JPH01287178A - Resin composition excellent in pigment dispersibility for coating - Google Patents

Abstract

PURPOSE:To obtain the subject composition, consisting of a specific acrylic copolymer and polyisocyanate and amino resin as a crosslinking agent component, excellent in weather resistance and colorability of resins without amino smell. CONSTITUTION:The objective composition consisting of (A) an acrylic copolymer, prepared by copolymerizing (i) 0.1-20wt.% copolymerizable unsaturated bond-containing polyester resin with (ii) 1-50wt.% hydroxyl group-containing vinylic monomer, (iii) 0.1-5wt.% carboxy group-containing vinylic monomer [e.g. (meth)acrylic acid], (iv) 0-5wt.% phosphorus atom-containing vinylic monomer {e.g. dialkyl[(meth)acryloyloxyalkyl]phosphates} and (v) 20-98.8wt.% vinylic monomer copolymerizable with the components (i)-(iv) in the presence of a radical former and having 4,000-30,000 number-average molecular weight (Mn) and 2-25 ratio of [weight-average molecular weight (Mw)](Mn) and (B) a polyisocyanate and/or amino resin as a crosslinking agent component.

Description

Detailed Description of the Invention (Objective of the Invention) (Industrial Field of Application) The present invention relates to a method for producing a new and useful resin composition for coatings, and more particularly, the present invention relates to a method for producing a new and useful resin composition for coatings, and more specifically, The present invention relates to a coating resin that is mainly composed of a combination of a polyester resin containing a polyester monomer and a copolymerizable unsaturated bond, and has particularly excellent pigment dispersibility.

(Conventional technology and its problems) Copolymers obtained by copolymerizing vinyl monomers such as acrylic resins and vinyl acetate/acrylic resins have excellent coating performance, but also have good pigment dispersibility. Because of this, it takes a long time to mix the meat, pigments separate during storage, and there are various problems such as uneven coloring when mixing colors, and difficulty in matching colors and differences. This is a fatal drawback of the resin paint.

In order to eliminate these defects, have there been any attempts to add pigment dispersion improvers such as surfactants, silicon compounds, or organic acid metal salts during the preparation of paints? The current situation is that the level of damage remains at such a low level that it is far from reaching the target level.

In addition, various proposals have been made to improve pigment dispersibility by modifying vinyl copolymers with polynisder resins, but the dispersibility of pigments with large oil absorption such as carbon black and organic face F1 has been improved. In order to improve the dispersibility when toning a certain mixed color using several primary colors, the dispersibility will be improved unless the amount of modification is increased, and if the amount of modification is increased, On the contrary, weather resistance, yellowing resistance, curling resistance, leveling property, spray workability, etc. are reduced.

Furthermore, when modifying the vinyl copolymer with polynisder resin, a small amount of dialkylaminoalkyl (meth)
The use of acrylate as an essential component or the use of this dialkylamino)norkyl(meth)acrylate
1~ and the phosphoric acid ester bond-containing vinyl monomer
Although other methods for improving pigment dispersibility have been proposed, such as using f.
When using this method, it is possible to obtain a resin with a much higher level of Bi (crab), but due to this dialkylaminoalkyl (meth)acrylate, the resin is colored yellowish during preparation. The resulting resin solution has an amino odor, and in addition, the coating film tends to yellow when exposed to ultraviolet light due to its poor UV resistance. When polyisocyanes 1 to 1 are used, there are disadvantages such as a shortened pot life of the blended coating material.

In addition, in order to improve the defects of such systems using dialkylaminoalkyl (meth)acrylate, an improvement method using a vinyl monomer containing an amide bond in place of dialkylaminoalkyl (meth)acrylate has been proposed. (Japanese Patent Application Laid-Open No. 61-23652), pigment dispersibility and gloss retention during weather resistance tests achieved the desired objectives, but UV resistance (Δb) and color difference during weather resistance tests (ΔF ) still has a slight tendency to yellow.

(Problem to be Solved by the Invention) However, as a result of intensive study to solve the various problems in the conventional techniques as described above, the present inventors found that a vinyl-based resin containing a specific functional group was used as a base resin component of the paint. It was discovered that by using a combination of a monomer and a copolymerizable unsaturated bond-containing polyester resin, a resin composition for coatings meeting the intended purpose could be created, and the present invention was completed. I reached the point.

[Structure of the invention]

(Means for Solving the Problems) To summarize the present invention, (A) (1) Copolymerizable unsaturated bond-containing polynisple resin 0.1 to 20 wt%■ Hydroxyl group-containing vinyl monomer to 50 wt% ■ Carboxyl group-containing vinyl monomer 0.1-5
wt% 0) Phosphorus atom-containing vinyl monomer 0 to 5 wt% ■ Vinyl monomer 2 copolymerizable with (1) to (4)
A mixture consisting of 0-98.8 wt% is copolymerized with C in the presence of a radical generator to obtain a number average molecular weight (West) of 4,000 to 30,000.
．． Weight average molecular weight (flat)/number average molecular weight (qn>-2-
The acrylic co-polymer 25 is added with polyisocyanes 1 to 1 as a crosslinking component.
The present invention relates to a coating resin composition with excellent pigment dispersibility, which is characterized by containing an amino resin and/or an amino resin.

Hereinafter, the configuration of the present invention will be explained in detail.

First, a method for preparing the acrylic copolymer, which is the component (4) used in the coating resin composition of the present invention, will be explained.

In the preparation of the above (4) acrylic copolymer, the copolymerizable unsaturated bond-containing polyester resin used as component (1) may be a so-called alkyd resin modified with oil or fatty acid, or any of these. A type of unmodified so-called oil-free alkyd resin containing an ethylenically unsaturated bond copolymerizable with a vinyl monomer is suitable. Typical examples of such unsaturated bond-containing polyester resins include Japanese Patent Publication Nos. 44-7134, 45-22011, and 4B.
-20502, JP-A-48-78233 and 50
-58123@, etc., one raw material having a copolymerizable unsaturated bond is essential and is reacted with other raw material components to form this unsaturated bond in the resin skeleton. The unsaturated polyester which does not have a copolymerizable unsaturated bond, as described in Japanese Patent Publications No. 49-17916 and No. 50-6223, etc. Then, a functional group (polar group) that is reactive with a functional group (polar group) such as a hydroxyl group and/or a carboxyl group present in the polyester, and a copolymerizable unsaturated bond (vinyl group) are added. For example, glycidyl (meth)crylyl 1
A heptamer having an epoxy group and a vinyl group such as 1-7mers having an epoxy group and a vinyl group, 1-7mers having an alkoxysilyl group and a vinyl group, such as 1-xysilane or (meth)acryloyloxyl-1-xysilane, 1-maleic anhydride. Monomers having an acid anhydride group and a vinyl group, such as, or equimolar adducts of isocyanate ethyl methacrylate-1 or 2-hydroxy (meth)acrylate and power 1nomethylene diisocyanate-1. It is made by adding a monomer having one or more isocyanate groups and a vinyl group to an unsaturated polyester to similarly have unsaturated bonds in the resin skeleton.

