum tris (ethyl acetoacetate), aluminum tris (acetyl acetate), aluminum bisethyl acetoacetate monoacetylacetonate, and aluminum monoacetylacetonate bis (alkyl Acetoacetate) (the alkyl group has 2 to 18 carbon atoms). These compounds may be used alone or as a mixture of two or more. Among the above compounds, aluminum tris (acetylacetate) and aluminum monoacetylacetonate bis (alkylacetoacetate) (the alkyl group has 2 to 18 carbon atoms) can be particularly preferably used.

Aluminum tris (acetylacetate) tends to improve the low-temperature curability of coatings, and aluminum monoacetylacetonate bis (alkylacetoacetate) (where the alkyl group has 2 to 18 carbon atoms) tends to improve storage stability.

The above compound is used in an amount of 0.02 to 200 parts by weight (0.2 to 200 parts by weight) based on 100 parts by weight of the resin for coating material (A).
PHR)), preferably 0.05 to 150 parts by weight (=
(0.05 to 150 PHR).
If the compounding amount is less than 0.02 PHR, the low-temperature curability of the paint may be slightly deteriorated, and satisfactory results in water resistance, adhesion, weather resistance, etc. may not be obtained. In addition, the blending amount is 2
If the amount is more than 00 PHR, the storage stability of the coating tends to deteriorate, and the coating is likely to be colored or blemishes are likely to occur, which may impair the appearance of the coating.

Examples of the polyisocyanate compound (f) include compounds having at least two isocyanate groups in a molecule such as hexamethylene diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate; Blocked polyisocyanate compounds in which isocyanate groups are temporarily blocked (protected) by a compound can be exemplified. The polyisocyanate compound (f) may be a single compound or a mixture of two or more compounds. Among these compounds, non-yellowing type hexamethylene diisocyanate and addition / condensation products thereof, adduct type, those having an isocyanurate ring in the molecule, those having a triazine ring in the molecule are those having weather resistance. It is recommended in terms of improvement of chemical resistance. The above compound reacts with the hydroxyl group of the coating resin (A) (or
When other compounds having a hydroxyl group and polymers are blended, the molar ratio of the hydroxyl group to the isocyanate group is from 0.5 to 2.0, preferably from 0.8 to 2.0, based on the total of those hydroxyl groups. It is desirable to blend the polyisocyanate compound (f) so as to be 1.2. If the molar ratio is less than 0.5, the curability of the coating and the crosslink density of the coating may be slightly insufficient, and the weather resistance and scratch resistance of the coating tend to slightly decrease. If the molar ratio is more than 2.0, the drying properties (complete curing and dryness to the touch) of the paint tend to be slightly slow, and the non-adhesive drying properties and blocking properties of the coating film are slightly deteriorated. May be.

Here, the compounds and polymers having a hydroxyl group are compounds having at least two alcoholic hydroxyl groups in the molecule and having a number average molecular weight of 50 to 200,000. Examples of the compound include ethylene glycol, diethylene glycol, triethylene glycol, polypropylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, polyvinyl alcohol, polyester resin, fluororesin, acrylic resin, and furan resin. . These compounds can be used alone or
It may be a mixture of more than one kind.

Examples of the melamine resin (g) include hexamethylolmelamine resin, hexamethoxymelamine resin, methoxybutoxymelamine resin, hexabutoxymelamine resin and the like. In the present invention, those used for paints and inks can be used. These compounds may be used alone or as a mixture of two or more. The compound is preferably from 5 to 80 PHR, more preferably from 5 to 80 PHR, based on the resin (A) for paint (or other compound having a hydroxyl group and a polymer when the polymer is blended). Preferably 8-6
It is desirable to be blended so as to be 0 PHR. If the amount is less than 5 PHR, the crosslinkability of the coating film may be insufficient, and the hardness of the coating film may be reduced. When the amount is more than 80 PHR, the initial curability of the paint and the weather resistance of the coating film may be deteriorated.

The reactive silane compound (h) used in the present invention includes tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, 3-glycidyl Xypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3,4-epoxycyclohexylmethyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltriethoxysilane,
Examples thereof include compounds having at least one hydrolyzable alkoxysilane group in one molecule such as 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and condensates of the compound. These compounds may be used alone or as a mixture of two or more.

The addition of these compounds is preferable because the low-temperature curability and weather resistance of the paint tend to be remarkably improved. The above compound is used in an amount of 0.5 to 1000 parts by weight (0.5 to 1000 PH) based on 100 parts by weight of the resin for coating (A).
R), preferably 2 to 500 parts by weight (2 to 500 PH)
R) It is desirable to be blended. 0.5PHR
If less than, the low-temperature curability of the paint is not sufficiently improved,
The weather resistance, scratch resistance, etc. may be slightly inferior. Also,
When the compounding amount is more than 1,000 PHR, the wettability of the coating material to the object to be coated is deteriorated, and the adhesion and the appearance of the coating film may be deteriorated.

Among the above compounds, an organoalkoxysilane compound (j) having at least one epoxy group and a hydrolyzable alkoxysilane group in one molecule can be preferably used.