In the present invention, the above-mentioned unsaturated bond-containing polyester resin is mainly used for adjusting the uniformity/aspect ratio, and is octylic acid, lauric acid, stearic acid or "persatic acid" (Shell, Netherlands). unsaturated fatty acids such as oleic acid, linoleic acid, lyluic acid, eleostearic acid or ricinoleic acid;
OLYN) 200 or 300J (synthetic drying oil fatty acid manufactured by Vercules, USA), Chinese tung oil (fatty acid),
Linseed oil (fatty acid), dehydrated castor oil (fatty acid), tall oil (fatty acid), cottonseed oil (fatty acid), soybean oil (fatty acid),
(semi-)drying oils (fatty acids) such as delta leaves (fatty acids), safflower oil (fatty acids), castor oil (fatty acids) or rice bran oil (fatty acids); or hydrogenated coconut oil (fatty acids), coconut oil (fatty acids) 〉 or non-drying oils (fatty acids) such as palm oil kernels (fatty acids), etc., with or without the use of one type -q- or a mixture of two or more types selected from various oils or fatty acids such as non-drying oils (fatty acids) such as palm oil kernels (fatty acids). , propylene glycol, glycerin, i-rimethylolethane, i-rimedylopropane, neopentyl glycol, 1,6-hexyl diol, 1,2,6-hexane i-liol, pentaerythryl or sorbitol. one or more polyhydric alcohols such as benzoic acid, p-te
rt-Butylbenzoic acid, (anhydrous) phthalic acid, 1-nahydro (anhydride) phthalic acid, 1-rahydro (anhydride) phthalic acid, 1-pomegranate (anhydride) phthalic acid, de 1-ra bromo (anhydride) Phthalic acid, 1~limellitic acid, "Himic acid" [endomethylene 1~rahitrophthalic anhydride manufactured by Hitachi Chemical ■], succinic acid (anhydride), maleic acid (anhydride), fumaric acid, itaconic acid (anhydride) , one or more polyhydric carboxylic acids such as adipic acid, zebadic acid or oxalic acid in a conventional manner, and if necessary, "Cardura E-104" (manufactured by Shell, Netherlands). monoepoxy compounds such as the synthetic branched fatty acid glycidylnisdel);
Polyepoxy compounds such as 28 or 100 IJ (epoxy resin manufactured by Shell, Netherlands), or tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or 4,4'-
Diisocyanates such as methylene bis(cyclohexyl isocyanate), polyisocyanates obtained by addition reaction of these diisocyanates with the above-mentioned polyhydric alcohols and water (isocyane 1 to prepolymers), or combinations of diisocyanates with each other. ) Typical examples include one or more polyisocyanates having an isocyanuric ring obtained by polymerization, replacing a part of the polyhydric alcohol or carboxylic acid mentioned above, and reacting by a conventional method. It is.

There are also types of polynisder resins (so-called alkyd resins) modified with saturated fatty acids or non-drying oils (fatty acids) that have no copolymerizable unsaturated bonds in the polyester resin skeleton, or (semi-drying oils). Or, add copolymerizable unsaturated bonds that serve as grafting points for vinyl monomers to polyester resins (so-called oil-free alkyd resins) that have not been modified by these fatty acids (゛゛↑11). Maleic acid or fumaric acid (anhydride) In the case of using unsaturated polycarboxylic acids such as The amount of the compound used as a source of copolymerizable unsaturated bonds is shown in graph 1 below.
~0.1 to 10 parts by weight considering the risk of turbidity, thickening, or gelation during copolymerization
, preferably within a range of 0.5 to 5% by weight; on the other hand, such an unsaturated bond source is selected from unsaturated fatty acids or (
When only semi-drying oils (fatty acids) are required (13), it is recommended to use a range of 5 to 80% by weight, especially 15 to 70% by weight in terms of oil length, to prevent turbidity and thickening. This is preferable in view of the risk of gelation.

-12= Furthermore, in the case of using both of the above-mentioned methods together, it goes without saying that the optimum conditions may be selected according to the respective usage ranges.

When the amount of the unsaturated bond-containing polyester resin used is less than 0.1% by weight, it is difficult to improve pigment dispersibility, and on the other hand, when it exceeds 20% by weight, although pigment dispersibility improves, weather resistance It is preferable to use 0.1 to 20% by weight, especially 0.1 to 20% by weight.
．． It is preferably within the range of 5 to 1 ol 1%.

In the present invention, as described above, an acrylic copolymer (
The torsion/tower ratio of component A) is mainly adjusted by copolymerizing the unsaturated bond-containing polyester resin (2), but when this ratio is less than 2, the pigment dispersibility cannot be improved at all; On the other hand, when this ratio exceeds 25, pigment dispersion and properties are not improved that much, but rather there are disadvantages in terms of painting workability, dilutability, non-volatile content during painting, pot life, etc. Both are undesirable because they are more likely to occur.

Therefore, the ratio of round to round is within the range of 2. to 25, more preferably 3 to 20, which is appropriate.

In order to prepare the acrylic copolymer (4) that maintains the above-mentioned preferred ratio of roundness to roundness, the following points must be kept in mind. Since the ratio (relative amount) of the lower molecular weight portion to the lower molecular weight portion and the absolute amount of each are major factors, how to create these two portions is an important point.

This should be controlled by a combination of reactivity in the reaction step that mainly produces the high molecular weight part and the reaction step that mainly produces the low molecular weight part. Combine (4
) can be achieved by carrying out the reaction with a low initiator concentration and a high 7mer concentration.On the other hand, in order to obtain an acrylic copolymer (4) mainly in the low molecular weight range, the above procedure is reversed. ζ1-1 (i.e. low monomer concentration, initiator)
Depending on the desired uniformity/aspect ratio, appropriate combinations of reaction conditions may be selected from those that can be achieved by carrying out the reaction in a state with the lowest opening degree.

Next, other vinyl monomers other than the copolymerizable unsaturated bond-containing polyester (1) used in the preparation of the acrylic copolymer, which is component (i) of the present invention, will be explained.

In the present invention, component (4) is an acrylic copolymer, which is named because acrylic monomers are often used as shown below, and the name does not impose any restrictions. (It's not something to write.

In preparing component G) of the present invention, a hydroxyl group-containing vinyl monomer (2) is used in addition to the copolymerizable unsaturated group-containing polynis-al 0) described above.

As for such hydroxyl group-containing vinyl monomers,
For example, 2-hydroxy"nityl(meth)acrylate-1
~, 2-hydroxypropyl (meth)acrylate-1~,
3-Hydroxypropyl(meth)acrylate-1-,2-
Hydroxybutyl (meth)acrylate 1~. 3-Human [
1xybutyl(meth)acryle-1~, 4-hydroxybutyl(meth)acryle-1~, 3-chloro-2-human]21xypropyl(meth)acryle-1~, G? −
Hydroxyethyl tumarate, mono-2-human 1'' xini[tyl-7-nodil fumale-1~ or polypropylene glycol or polyethylene glycol mono(meth)acrylate-1~, Plaxel FMXFA mono-(
α, β-ethylenically unsaturated saturated carboxylic acid droxyalkyl esters such as caprolactone adduct (manufactured by Daicel Chemical Co., Ltd.) or adducts of these with ε-caprolactone; (meth)acrylic acid, [alpha, beta-] dithyrenically unsaturated heptamer or dicarboxylic acids such as tonic acid, maleic acid, fumaric acid, itaconic acid or cynic acid, as well as these dicarboxylic acids and monovalent alkaline acids] α, β-edylene unsaturated carboxylic acids such as mononisdales, or α, β-ethylenic unsaturated carboxylic acids such as human [1-xyalkyl nisfurs and maleic acid, succinic acid, phthalic acid] , hekylyhydrophthalic acid, di-1-lahydrophthalic acid, benzene-1-licarboxylic acid, benzene-1-lacarboxylic acid, "Himic acid" (Hitachi Chemical ■ product), polycarboxylic acid such as di-1-lachlornotaric acid or dodecenylsuccinic acid Various unsaturated carboxylic acids such as adducts of acids with anhydrides, 1Cardeula F (glycidyl ester of branched synthetic fatty acids manufactured by Shell in the Netherlands), coconut oil fatty acid glycidyl ester or ocdylate glycidyl ester. with monoglycidyl esters of monohydric carboxylic acids such as or monoepoxy compounds such as butylglycidyl needles, ethylene oxide or propylene oxide.
Additives or adducts of these with ε-prolactone; hydroxyethyl vinyl derivatives and the like.

The above-mentioned hydroxyl group-containing 7-mer is used to impart a function as a crosslinking point to the obtained acrylic copolymer of component (4), and the amount used is 1 to 50 wt.
%, particularly in the range from 5 to 40 wt%. If the amount used is less than 1%, sufficient crosslinking points cannot be obtained, and 50w
If it is less than t%, there will be too many crosslinking points (7%), and the strain stress during curing will become large, which tends to lead to a decrease in adhesion, which is not preferable.

In preparing the acrylic copolymer of component (4) of the present invention, carboxyl-containing vinyl monomer (2) is used. Examples of such vinyl monomers having a carboxyl group include α,β-ethylenically unsaturated hexachloromethane such as (meth)acrylic acid, chloric acid, maleic acid, fumaric acid, itaconic acid, or citraconic acid. α,β-ethylenically unsaturated saturated carboxylic acids such as mono- or dicarboxylic acids, monoesters of these dicarboxylic acids and monohydric alcohols - hydroxyethyl (meth)acrylate-1-, 2-hydroxypropyl (meth) ) Acryle-i~, 3-hydroxypropyl (meth)acryle-
i~, 2-hydroxybutyl(meth)acrylate-i,
3-human 1]xybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate-1~, 3-chloro'1
α, β such as -2-human lxib L1 pill (meth)acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl-monobutyl fumarate-1 or polyethylenefucacol mono(meth)acrylate −
Ethylenic unsaturated carboxylic acid hydroxyalkyl esters and maleic acid, succinic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, benzenetricarboxylic acid, benzenetricarboxylic acid, "hymic acid"
[Hitachi Chemical ■ products], additions of polycarboxylic acids such as tetrachlorophthalic acid or dodecenylsuccinic acid with anhydrides, etc.

The carbo/xyl group-containing vinyl monomer often exhibits an internal catalytic action when mixed with a polyisocyanate as a crosslinking agent, which is component (B) described below, and this shortens the storage stability of the paint. Taking into consideration effects such as pot life, improved adhesion to substrates, and improved compatibility with other resins, the amount used is 0.1 to 5% by weight, particularly preferably 0.1 to 2% by weight. It is preferable to keep it within this range.

= 19-Next -C1 In the present invention, as component (4), 1' (a phosphorus atom-containing vinyl monomer can be used).

Typical examples of such vinyl monomers include:
Dialkyl represented by the general formula [(meth)oxyloxylalkyl]bosphe-1 to (meth)oxylylalkyl] small groups; or -2C)- [However, R1, R2 and R3 in the formula are as described above. ] Dialkyl represented by [(meth)acryloyloxyalkyl ubosphie I-s or (meth)acryloyloxyalkyl acid phosphates-1~, etc., and each of the above-mentioned (meth)acryloyloxyalkyl acid phosphates or alkylene oxide adducts of acid phosphites 1 to 1; epoxy group-containing vinyl monomers, such as glycidyl (meth)acrylate-1- and methylglycidyl (meth)acrylate-1, and phosphoric acid or phosphorous acid, or acidic acids thereof Esterified products with esters; or 3-chloro-2-acid phosphoxypropyl (meth)acrylate-1 and the like, among which dibutyl (2-(meth)acryloyloxylethyl) phosphate, diphenyl [2 −
(meth)acryloyloxyethyl]bosphae-1~,
2-(meth)acryloyloxybrobyl acid phosphate, 2-(meth)acryloyloxybrobyl acid phosphate 1~.2-(meth)acryloyloxybrobyl acid phosphate 1~. 2- (meth)acrylic acid phosphite,
Particularly preferred are glycidyl (meth)acrylate/phosphoric acid i'adduct or 3-ri II 1.1-2-acytphosph A xypropyl (meth)acrylate-1.

The appropriate amount of the phosphorus atom-containing vinyl monomer 0) used is within the range of 0 to 5% by weight.

As described above, in the present invention, the phosphorus atom-containing heptamer
By using the above-mentioned unsaturated bond-containing polynisder resin (2) without using (a) at all, the ratio of ratio of acrylic copolymer (4) for paints, which is the object product of the present invention, is 2 to 25. If it is possible to modify the pigments within the range shown in graph 1, the pigment dispersibility, which is one of the objects of the present invention, can be greatly improved.However, azo-based pigments,
Pigments consisting of quinacridone or phthalocyanine pigments, such as η′, still have insufficient dispersibility when made into paints under somewhat harsh conditions, such as the need to raise the pigment temperature. Therefore, it is preferable to use the phosphorus atom-containing vinyl monomer ←) in order to further increase the level of dispersibility.

In addition, by using the upper tool (a), improvements in adhesion, corrosion resistance, hardenability, etc. can be expected.