Examples of the organoalkoxysilane compound (j) having at least one epoxy group and a hydrolyzable alkoxysilane group in one molecule include 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane. , 3,4-epoxycyclohexylmethyltriethoxysilane, and hydrolysates and condensates of the compound. When the compound is blended, it reacts complementarily with the reactive functional group of the coating resin (A) to form a densely crosslinked coating film. As a result, it is possible to form a coating film having excellent scratch resistance, chemical resistance, water resistance, and weather resistance, which is relatively difficult to achieve with a normal organic coating film.

In the present invention, the nonionic surfactant (C)
Is a fluorosurfactant (k) having a perfluoroalkyl group in the molecule, the storage stability of the coating, curability, appearance of the coating film, chemical resistance, weather resistance, scratch resistance, etc. are further improved Excellent and recommended. This is considered to be related to the electrical properties and molecular properties of the fluorine atom and the perfluoroalkyl group. The storage stability of an acrylic resin having an alkoxysilane group on the side chain is not always good, and the alkoxysilane group is gradually hydrolyzed due to the moisture and other factors present in the coating over time, and finally becomes a silanol group. Has a tendency to form a siloxane bond between the molecules to increase the viscosity and gel. The fluorine-based surfactant (k) has an action of firmly suppressing and preventing this tendency and phenomenon. That is, as long as it is stored as a paint, even if it is stored for a very long time, it prevents the paint from thickening and gelling, and does not cause any change in the paint. On the other hand, once the coating film is formed, it has an effect of actively promoting the crosslinking reaction of the coating material and promoting the formation of a strong and excellent coating film. In addition, due to its outstanding surface activity, it improves the leveling property of the coating film and the wettability of the coating material, significantly improves the appearance of the coating film (excellent leveling property, does not cause shrinkage), and adheres to various coating materials. The improvement of the property is exhibited.

The fluorosurfactant (k) having a perfluoroalkyl group in the molecule used in the present invention includes perfluoroalkylethylene oxide adducts, perfluoroalkylamine oxides, perfluoroalkyl-containing oligomers, specifically For example, "SURFLON S-141", "SURFLON S-1"
45 "," Surflon S-381 "," Surflon S-
383 "," Surflon S-393 "," Surflon S "
C-101 "," Surflon SC-105 "," Surflon KH-40 "," Surflon SA-100 "(these are products of Seimi Chemical Co., Ltd.)," MegaFac F
-171 "," MegaFac F-172 "," MegaFac F-173 "," MegaFac F-177 "," MegaFac F-178A "," MegaFac F-178 "
K ”,“ Mega Fuck F-179 ”,“ Mega Fuck F ”
-183 "," MegaFac F-184 "," MegaFac F-815 "," MegaFac F-470 "," MegaFac F-471 "(all products of Dainippon Ink and Chemicals, Inc.), etc. Can be exemplified. (Reference: "137
00 Chemical Products ", p1239-p1242, Kagaku Kogyo Nippo (2000). The fluorine-based surfactant (k) having a perfluoroalkyl group may be used alone or in a mixture of two or more.

Further, in the present invention, HLB (hydrophilic-lipophilic balance value) (reference material: http://chemical.kao.co.
jp / TechnicalInformation / ChemicalPlaza / su ... / surfac
tant2-7.ht) is preferably 0 to 20, preferably 2 to 18, and more preferably 5 to 15 nonionic surfactant (C). Nonionic surfactants capable of determining HLB include polyoxyethylene groups as hydrophilic groups,
Alternatively, it has a substance derived from a high alcohol such as glycol, glycerol, pentaerythritol, or sorbitan. Although the HLB is in the range of 0 to 20, the storage stability of the paint can be further enhanced by using a nonionic surfactant capable of obtaining the HLB. Furthermore, in the present invention,
An HLB having a range of 5 to 15 and a slightly increased hydrophilicity can be more preferably used.

More specifically, the nonionic surfactant (C) is a fluorinated surfactant (k) and the HLB is 5%.
-12 or a number average molecular weight of 500-1
Those which are 0000 oligomers can be suitably used.

At this time, if the HLB is less than 5, the effect of improving storage stability may not be noticeable. HLB is 1
If it exceeds 2, the water resistance and chemical resistance of the coating film tend to slightly deteriorate. If the number average molecular weight of the oligomer is less than 500, the storage stability may not be sufficiently improved and compensated. When the number average molecular weight exceeds 10,000, the paint tends to repel, and the appearance of the coating film may deteriorate.

Further, the resin composition for coating of the present invention may be used, if necessary, by converting a photostable compound (HALS) having no hydrogen atom directly bonded to a nitrogen atom into a resin (A) 1 for coating.
0.2 to 50 parts by weight (0.2 to 50 parts by weight)
PHR), more preferably 0.5 to 20 PHR.

As HALS, "13700 Chemical Products" (Kagaku Kogyo Nippo) (2000), p. 1069-1
070, “Sanol, a polymer stabilizer” (manufactured by Sankyo Co., Ltd., product catalog (1994)).
LS can be exemplified. In the present invention, among these,
HALS having no hydrogen atom directly bonded to the nitrogen atom can be suitably blended. HALS having no hydrogen atom directly bonded to a nitrogen atom include bis (1,2,2,6,6
-Pentamethyl-4-piperidyl) sebacate, 1-
{2- (3-((3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6
-Tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro {4.5} decane-2,4-dio and the like. These compounds may be used alone or as a mixture of two or more. By blending the HALS, the weather resistance of the coating film is drastically improved without coloring the coating material and the coating film.

When the amount of the HALS is less than 0.2 PHR, no significant improvement in the weather resistance of the coating film may be observed. Or a large amount of shrinkage may occur in the coating film.

Further, it is more preferable that the coating resin composition of the present invention contains a light stable compound (HALS) having a base constant (PKb) of 8 or more. By compounding the compound,
It is possible to dramatically improve the weather resistance of the coating film without impairing the basic performance such as the storage stability and the low-temperature curability of the coating material.

HALS of PKb8 or more include 1-
{2- (3-((3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6
-Tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro {4.5} decane-2,4-dione. These compounds may be used alone or as a mixture of two or more. When PKb is less than 8, the paint tends to cause poor curing, or storage stability tends to deteriorate.

The resin composition for coating of the present invention can be produced, for example, by adding a curing agent (B) to the resin for coating (A), stirring and mixing. In addition, if necessary, paint production (eg, pigment dispersion) using paint resin (A)
And, if necessary, diluting solvent, paint additive (antifoaming agent,
A pigment dispersant, a leveling agent, an anti-settling agent, etc.) may be added to form a paint, and the curing agent (B) may be blended immediately before coating.

The coating resin composition of the present invention may further comprise toluene, xylene, ethyl acetate, butyl acetate, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, Organic solvents such as acetone alcohol, hexafluoroisopropanol, 3-methyl-3-methoxybutanol, methyl ethyl ketone, dioxane, methyl isobutyl ketone, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, and acetylacetone , Titanium oxide, calcium carbonate, carbon black, silica sol, titania sol, navy blue, iron oxide and other pigments, leveling agents, thickeners, pigment dispersion , Antifoaming agents, UV absorbers (benzotriazole-based ultraviolet absorber is preferred), HA
LS (PKb (preferably having a base constant of 8 or more), coating additives well known in the art such as antioxidants, resins and coatings for various coatings (Reference: 13599)
Chemicals, p1237 to p1259, Chemical Daily Co., Ltd. (1999)), rubbers such as silicone rubber (and intermediate), butyl rubber, chloride rubber, isoprene rubber, polyurethane rubber, rubber-modified epoxy resin, silane compounds (silanol group Is undesirable because storage stability deteriorates), silane oligomers and polymers having a reactive functional group (hydroxyl or alkoxysilane group) at the polymer terminal or side chain, and fluorine for paints having a hydroxyl group in the side chain Resin (for example, “Lumiflon” (Asahi Glass Co., Ltd.)
Products)), chlorinated polypropylene resins, chlorinated polypropylene resins modified with acrylic resins (eg, "Cotax""LG-950" (product of Toray Industries, Inc.), and other coating resins, and coating resins Epoxy resins (particularly, alicyclic epoxy resins are preferred) such as oligomers and polymers for modification, and any other substances necessary for compounding the paint can be compounded and used without any problem.

The coating containing the coating resin composition of the present invention can be applied by various coating methods applied to general coatings. That is, spray coating, roll coating,
Curtain coating, brush coating, electrostatic coating, anion, cationic electrodeposition coating, dipping and the like can be exemplified. It can be used as a primer (adhesive layer), as a base coat (usually colored paint), or as a top coat (usually clear paint).
It can also be used as, and can also serve as all at the same time. Further, the above-mentioned paints (resins and paints for paints (reference: 13599 chemical products, p1237 to p125)
9, Chemical Daily Co., Ltd. (1999))).

The base material (substrate) to which the coating containing the coating resin composition of the present invention can be applied includes polystyrene resin, acrylic resin, acrylonitrile-styrene-butadiene resin (ABS), polypropylene, and ethylene-propylene resin. Plastics such as polycarbonate resin, noryl resin, nylon resin, polyester resin, and blends of these and polyolefins, fillers, reinforcing materials such as glass and carbon fiber (alloys), heat of epoxy resins, unsaturated polyester resins, etc. Curable resin, the above-mentioned paint (resin and paint for paint (reference: 13599, chemical products, p1237 to p1259, Chemical Daily Inc. (19
99))) Painted articles, minerals such as glass, mortar, asbestos cement slate, rocks, and metals such as iron (and alloy), copper (and alloy), aluminum (and alloy), magnesium (and alloy) Flammable materials such as paper, vinyl cloth and the like.

[0095] In addition, the applications in which these are used include:
Plastic parts and metal parts such as automobiles and motorcycles, glass parts (bumpers, air spoilers, door handles, wheel caps, bodies, fuel tanks, manifolds, windows, etc.), decorative and craft products, glass products for practical use, Ceramics (glass bottles, vases, flower pots, various equipment for gardening (fences, benches, chairs, shelves, etc.), window glass, polycarbonate glass, acrylic glass, tables and chairs, cupboards, closets, closets, woodworking, etc. Products and printed finished products), inorganic materials used in construction and building materials, glass, metals (curtain walls, aluminum sashes, entrance doors, gates, siding boards, walls, roof tiles, etc.), plastics and metal parts for home appliances (Refrigerator, washing machine, TV, video, telephone, facsimile, personal computer, etc.), plastic accessories Click, metal, crockery can be exemplified (buttons, accessories, clothes, etc.) and the like.