If the amount used exceeds 5% by weight, it may affect the stability of the paint, especially the storage stability of the paint when a crosslinking agent component is used, that is, the bot life, or the resin. This is not preferable because it tends to cause problems in appearance (turbidity), resin viscosity, etc.

In the present invention, in preparing the acrylic copolymer of component (4), a vinyl monomer (2) that is copolymerizable with the components ω to (a) is further used.

Examples of such vinyl monomers include (1):
Aromatic vinyl monomers such as styrene, α-methylstyrene, p-tert-butylstyrene, vinyltoluene, @: medyl (meth) acrylate, ethyl (meth) =
23-Acryle-1~, r)-propyl (meth)acrylate, i-propyl (meth)acryle-1~, n-butyl (
meth>acrylate-1-1i-butyl (meth>acrylate)
to 1-1i-butyl(meth)acryle-1, ↑-butyl(meth)acryle-1~, 2-2'nizal l\xyl(
meth)acryle-1~, cyclohegycyl (meth)acryle-1~, benzyl (meth)acrylate, dibromopropyl (meth)acryle-1~, 1-ribromonoenyl (meth)acryle-1~, or alkoxyargyl (meth)acryle-1~ ) (meth)acrylate-1 such as acrylate-1; diesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid and monohydric alcohols;
Vinyl esters such as vinyl acetate, vinyl benzoate, "Beoba" (vinyl ester manufactured by Shell); [Viscoat 8F, 8FM, 17FM, 3F or 3FMJ
[Fluorine-containing) 7-crylic monomer manufactured by Osaka Organic Chemical Co., Ltd.]
, Perflu-A-o Schiff n hexyl (meth) acrylate
1~, to diperfluorocyclohexyl fumale-1 or N-1-p1'' bilperful 1st 1A-ri~2
4- Fluorine-containing vinyl esters, vinyl ethers, (meth)acrylates containing (per)fluoroalkyl groups such as tansulfonamide ethyl (meth)acrylate-1 or unsaturated polycarboxylic acid esters Polymerizable compounds; or vinyl monomers without functional groups such as (meth)acrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride, and various olefins such as vinylidene fluoride.

(c); In addition, examples of vinyl monomers used as component 0 include glycidyl (meth)acrylate, (β-methyl)glycidyl (meth)cryl 1,
(meth)allyl glycidyl ether or α,β-ethylenically unsaturated carboxylic acids are mono-2-(meth)
Various unsaturated carboxylic acids such as equimolar adducts of hydroxyl group-containing vinyl monomers such as acryloyloxymonoethyl phthalate and the above polycarboxylic acid anhydrides,
J (epoxy resin manufactured by Dainippon Ink & Chemicals @),
Epicoat 828°10rJ1 or 1004J
(epoxy resin manufactured by Shell), “Araldai 1-607
1 or 6084j (Epoxy compound manufactured by Giba-Geigy, Switzerland) [Chissonox 221J (
Chisso's Eponylic compound) or ``Bunacol EX''
-611j (Epoxy compound manufactured by Nagase Sangyo Co., Ltd., USA), which is obtained by adding various polyepoxy compounds having at least two epoxy groups in one molecule in equimolar ratios. jPolymerizable compounds, etc. ←) H'nylic 1~xysilane, α-methacrylic 1'' = l
2'dipropyl 1-rimej-xysilane, j.limethylsiloxyethyl (meth)) tucrylate or KR-21
5. Silicon-based monomers such as X-22-5002 (Shin-Etsu Chemical ■) are available.Alternatively, to improve weather resistance, use X-37 or 1-Δ-82.
It is also possible to copolymerize polymerizable ultraviolet absorbers and light stabilizers such as those available from Adeka Argus Chemical ■.

The various seven-mers as the above-mentioned 0 component are (1) to ←)
Compatibility with components, copolymerizability, coating workability, gloss, hardness, flexibility, weather resistance, drying properties, solvent resistance, compatibility, dilutability, potency to life, Ol-1 value, etc. From this point of view, the amount of each hexamer component to be used and the combination thereof may be determined within the range of 20 to 98.8% by weight. Especially styrene, vinyl 1~
When weather resistance and yellowing resistance are required, the use of aromatic vinyl monomers such as toluene is preferably limited to 40% by weight or less, particularly preferably 35% by weight or less.

Also, in the case of silicone monomers such as vinyl ethoxysilane that have a hydrolyzable alkoxy group, they may gel if used in too large a quantity.
When using, it is preferable to keep the usage amount to 10W1% or less, particularly preferably 5wt% or less.

The production of the acrylic copolymer (i) component of the present invention is carried out by making full use of the known and commonly used copolymerization reaction method or graft copolymerization reaction method using the above-mentioned raw materials (1) to (4) components. In this case, azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO
), butyl perbenzony 1 to 27 = (diBPB), t-butylhydropa-)cyto,
Radical-generating polymerization catalysts such as di-t-butyl peroxide (DT'BI) and cumenehyde l]perΔ2-cyto (CIIP) are used alone or in combination.

In addition, at that time, the solvent used is - ('IJ, 1 to 1 - run, xylene, Tsurpetz 100. 150 (Ci' - 1 Oil Chemical ■) Swasol 1000.1500
Aromatic hydrocarbons such as (round neck petroleum ■), [)-hexane, hedutane, octane, mineral spitz 1~,
Aliphatic or alicyclic hydrocarbons such as Methylschiff 1-1 hexane, ethylsic]]hexane, LAWS (Shell Petrochemical ■), ethyl acetate, butyl acetate, isodityl acetate, Zerosolve Azete-1-, 3- Used are nitrogen-based solvents such as nitrogen, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanthine. In addition, when using U7 polyisocyanate or amino resin as a crosslinking agent component (, Jl,
Alcohol-based solvents such as butanol and ButiZerosolve, as well as needle alcohol-based solvents, are also used. Second, the crosslinking agent component as component (B) used in the present invention will be explained.

First, the crosslinking agent component used in the present invention is as follows:
There are polyisocyanes 1 to 1.

This J: Una polyisocyanes 1- include tolylene diisocyanes 1-, aromatic diisocyanes 1- such as diphenylmethane diisocyanate; hexamethylene diisocyanes 1-. Aliphatic diisocyanes such as 1-limethylhexane diisocyanate 1-; isophorone diisocyanate, methylcyclohexane-2,4 (or 2,6)-diisocyanate, 4,4-methylene bis(
cyclohexyl isocyane-1~), 1,3-(isocyanatomethyl)cyclohexane and other alicyclic diisocyanes-1~; or these diisocyanates and ethylene glycol, polyneedle polyol (polyethylene glycol, polypropylene glycol, etc.), caprolav Low molecular weight polynisder resins (including 1 type of Urayasu 1) and acrylic copolymers that have functional groups that react with polyhydric alcohols and isocyanate groups such as 1-1 polyol, 1-rimedylolethane, and trimethylolpropane. Combination, addition with water, etc.; or Buret 1~
Body; Copolymer (oligomer) of diisocyanate 1 and the same
; or L; to 2-diroxypropyl (meth)acrylate-1~... to E1 rimethylene diisocyanate 1~
Equimolar (= J additive, isocyanate A copolymer containing 1 to 1 isocyanate group such as isocyanate methyl (meth)crylate 1 to 1 and copolymerizable unsaturated group with a vinyl monomer as an essential component ; Alternatively, these polyisocyanates can be combined with lower monohydric alkyl, methyl ethyl alcohol, etc.
Suitable materials are those blocked with known blocking agents such as A-xime and lactam. In particular, when using an amino resin as a crosslinking agent component (2) and (2), block type polyisocyanes 1 to 1 are preferred.