Furthermore, at the same time, the present invention provides these coated articles. The coated article according to the present invention is excellent in various performances and functions such as durability, decorativeness, workability and the like.

[0097]

The present invention will be described below in detail with reference to examples. In addition, unless otherwise specified, the composition ratio indicates weight%,
The compounding amount indicates the number of parts. In addition, the compounding amount indicated by PHR is an amount based on the solid content.

Before showing the examples and comparative examples, each raw material (silane-containing acrylic resin (P
-), A production example of an epoxy group-containing acrylic resin (Q-), a coating resin (A-), a macromonomer (M-), and a production example of a graft copolymer (G-)).

Incidentally, the amount of the unreacted epoxy group-containing unsaturated monomer (b) was measured using a Waters 600E
/ 2487 / SSV liquid chromatography system "
(Nippon Waters Co., Ltd.) and a Purecil C18 column (highly packed silica gel base reverse phase column) (Nippon Waters Co., Ltd.) (filler MightysilRP)
-18 (GP (ODS), column size 45 mm × 25 cm, filter size 2 μm, pore size 120 Å, particle size 5 μm), water / acetonitrile (= 40/60 vol%) as solvent, 0.1% phosphoric acid / ion exchange Using water / acetonitrile (= 50/20/30 vol%), the sample (analyte) was analyzed as a 10% methanol solution.

The amount of the unreacted epoxy group-containing unsaturated monomer (b) in the paint can be analyzed as follows.

The heating residue (solid content%) of the coating was determined according to JIS K
It is measured according to 5400 (α%). Next, the paint (βg) is diluted 5-fold with acetone and stirred well until uniform. This was centrifuged at 10,000
Processing is performed at a rotation speed of min-1 for 180 minutes. The precipitate is collected, dried at 140 ° C. for 30 minutes, and βg
(Γg). The resin component in the paint βg (this is referred to as paint resin (A) in the present invention) is calculated according to the following equation. Resin content (δg) = β × α / 100-γ Separately, the supernatant liquid after centrifugation was analyzed according to the separately described method for analyzing an epoxy group-containing unsaturated monomer (b), and the epoxy group in the paint βg was analyzed. The content of the unsaturated monomer (b) is measured (ε ppm). The amount of the epoxy group-containing unsaturated monomer (b) in the coating resin (A) is calculated by the following equation. Epoxy group-containing unsaturated monomer (b) amount (ppm) = δ /
β × ε [Production example of hydroxyl group-containing acrylic resin (P-)] [Production example of P-1] α, α′-azobisisopropane using γ-butyrolactone (GBL) (aprotic polar solvent) as a polymerization solvent Butylonitrile (AIBN) (10 hour decomposition half-life temperature 72 ° C.) was used as the polymerization initiator, and the polymerization temperature was 90 ° C.
With methyl methacrylate (MMA) / methacrylic acid 2-
A hydroxyl group-containing acrylic resin (P-1) composed of hydroxyethyl (HEMA) (hydroxyl group-containing unsaturated monomer) (= 90/10) was produced. Hydroxyl-containing acrylic resin (P-
The number average molecular weight of 1) is 15,000, and the hydroxyl value is 43.2.
mg KOH, the solid content was 50%.

[Production Example of P-2]
Using IBN as a polymerization initiator and thioglycolic acid (TGH)
Is used as a chain transfer agent at a polymerization temperature of 90 ° C. and MMA / HE
A hydroxyl group-containing acrylic resin (P-2) composed of MA (= 80/20) was produced. Hydroxyl-containing acrylic resin (P-
2) has a number average molecular weight of 8,000 and an acid value of 13.7 mg.
KOH, hydroxyl value: 86.3 mg KOH, solid content: 50
%Met.

[Production Example of P-3]
Using IBN as a polymerization initiator and TGH as a chain transfer agent
At a polymerization temperature of 90 ° C., MMA / HEMA / “Fluowet MAE-800” (perfluorooctylethyl methacrylate (an unsaturated monomer having a fluoroalkyl group), a product of Clariant Co., Ltd.) = 70/10/20) to produce a hydroxyl group-containing acrylic resin (P-3). The hydroxyl group-containing acrylic resin (P-3) has a number average molecular weight of 10,000 and an acid value of 1
3.7 mg KOH, the hydroxyl value was 43.2 mg KOH, and the solid content was 50%.

[Production Example of Epoxy Group-Containing Acrylic Resin (Q-)] [Production Example of Q-1] Using toluene (TOL) / n-butyl alcohol (NBAL) (= 60/40) as a solvent,
Using IBN as a polymerization initiator, at a polymerization temperature of 90 ° C., MMA
/ N-butyl methacrylate (BMA) / n-acrylate
Butyl (BA) / “A-200” (3,4-epoxycyclohexylmethyl acrylate (alicyclic epoxy group-containing unsaturated monomer), a product of Daicel Chemical Industries, Ltd.)
(= 40/20/20/20) to produce an epoxy group-containing acrylic resin (Q-1). The number average molecular weight of the epoxy group-containing acrylic resin (Q-1) is 18,000,
The epoxy equivalent was 910 and the solid content was 50%.