Acrylic copolymer and polyisocyanate of component (a) above
From the viewpoint of coating film performance, the blending ratio of 1 to 011/NC0=11
It is preferable to mix them so that the ratio is 0.5 to 1/1.5 (equivalent ratio). If NGO is 0.5 equivalent to 0111 and unplanted, the specified coating film/Pl will not come out, and 1,
If the amount exceeds 5 equivalents, the physical properties of the coating film may be sufficiently improved, but it is unfavorable from the viewpoint of cost.

Next, in the present invention, an amino resin is used as the crosslinking agent component (B).

Such amino resins are produced by polymerizing the product obtained by adding formaldehyde to amino compounds such as urea, melamine, and guanamine, and then adding methanol,
It is obtained by etherification with a lower monohydric alcohol such as butanol, and melamine resin is most preferable in terms of coating film performance and weather resistance.

If the amount of amino resin used is 10% without vortexing, crosslinking will not be sufficient and the physical properties such as solvent resistance, stain resistance, and weather resistance will be insufficient, and if it exceeds 40%, crosslinking will not progress. Considering that the coating film becomes brittle, which is undesirable, acrylic copolymer/amino resin -60-90%/10-40 (
It is preferable because it is blended at a ratio of (solid content ratio).

When using polyisocyanate and amino resin together,
After determining the amount of the - one, the amount of the other may be determined in accordance with the mixing ratios in each of the above-mentioned cases.

When polyisocyanene 1 is used, the cured strip A' is dried at room temperature, forced drying at 40 to 100'C for about 10 to 60 minutes, and then cured by drying at room temperature for about 10 to 60 minutes.
When using Mino Resin, it is sufficient to bake and dry at 100-180°C for 20-40 minutes, but
It is not limited to this.

The resin composition for coating vermilion 1, which is made from the above-mentioned components (4) and (B) of the present invention, may optionally include nitrified cotton (2I to mouth cell).
NC) or cellulose acede 1 to butyre 1
～(CAD) like fiber cord system compound, A/L,=nito'
resins, polyester resins, silicone resins or other acrylic resins or chlorinated polyolefins, or various types of public lambda 1 law 4 such as plasticizers, pigment dispersants, leveling agents, ultraviolet absorbers, antioxidants or hardening accelerators. It is also possible to incorporate the additives used in the composition in conventional amounts.

The resin composition used in the present invention obtained as described above can be applied to various crucibles 4Δ by known and commonly used methods such as spray coating, roll coating, brush coating, etc.

For example, the paint resin composition of the present invention can be used for automobiles, automobile repair, large vehicles, building exteriors, bridges, floors, metals, plastics, paper, general purposes, home appliances, and non-1N trade. Depending on the type of crosslinking agent component and curing conditions, it can be applied to a wide range of application fields, such as for materials or for plans 1 to 1.

The resin composition for paints of the present invention can of course be used as an enamel paint using pigments, but it goes without saying that it can also be used as a clear paint without using pigments, if desired. Nor.

〔Example〕

Next, the present invention will be specifically explained using reference examples, working examples, comparative examples, applied examples, and comparative applied examples, and the present invention is not limited to these examples unless the gist of the present invention is exceeded. Note that all parts and percentages hereinafter are based on weight unless otherwise specified.

Reference Example 1 [Preparation agent for polyvarnish seal resin containing 0 unsaturated bonds] 382 parts of dehydrated castor oil fatty acid and anhydrous maleic were placed in a four-piece [1 flask] equipped with a stirrer, a thermometer, a reaction product water removal device, and a nitrogen gas introduction tube. 5 parts of acid, 3 parts of phthalic anhydride
49 parts, 134 parts of neopentyl glycol, 1 to 98 parts of rimedylolpropane, 1 part of bentaeryswattol
00 parts and 0.005 parts of antifoaming agent and heated to 180°.
C and held at the same temperature for 2 hours, then heated to 220'C over 3 hours, held at the same temperature in a nitrogen atmosphere until the acid value became 9 or less, and then cooled. Add 1 to luene so that the non-performance ratio (NV) is about 50%, and at NV or 50.1%, 25°CG, J&J Leforce'-1
"-1-O (G, V: S) is 1--M, acid value (AV) lfi 3.0, hydroxyl value (OIIV)
A solution of an unsaturated polynisder resin modified with dehydrated castor oil fatty acid and having an oil length of 1fi45 and an oil length of 40% was prepared. Hereinafter, this will be abbreviated as resin (c-1).

Reference example 2 (same as above) 92 parts of soybean oil fatty acid, 100 parts of Zafra 1 no oil fatty acid
parts, 464 parts of phthalic anhydride, 212 parts of neopentyl glycol, 102 parts of 1 to rimedylolpropane, 100 parts of pentaerythritol and 0.00 parts of antifoaming agent.
Same as Reference Example 1 except that 5 parts were used as raw material for preparation, NV was 50.0%, G, Vis, lfi O.

A solution of an unsaturated polyester resin modified with soybean oil fatty acid and safflower oil fatty acid and having an AV of 4.0 Te, an OHV of 70 Te, and a cutlet oil length of 40% was obtained. Hereinafter, this will be abbreviated as resin (C-2).

Reference Example 3 (same as above) 513 parts of isophthalic acid, 19 parts of maleic anhydride, 106 parts of adipic acid, 391 parts of neopentyl glycol
83 parts of trimethylolpropane, 30 parts of pentaerythritol and 0.005 parts of an antifoaming agent were used as raw materials, and toluene/ethyl acetate-5 was used as a diluting solvent.
NV was 50.0%,
A solution of an unsaturated bond-containing polyester resin having G, Vis of N, AV of 4.2, and OHV of 67 was obtained. Hereinafter, this will be abbreviated as resin (C-3).

Reference Example 4 (same as above) In a flask similar to Reference Example 1, 200 parts of phthalic anhydride, 208 parts of adipic acid, 6 parts of neopentyl glycol, 51 parts of 1-rimethylolbroban, and an antifoaming agent were added. After charging 0.005 parts, the temperature was raised to 160°C, and when the same temperature was reached, the temperature was increased to 180°C for 3 hours, and then the temperature was raised to 160 The temperature was raised to .degree. C. and maintained at this temperature under a nitrogen atmosphere until the acid value became 6 or less.

When the predetermined acid value is reached, the temperature is lowered to 60°C, and while maintaining this temperature, 300 parts a3 of butyl acetate and 0.006 parts of dibdeltin dilaure i are added and homogenized. Gradually add 200 parts of isocyanate I over a period of 2 hours while being careful not to generate heat, then maintain the temperature at 60°C until the viscosity becomes constant, and when the viscosity reaches a certain level, add 10 parts of maleic anhydride. After the addition, the temperature was raised to 120°C and maintained at this temperature for 14 hours.

After that, after cooling the temperature a little, xylene was added so that the NV was about 50%, and the NV was 50.1%, G, Vi
A solution of an unsaturated polyester resin having S, KaP, and AV of 7.5 and Kap OHV of 115 was obtained. Hereinafter, this will be abbreviated as resin (c-4).

Reference Example 5 (same as above) In a flask similar to Reference Example 1, 200 parts of coconut oil fatty acid, 484 parts of isophthalic acid, 355 parts of neopentyl glycol, 36 parts of trimethylolpropane, and 30 parts of pentaerythritol were added. : Add 0.005 part of antifoaming agent, raise the temperature to 160℃, and then heat to 180℃ over 3 hours.
The temperature was raised to 230°C, held at the same temperature for 3 hours, and then further raised to 230°C for 2 hours.

The temperature was maintained at 230°C until the acid value became 10 or less, and when the predetermined acid value was reached, the temperature was raised to 100°C to remove the 4% concentration of acetic acid.
00 parts, 10 parts of γ-methacrylic 1-coyloxyethyltrimethoxyrane, 0 parts of methyl needled hydroquinone
．． 02 parts and 0.001 of Zibdeltin dioctoate
After adding 50% and holding at 100'C, NV is about 50%.
Add toluene so that NV is 49, '8%,
G, Vis, is N-0, AV is 4.0. OHV is 79
1 q of a solution of 0 coconut oil fatty acid-modified unsaturated polyester resin with an oil length of 20%. Below, this (or 1
It is abbreviated as fat (C-5).

Example 1 100 parts of resin (C-1>,
1~300 copies of Ruen and i! ! Butyl 11ate 40
0 parts, 300 parts of styrene, 1 to 1 methyl methacrylate
210 parts of n-butyl methacrylate-1~, 180 parts of n-butyl acrylate-1~, 150 parts of 2-hydroxyethyl methacrylate-1~, 8 parts of methacrylic acid, and 2-methacryloylonitrile. Monomer mixture consisting of 2 parts of 1-ethyl acid phosphate i 950
250 parts and tert-butyl peroctoate
1 to 2 parts of BPO and 2 parts of BPO were heated to 110'C, maintained for 2 hours while being careful not to generate heat, and then added with the remaining 700 parts of the Ezummer mixture and tert-butyl peroxide. 10 copies of Octo A-1 and 3 of D-cho BPO
A mixture of 1 to 175 parts of toluene and 75 parts of butyl acetate was added dropwise over 4 hours, kept at the same temperature for roughly 4 hours, and then heated to 115°C for 30 minutes.
and held at this temperature for about 15 hours until the NV was 50.
．． 1%, G, Vis, II, AV Ka3.0te, 0
11v is 38te, cart f--color (G, C,)/
')'; A solution of a paint resin having a ratio of less than 1 and a ratio of 8.2 was obtained.

Example 2 Into the same flask as in Example 1, 100% of resin (c-2) was added.
350 parts of xylene and 100 parts of 1so-butyl acetate, 420 parts of methyl methacrylate, 200 parts of n-butyl methacrylate, 135 parts of 1so-butyl methacrylate, 2-human[1xethyl 695 parts of a monomer mixture consisting of 130 parts of methacrylate-1~, 50 parts of 2-hydroxyethyl acrylate-1~, 5 parts of acrylic acid, and 10 parts of 2-methacryloyloxypropyl acid phosphate-1~ 200 copies of mine and
2 parts of t-butylperoct and 1 part of BPO were heated to 90°C, kept at this temperature for 1 hour, and then heated to 110°C for 1 hour. Warm and hold at this temperature for 30 minutes before adding the remaining 495 parts of the 7-mer mixture, 3 parts of AIBltl, tert-
5 parts of butylbar octyl-1-1 and 3 parts of [BPB]
A mixture consisting of 1 part of
00 copies and 200 copies of "Tsurupets 100", NV is 50.8%, G, ViSJX-Y, AV Ka4.9.011v is 47, G, C, lfi 1 or less Te1. A coating resin solution having Mw/Mn of 19.8 was obtained.

Example 3 In a flask similar to that used in Example 1'C'', resin ((>
3>, 200 parts of xylene, 480 parts of acid-resistant butyl, 200 parts of styrene, and methyl methacrylate.
200 parts of n-butyl methacrylate, 110 parts of 1so-butyl methacrylate, 121 parts of n-butyl acrylate 1, 224 parts of 2-hydroxyethyl methacrylate, mono(2-hydroxy ethyl) monomethacryloyloxyethyl phthalate 1
5 parts of methacrylic acid, 380 parts of 980 parts of a 7-mer mixture consisting of 8 parts of methacrylic acid and 1 to 2 parts of 2-acryloylonitoethyl funoside, and 2 parts of tert-butyl peroxide and The temperature was raised to 90°C, held at this temperature for 1 hour, then raised to 120°C over 30 minutes, and kept at this temperature for 30 minutes.
600 parts of the remaining monomer mixture;
10 parts of tert-butyl peroff 1-ate, AIB
A mixture consisting of 3 parts of N and 2 parts of D-BPO and 300 parts of xylene was added dropwise at 120 °C over 4 hours,
It was maintained for about 15 hours after the completion of dropping, and the NV was 50.8% and the G
, ViS, is X, 'AV is 3.01011V 1fiF
A, G, C, lfi 1 or less Te, Ka Mw/MJ
J'6. A resin solution for paint was obtained.

Example 4 In a flask similar to Example 1, 360% of resin (c-3) was added.
40 out of 1180 parts of a monomer mixture consisting of 300 parts of styrene, 1 to 200 parts of methyl methacrylate, 204 parts of ethyl acrylate, 106 parts of 2-hydroxyethyl methacrylate, and 10 parts of methacrylic acid.
0 parts, 220 parts of xylene, 1 to 100 parts of luene,
[100 parts of Tsurpetz 100J and 2 parts of butyl acetate
00 parts, 2 parts of BPO, 0.5 parts of tert-butyl peroctoate and 0.5 parts of AIBN were heated to 90°C, kept at this temperature for 1 hour, and then , the temperature was raised to 120°C over a period of 114 minutes and held at this temperature for 30 minutes, followed by heating the remaining 80°C of the monomer mixture.
A mixture consisting of 0 parts of acid-resistant butyl, 14 parts of tert-butyl peroct, 5 parts of DTB+)0, and 3 parts of AIBN was added dropwise over 4 hours. Even after the end, the temperature is kept at about 151), and the NV
is 51.0%, G, Vis, is X, AV is 3.8%.
011v is 39, G, C, is less than 1, Te is 9. A solution of paint resin was obtained.