[Production Example of Q-2] TOL / xylene (X
YL) (= 60/40) as a solvent, AIBN as a polymerization initiator, MMA / BMA / BA at a polymerization temperature of 90 ° C.
/ [A-200] / HEMA (= 30/20/20/2)
0/10) epoxy resin containing epoxy group (Q-
2) was manufactured. Epoxy group-containing acrylic resin (Q-
2) has a number average molecular weight of 12,000 and an epoxy equivalent of 9
10, hydroxyl value is 43.2mgKOH, solid content is 50%
Met.

[Production Example of Paint Resin (A-)] [Production Example of A-1] Hydroxyl group-containing acrylic resin (P-1)
And an epoxy group-containing acrylic resin (Q-1) at 20:80.
To produce a coating resin (A-1). The amount of epoxy group-containing unsaturated monomer in the coating resin (A-1) is 50.
ppm. The solid content was 50%.

[Production Example of A-2] Acrylic resin containing hydroxyl group (P-1) and acrylic resin containing epoxy group (Q-2)
Were mixed at a ratio of 10:90 to produce a coating resin (A-2). The amount of the epoxy group-containing unsaturated monomer in the coating resin (A-2) was 5 ppm. The solid content was 50%.

[Production Example of Macromonomer (M-)] [Production Example of M-1] Hydroxyl group-containing acrylic resin (P-2)
And the mole number of the carboxyl group of the silane group-containing acrylic resin (P-2) and the mole number of GMA are 1: 1.25.
And heated to 95 ° C. Tetraethylbenzylammonium chloride (TEBAC) is used as a catalyst for the addition reaction between the carboxyl group and the epoxy group, 2% of the total amount of the solid content of the hydroxyl group-containing acrylic resin (P-2) and GMA, and p-methoxyphenol is used as a polymerization inhibitor. Is the solid content of the hydroxyl group-containing acrylic resin (P-2) and GM
0.2% based on the total amount of A and 8% oxygen concentration
A time addition reaction was performed to produce a macromonomer (M-1). The acid value of the macromonomer (M-1) is 0.1 mg
KOH, solid content was 50%.

[Production Example of M-2] GMA was added to the hydroxyl-containing acrylic resin (P-3), and the hydroxyl-containing acrylic resin (P-3) was used.
-3) The molar number of carboxyl groups and the molar number of GMA were set to 1: 1.25, and trimethyl orthoacetate (TM) (a dehydrating agent) was further added to the solid content of the hydroxyl group-containing acrylic resin (P-3). And GMA were added so as to be 0.5% of the total amount, and the temperature was raised to 95 ° C. TEBAC is 2% based on the total amount of the solid content of the hydroxyl group-containing acrylic resin (P-3) and GMA, and p-methoxyphenol is 0% based on the total amount of the solid content of the hydroxyl group-containing acrylic resin (P-3) and GMA. An addition reaction was performed for 8 hours at a charge of .25% and an oxygen concentration of 8% to produce a macromonomer (M-2). The acid value of the macromonomer (M-2) was 0.0 mg KOH, and the solid content was 50%.

[Production Example of Graft Copolymer (G-)] [Production Example of G-1] A 3 L four-necked flask equipped with a stirrer, nitrogen introduction tube, thermometer, monomer dropping device, and reflux condenser was provided. , TOL / NBAL (= 80/20) 629 g,
(M-1) 400 g was charged, and the temperature was raised to 92 ° C. while stirring. MMA / BMA / BA / GMA / HEMA (=
40/20/20/10/10) AIBN1 to 800 g
The mixed monomer in which 5 g was dissolved was dropped into the flask in 3 hours. After the polymerization was further continued for 1 hour,
A mixed solution of 0 g and 6 g of AIBN was added in three portions every 30 minutes, and after the addition was completed, polymerization was further performed for 1 hour. Cooled to room temperature, and a branched polymer having (P-2) as a branched polymer /
Backbone polymer = 20/80 graft copolymer (G-1)
Was manufactured. The number average molecular weight of (G-1) is 22,000
0, the epoxy equivalent was 1,775, the amount of unreacted epoxy group-containing unsaturated monomer was 20 ppm, and the hydroxyl value was 43.2 mg.
KOH, solid content was 50%.

[Production Example of G-2] 3 equipped with a stirrer, a nitrogen inlet tube, a thermometer, a monomer dropping device, and a reflux condenser.
To the L four-necked flask, add TOL / NBAL (= 80/2
629 g of (0) and 400 g of (M-2) were charged, and the temperature was raised to 92 ° C. while stirring. MMA / BMA / BA / "A-
200 "/ HEMA /" SZ-6040 "(SZ) (3
-Methacryloyloxypropyltrimethoxysilane (an unsaturated monomer containing an alkoxysilane group), a product of Dow Corning Toray Silicone Co., Ltd.) (= 30/20)
/ 20/10/10/10) 800 g to AIBN 15 g
Was dissolved in the flask over 3 hours. After the polymerization was further continued for 1 hour, TOL150
g and 6 g of AIBN were added in three portions every 30 minutes, and after the addition was completed, polymerization was further performed for 1 hour. After cooling to room temperature, a graft copolymer (G-2) having a branch polymer / stem polymer = 20/80 using (P-3) as a branch polymer was produced. The graft copolymer (G-2) had a number average molecular weight of 18,000, an epoxy equivalent of 2,275, an unreacted epoxy group-containing unsaturated monomer amount of 30 ppm, and a hydroxyl value of 4
7.5 mg KOH, 50% solids.

[0112]

(Example 1) A resin (A-1) for paint was coated with "Surflon KH-40" (perfluoroalkylethylene oxide adduct (fluorinated nonionic surfactant, H
LB9.8), a product of Seimi Chemical Co., Ltd.) was added to the resin composition for coating so as to be 5000 ppm, and the mixture was stirred and mixed until it became uniform. Next, “Aluminum chelate A (W)” (A (W)) (aluminum tris (acetylacetonate) (aluminum chelate compound, curing agent), a product of Kawaken Fine Chemical Co., Ltd.) is 3PHR and acetylacetone (AcAc) 6PHR. Was added, and the mixture was stirred and mixed until a homogeneous solution was obtained, whereby a resin composition for a coating material of Example 1 was produced. The content of the epoxy group-containing unsaturated monomer (b) in the coating resin composition was 10 ppm. The polymerization temperature of the epoxy group-containing acrylic resin (Q-1) was set to 90 ° C., and the AIBN 10-hour half-life temperature (7
(2 ° C.) + 18 ° C. makes it possible to reduce the amount of unreacted epoxy group-containing unsaturated monomers.

(Example 2) The resin for paint (A-2)
"MegaFac F-471" (perfluoroalkyl group-containing oligomer (fluorinated nonionic surfactant),
(A product of Dainippon Ink and Chemicals, Inc.) was added to the coating resin composition so as to be 500 ppm, and the mixture was stirred and mixed until it became uniform. Next, “A (W)” is 3PHR,
Add 6PHR of AcAc and stir until a homogeneous solution is obtained,
By mixing, a resin composition for coating of Example 2 was produced. The content of the epoxy group-containing unsaturated monomer (b) in the coating resin composition was 1 ppm. The polymerization temperature of the epoxy group-containing acrylic resin (Q-2) was set to 90 ° C.
By setting the time half-life temperature (72 ° C) + 18 ° C,
It has become possible to reduce the amount of unreacted epoxy group-containing unsaturated monomers.

Example 3 A resin for paint (A-2)
"Newcol 564" (polyoxyethylene nonylphenyl ether (nonionic surfactant, HLB1
2.3), a product of Nippon Emulsifier Co., Ltd.) was added to the resin composition for coating so as to have a concentration of 20,000 ppm, and the mixture was stirred and mixed until it became uniform. Next, “A (W)” is 3PH
R and AcAc were added to 6 PHR, and the mixture was stirred and mixed until a uniform solution was obtained, whereby a coating resin composition of Example 3 was produced.
The content of the epoxy group-containing unsaturated monomer (b) in the coating resin composition was 1 ppm. The polymerization temperature of the epoxy group-containing acrylic resin (Q-2) was set to 90 ° C., and AIB
By setting the 10-hour half-life temperature of N (72 ° C.) + 18 ° C., it became possible to reduce the amount of unreacted epoxy group-containing unsaturated monomers.

Example 4 The resin for paint (A-2)
"Megafac F-471" was added to the resin composition for coating so as to be 500 ppm, and the mixture was stirred until uniform.
Mixed. Next, “SH-6040” (SH) (3-
Glycidoxypropyltrimethoxysilane (silane group-containing compound, curing agent), 20 PHR for Toray Dow Corning Silicone Co., Ltd., and 3 A for "A (W)"
Add R, AcAc 6PHR and stir until uniform
The resin composition for coating of Example 4 was manufactured by mixing. The content of the epoxy group-containing unsaturated monomer (b) in the coating resin composition was 1 ppm. The polymerization temperature of the epoxy group-containing acrylic resin (Q-1) was set to 90 ° C.
By setting the time half-life temperature (72 ° C) + 18 ° C,
It has become possible to reduce the amount of unreacted epoxy group-containing unsaturated monomers. And "SH", the concentration was reduced by dilution.

(Example 4) The resin for paint (A-2)
"Megafac F-471" was added to the resin composition for coating so as to be 500 ppm, and the mixture was stirred until uniform.
Mixed. Next, "Sumijur N-3500"
(N-3500) (a polyisocyanate compound (curing agent), a product of Sumitomo Bayer Urethane Co., Ltd.) was obtained by adding the number of moles of hydroxyl groups of the coating resin (A-2) to "Sumidur N
-3500 "to give a molar ratio of isocyanate groups of 1: 1 to produce the coating resin composition of Example 5. The content of the epoxy group-containing unsaturated monomer (b) in the coating resin composition was 1 ppm. The polymerization temperature of the epoxy group-containing acrylic resin (Q-2) was set to 90 ° C., and AIB
It is possible to reduce the amount of the unreacted epoxy group-containing unsaturated monomer diluted by setting the 10-hour half-life temperature of N (72 ° C.) + 18 ° C. and by adding “N-3500”. became.