Example 5 In a flask similar to Example 1, resin (C-3>200
parts, 305 parts of styrene, n~butyl methacrylate-1
110 parts of ~, 25 parts of tert-butyl methacrylate
0 parts, 50 parts of N-1so-propyl perfluoro A ctane sulfonamide ethyl methacrylate-1, 7 parts of 2-■derhexyl acrylate 1, 80 parts of 2-hydroxyethyl acrylate, monomethacryloyloxy Monomer mixture 1 consisting of 35 parts of ethyl phthale-1
．． 400 parts of 100 parts, 300 parts of xylene, 200 parts of butyl acetate, 1 part of BPO and te
1 part of rt-butylperoct 1-■-1 and heated to 90°C, held at this temperature for 1 hour, then heated to 120'C over 1 hour and held at this temperature for 30 minutes. Then, 00 parts of the remaining molecules of the monomer mixture, 200 parts of xylene and 200 parts of butyl acetate,
3 parts of AIBN, 1 to tert-butyl peroctoate
A mixture of 8 parts of N
V is 51.0%, G, ViS, is V-W, AV is 3.
5. A solution of a coating resin having an OHV of 30, G, C, h'i 1 or less, and a ratio of 12.1 was obtained.

Example 6 In a flask similar to Example 6, resin (c-4>300
300 parts of styrene, 2 parts of methyl methacrylate
00 parts, 100 parts of 1so-butyl methacrylate-1,
50 parts of [bis]-8FJ, 65 parts of 1so-butyl acrylate, 1 to 2-hydroxyethyl acrylate
and 30 parts of dibutyl(2-methacryloyloxy)phosphate-1 to 4μ) monomer mixture 1
545 parts of 145 parts, 5 parts of fumaric acid, 200 parts of xylene and 350 parts of butyl acetate, and BPO
and 1 part of tert-butyl peroc 1-ate
4. Prepare the portion and bring it to 90'C. Warm to 120'C and hold at the same humidity for 30 minutes, then heat to 120'C and hold at the same humidity for 30 minutes.
00 parts, 300 parts of xylene, 5 parts of BPO, tert
- 15 parts of Petyl Perocx 1 ~ Knee 1 ~ and TBPB
A mixture consisting of 3 parts of
,Q,Vis,KaY,tovKa4.3.011v is 5
3. G, C, are less than 1, and the hen/hen is 15.2! A solution of the resin was obtained.

Example 7 In a flask similar to Example 1, 16 parts of resin (c-5), 100 parts of methyl methacrylate-I, 100 parts of n-butyl methacrylate-1, and n-butyl acrylate-1 were added.
32 parts of ~, 75 parts of [Cardura '-1], 50 parts of 2-hydroxyethyl acrylate-1 and 10 parts of -l-diphenyl(2-methacryloyloxyethyl) phosphate-1, and mpo of 1 part and tert −
One part of butyl peroctoate, 300 parts of xylene, and 300 parts of butyl acetate were charged, heated to 90°C, held at this temperature for 30 minutes, and then heated to 120°C for 30 minutes. After heating and keeping at this temperature for 30 minutes, 292 parts of methyl methacrylate 1, 200 parts of n-butyl methacrylate 1, 50 parts of 2-hydroxyethyl acrylate 1, and methacrylic acid were added. 25 parts of acrylic acid, 48 parts of diphenyl (2-methacryloyloxyethyl) phosphate, and 2 parts of equimolar glycidyl methacrylate/phosphoric acid adduct, and 2 parts of xylene.
00 parts of TBPB, and 1 to 12 parts of tert-butyl peroctoate were added dropwise for 4 hours, and after the completion of the dropwise addition, the mixture was kept at 120°C for 2 hours, and then
Add a mixture of 0.1 part of F3 ethyl niteller 1~ and 2 parts of butyl acetate and hold as it is for about 15 hours, and the NV is 49.8% and G, V t S, is Y18V. is 3.2.011v is 40. A solution of a paint resin with G, C, Ka'l or less and a ratio of 3.2 was obtained.

Example 8 2-Acryloyl A xyethyl acid phosphonoe-1~
Example 3 was carried out in the same manner as in Example 3 except that the same phase ethyl knock relay 1- was used instead of NV.
0.4%, G, Vis, KaW, AV is 2.8.01
1v is 56, G, C, is less than 1, and rain/water is 6.
A solution of coating resin 0 was obtained.

Comparative Example 1 Instead of ioo part of resin (C-1), 2-hydro:1
Using 10.5 parts of di-ethyl methacrylate-1 and 39.5 parts of styrene, 25 parts of toluene and 25 parts of butyl acetate, 2-methacryloyloxyethyl acid phosphate-1 was prepared. Example 1 except that instead of 2 parts, 2 parts of methacrylic acid was used.
Similarly, NV is 50.0%, G, Vis.

is published by ■, AV Ka2.9.011v is 38 te, G, C,
A comparison resin solution for repainting with a strength of 1 or less and a ratio of 1.6 was obtained.

Comparative Example 2 Instead of 100 parts of resin (c-2), 16 parts of 2-hydroxyethyl methacrylate-1, 34 parts of )-butyl methacrylate, and 50 parts of xylene were used, and 2-
NV was 50.1 in the same manner as in Example 2, except that the same amount of methacrylic acid was used instead of 10 parts of methacryloyloxypropyl acid phosphate.
%, G, Vis, Y, AV is 3.5.01] v is 47
A resin solution for paint for comparison was obtained, in which T, G, and C were 1 or less, and Katsuben/Ku was 1.9.

Comparative Example 3 Instead of 40 parts of resin (c-3), 1 to 7 parts of 2-hydroxyethyl methacrylate, 13 parts of styrene, and 20 parts of xylene were used to prepare 2-acryloyloxyethyl acid phosphate. The procedure was the same as in Example 3, except that 2 parts of acrylic acid was used instead of 2 parts of 1 to 2, NV was 50.5%, G, Vis, KaV,
A comparative coating resin solution was obtained which had an AV of 3.2, a DIIV rating of 56%, G, and C of 1 or less, and a weight ratio of 1.5.