Example 5 Graft Copolymer (G-1)
In the "Surflon KH-40" was added so as to be 5000ppm in the coating resin composition, stirred until homogeneous, and mixed. Next, "SH" is changed to 20 PHR, "A"
(W) "was added to 3 PHR and AcAc to 6 PHR, and the mixture was stirred and mixed until a uniform solution was obtained, whereby a resin composition for coating of Example 5 was produced. The content of the epoxy group-containing unsaturated monomer (b) in the coating resin composition was 0.05 ppm. The aprotic polar solvent (GBL) was used during the production of the macromonomer (M-1), and the epoxy group-containing unsaturated monomer (GM) in the composition of the graft copolymer (G-1) was used.
A) By appropriately blending the amount and being diluted by the "SH" blend, it became possible to reduce the amount of unreacted epoxy group-containing unsaturated monomer.

(Example 6) Graft copolymer (G-1)
Was added to the resin composition for coating so as to be 5000 ppm, and the mixture was stirred and mixed until it became uniform. Next, "Symel C-285"
(Melamine resin, product of Mitsui Cytec Co., Ltd.)
PHR, "A (W)" is 3PHR, AcAc is 6PHR
The mixture was added, stirred and mixed until a uniform solution was obtained, whereby a resin composition for coating of Example 6 was produced. The content of the epoxy group-containing unsaturated monomer (b) in the coating resin composition is 0.05 p.
pm. Proper use of aprotic polar solvent (GBL) during the production of macromonomer (M-1) and proper blending of epoxy group-containing unsaturated monomer (GMA) in the composition of graft copolymer (G-1) As a result, the amount of the unreacted epoxy group-containing unsaturated monomer can be reduced by being diluted with “Cymel C-285”.

Example 7 Graft Copolymer (G-2)
In the "Surflon KH-40" was added so as to be 5000ppm in the coating resin composition, stirred until homogeneous, and mixed. Next, "SH" is changed to 20 PHR, "A"
(W) "was added to 3 PHR and AcAc to 6 PHR, and the mixture was stirred and mixed until a uniform solution was obtained, whereby a resin composition for coating of Example 5 was produced. The content of the epoxy group-containing unsaturated monomer (b) in the coating resin composition was 0.05 ppm. The aprotic polar solvent (GBL) was used during the production of the macromonomer (M-2), and the epoxy group-containing unsaturated monomer (“A
-200 "), and by being diluted by the" SH "formulation, it was possible to reduce the amount of unreacted epoxy group-containing unsaturated monomers.

(Comparative Example 1) A coating resin composition of Comparative Example 1 was produced in the same manner as in Example 1, except that "Surflon KH-40" was not blended.

Comparative Example 2 A coating resin composition of Comparative Example 2 was produced in the same manner as in Example 7, except that “Surflon KH-40” was not used.

(Comparative Example 3) "A-200" was added to the resin composition for coating of Example 7 so as to have a concentration of 10,000 ppm, and the mixture was stirred and mixed until it became uniform. A resin composition was manufactured.

[Test Method and Test Results of Paint] The results of tests using the resin compositions for paints produced in Examples and Comparative Examples are shown below.

[0124] 1. Manufacture of paint Each resin composition for paint obtained in each of the above Examples and Comparative Examples was subjected to toluene (TOL) / butyl acetate (BAC).
/ Xylene (XYL) / cyclohexanone (CN) / isobutyl alcohol (IBAL) (= 30/20/5 /
20/20/5) using Ford Cup No. 4 was diluted to a viscosity of 15 seconds (25 ° C.). This was used as a clear paint for testing.

[0125] 2. Coating 1) Production of test coated plate Aluminum alloy (JIS A 110
0) Test piece (AL), magnesium alloy (AS)
TM AZ91D) test piece (Mg), glass plate (G), acrylonitrile-styrene-butadiene resin (ABS resin) plate (ABS), polycarbonate resin (PC) plate (PC), bond steel plate (BD), asbestos cement slate Plate (KF), test plate (BP) coated with chlorinated polypropylene primer on polypropylene alloy resin (PP) for automobile bumpers, carbon fiber reinforced plate (manufactured from carbon fiber and bisphenol A type epoxy resin) (CFRP )It was used.

These were treated with isopropyl alcohol (IP
After degreasing in A), using each of the above paints, at a temperature of 23 ° C,
Spray coating was performed under an atmosphere of humidity of 65% so that the coating film thickness after drying was 40 μm. The coated substrate (substrate to be coated) was dried at room temperature for 10 minutes, baked and dried at 80 ° C. for 30 minutes, and used for various tests.

2) Preparation of Painted Plate for Evaluation of Appearance of Coating Film (for Judging) An ABS resin plate was used as a base material. After degreased with isopropyl alcohol (IPA), spray coating was performed using the above-mentioned paints in an atmosphere at a temperature of 5 ° C. and a humidity of 20% so that the film thickness after drying was 60 μm.
The coated substrate (substrate to be coated) was dried for 10 minutes in an atmosphere at a temperature of 5 ° C. and a humidity of 20%, and baked and dried at 80 ° C. for 30 minutes.

3. Adhesion (JIS K 5400 8.
Refer to 5.2 (JIS Handbook, Paints-1997). ) 100/100 is acceptable, otherwise it is unacceptable.

4. Coating Film Appearance The coating film was visually judged according to the following criteria, and those without blemishes were judged as acceptable. ：: There is no shrinkage, and the coating film is smooth and good. Pass. Δ: The shrinking is fine, but the coating film is glossy. failure. ×: Scratch is observed on the entire coating film. failure.

[0130] 5. Curability (solvent resistance of coating film) The coated coating film was dried at room temperature for further 3 days to obtain IPA,
Rub 50 times with felt impregnated with TOL (rubbing)
The degree of glossiness and peeling of the coating film was visually determined according to the following criteria. ：: The coating film does not change at all. Pass. ×: The coating film is glossy or peeled. failure.

6. Storage stability Approx. 400 pieces of clear paint for each test are placed in a 500 ml glass bottle.
g and sealed. After allowing this to stand at 23 ° C. and 50 ° C. for 30 days, the viscosity (seconds of Ford Cup No. 4)
(25 ° C.) and measure the viscosity (Ford Cup N) before the test.
o. 4 seconds = 15 seconds). A pass was accepted only when the change in viscosity (increase or decrease) was within 2.0 times.

The results of the above Examples and Comparative Examples were
The results are shown in Tables 1 and 2 below.

[0133]

[Table 1]

[0134]

[Table 2]

[0135]

The resin composition for coatings of the present invention is excellent in storage stability, curability at a low temperature (80 ° C. or lower), adhesion to various materials, weather resistance, and other properties required for various coatings. It is a resin composition for paints that exhibits well-balanced performance.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 163/00 C09D 163/00 175/04 175/04 183/04 183/04 F term (Reference) 4J026 AA44 AA45 AC23 AC24 BA26 BA27 BA50 GA01 4J038 CG141 CG142 CH121 CH122 CH171 CH172 CL001 CP071 CP072 DB211 DB212 DG161 DG191 DG261 DL022 DL032 DL052 DL082 DL112 GA03 GA07 GA12 GA15 HA216 JA46 JA47 JC32 JC34 J03 NA03 PC03 NA03 PC03 PC08 PC10

Claims (12)

[Claims] 1. A hydroxyl group-containing unsaturated monomer (a) copolymerized with a hydroxyl group-containing number average molecular weight of 500 to 8 having a hydroxyl group in a side chain.
000 hydroxyl group-containing acrylic resin (P), epoxy group-containing unsaturated monomer (b) copolymerized with epoxy group-containing epoxy group-containing acrylic resin having an epoxy group on a side chain having a number average molecular weight of 500 to 80,000 ( Q) Resin for paint containing (A)
And a curing agent (B) and a nonionic surfactant (C), wherein the coating resin (A)
A resin composition for a paint, wherein the amount of the epoxy group-containing unsaturated monomer (b) contained therein is less than 5,000 ppm. 2. A coating resin (A) containing a hydroxyl group-containing acrylic resin (P) and an epoxy group-containing acrylic resin (Q).
Is a graft copolymer having a hydroxyl group-containing acrylic resin (P) and / or an epoxy group-containing acrylic resin (Q) as a branch polymer and a hydroxyl group-containing acrylic resin (P) and / or an epoxy group-containing acrylic resin (Q) as a trunk polymer. The coating resin composition according to claim 1, further comprising a polymer. 3. A hydroxyl group-containing acrylic resin (P) and / or
Alternatively, the epoxy group-containing acrylic resin (Q) is further copolymerized with a fluoroalkyl group-containing unsaturated monomer (c) (the fluoroalkyl group has 1 to 24 carbon atoms). Or the resin composition for coating according to 2. 4. An epoxy group-containing acrylic resin (Q),
The resin composition for a paint according to any one of claims 1 to 3, wherein the alkoxysilane group-containing unsaturated monomer (d) is further copolymerized. 5. The hydroxyl group-containing acrylic resin (P) and the epoxy group-containing acrylic resin (Q) are further copolymerized with an alkoxysilane group-containing unsaturated monomer (d). 4. The resin composition for a coating according to any one of the above items 3. 6. The weight ratio of the hydroxyl group-containing acrylic resin (P) and the epoxy group-containing acrylic resin (Q) is P / Q =
The resin composition for a coating according to any one of claims 1 to 4, wherein the resin composition is blended in an amount of 0.01 / 99.99 to 99.99 / 0.01. 7. The curing agent (B) contains at least one of an organometallic compound (e), a polyisocyanate compound (f), a melamine resin (g), and a reactive silane compound (h). The resin composition for a coating according to any one of the above. 8. The coating resin composition according to claim 6, wherein the organometallic compound (e) is an aluminum chelate compound (i). 9. The reactive silane compound (h) is an organoalkoxysilane compound (j) having at least one epoxy group and a hydrolyzable alkoxysilane group in one molecule. Paint resin composition. 10. The coating resin composition according to claim 1, wherein the nonionic surfactant (C) is incorporated in the coating resin composition in an amount of 20 to 50,000 ppm. 11. The nonionic surfactant (C) is a fluorinated surfactant (k) having a perfluoroalkyl group in the molecule, according to any one of claims 1 to 9, Resin composition for paint. 12. HLB of a nonionic surfactant (C)
Is from 0 to 20, and the resin composition for a coating material according to any one of claims 1 to 10.