Comparative Example 4 Instead of 360 parts of resin (C-4) (2), 83 parts of 2-hydro-2-1-delmethacrylate, 90 parts of "Tsurupez 100", and 90 parts of ethyl acetate were used. , 2-methacryl"yl Δxy" pluacid phosphate-1~ in the same manner as in Example 4 except that 1 part of methacrylic acid was used instead of 1 part of N\1 was 50 .6%, G. Vis. is V, A
V is 3.7, 011V is 39te, G. C. A comparative coating resin solution with a ratio of 1 or less and a ratio of 1.8 to 1.8 was obtained.

Comparative Example 5 Instead of 200 parts of resin (c-3), 31 parts of 2-dito[1-xyedyl methacrylate-1], 69 parts of styrene, and 100 parts of xylene were used. Except for j, Nv was 50.5%, G. V
is. Ka11, AV, l'J'i 3.3, OHV is 3 (), GC. 1 q of IJTJ resin solution was applied as a comparative control with a ratio of 1 or less and a ratio of 1.3 to 1.3.

Comparative Example 6 Instead of 300 parts of resin (c-14), 80 parts of 2-ditroxyethyl methacrylate 1 to 1, 70 parts of styrene, and 150 parts of xylene were used, and dibdel (2-methacryloyloxyethyl ) TNV was 50.3 in the same manner as in Example 6, except that 80 parts of n-butyl methacrylate was used instead of 30 parts of phosphate.
%, GAlis. is V-W, AV is 4.2, 0[1v
53 te, G. C. lfi 1 or less Te, Kak Mm
/Mn was obtained as a comparative coating resin solution of 1.7.

Comparative Example 7 Except that instead of 16 parts of resin ('c-5), 3 parts of 2-hydroxyethyl methacrylate-1 to 3 parts, 5 parts of methyl methacrylate, and 8 parts of xylene were used. , NV was 50.0%, G.I.
Vis. is X, AV power 3.2, OHV power 40T:
,G. C. A comparative coating resin solution with a ratio of 1 or less and a ratio of 1.3 to 1.3 was obtained.

Comparative Example 8 Example except that instead of 40 parts of the resin (c-5>, 7 parts of 2-hydroxyethyl methacrylate-1~, 13 parts of styrene, and 20 parts of xylene were used) Similarly to 8, NV is 50.3%, G.viS.KaV, ＼lKa 2.8, 011\'Ka5 (5 Te, G.viS.KaV).
C. A comparative coating resin solution with a ratio of less than 1 and a ratio of 1.4 to 1.4 was obtained.

Comparative Example 9 Same as Example 3 except that 10 parts of iso-butyl methacrylate was replaced with the same amount of dimethylaminoethyl methacrylate, with TNV of 50.6% and G.I. Vis. is Y, AV Ka 3, 3, 0
11v is 30te, G. C. Ka5-c, Kakni 4w/
Mnlfi 5.91Q: A comparative coating resin solution with an amino odor was obtained.

Comparative Example 10 The same procedure as in Example 3 was carried out except that the same amount of N-dimethylacrylamide was used in place of the 10 parts of iso-butyl methacrylate-1 to 1 to 1 with NV of 50. 0%, G.

Vis. is Z SAV is 3.0, OIIV is 40te, G
．． C. lfi 1 te, katsuhen/kame becomes 5.8,
1 q of a comparative paint resin solution that does not have an amino odor.

Application examples 1 to 8 and comparative application examples 1 to E3 Example 1 to
B and 100 parts of each of the resin solutions for coatings obtained in Comparative Examples 1 to 8 were added with PW as shown in Table 1) and ■.
Blend the specified pigment so that it becomes C (%), xylene/
40 parts of a mixed solvent of butyl acetate-50150 (weight ratio) was blended as a thinner, and 250 parts of glass peas were added.
and kneaded with a sand mill for 1 to 3 hours to prepare enamel bases for each.

Next, various types of pigment dispersibility were evaluated for each enamel base. Those results are shown in (1) and (
Shown in conjunction with 2).

In the evaluation of pigment dispersibility, the dispersion state is determined visually by the presence or absence of agglomeration of each enamel base and its degree (degree), and the dispersibility of flow coating is determined by the presence or absence of aggregation of each enamel base. A mixture containing 5 parts of toluene was poured onto paper and the degree of aggregation of the pigment was visually determined. Visually check the appearance
The sedimentation property was determined by separately preparing a mixture of color base/thinner = 50150 (weight ratio), and then centrifuging at 2500 ppm for 20 minutes.
The degree of sedimentation of the pigment was determined visually using a machine, and the thinner used for evaluating the sedimentation property was a mixed solvent of xylene/butyl acetate-50150 (weight ratio).

The criteria for determining the distributed state are as follows: ◎...
...No abnormality ○ ... Slight aggregation △ ...... Considerable aggregation X ...... Significant aggregation and flow coating The criteria IJ for dispersibility, luster, and the presence or absence of thixotropy of the enamel base are as follows.

◎・・・・・・・・・Excellent○・・・・・・Good Good△・・・・・・・・・Poor (inferior)X・・・・・・
... Impossible (significantly inferior) Application example 9 and comparative application examples 9 and 10 To 100 parts of each of the resin solutions for coatings obtained in Example ■ and Comparative Examples 9, J, and 10, PW shown in Table 2
Blend the specified pigment so that it becomes C (%), xylene/
Add 40 parts of a mixed solvent called butyl acetate-50150 (weight ratio) as a thinner, and add 250 parts of a glass piece.
and kneaded with a sand mill for 1 to 3 hours to prepare enamel bases for each.

Next, application examples 1 to 3 are applied to each enamel base.
The dispersion state and flow coating dispersibility were evaluated in the same manner as B and Comparative Application Examples 1 to B.

(However, regarding the evaluation of both of these performances, Application Example 9 is the same as Example "Pot life" and "Ultraviolet resistance (yellowing degree △b)""
Regarding the item "weather resistance", the system of the present invention, the system using amino group-containing vinyl monomer (Japanese Patent Application Laid-open No. 61-23652 technology), and the system using dialkylaminoalkyl (meth)acrylate (Japanese Patent Application Laid-open No. 54-62292 technology) In order to clarify the differences between the two, we performed a performance comparison.

-FIR- These results are summarized in Table 2, or the performance comparison of the above-mentioned "Potlife" is
(Polyisocyanate I manufactured by Dainippon Ink & Chemicals)
] was blended into each resin solution so that the amount of 011/NCO was equal, and then diluted with butyl acetate to a total non-active content of 45%. displayed.

In addition, to compare the performance of "ultraviolet resistance", 1 Pernock DN-950J was mixed with each resin solution on a white ceramic plate so that ON/NCO was equivalent, and then the total non-volatile content was reduced to 45% with butyl acetate. %, and then applied each coat separately to Homprite #144 treated dull steel plate using a 10 mil applicator, air-dried for about 30 minutes, baked at 60°C for 60 minutes, and then left to stand at room temperature. Each sample thus obtained was exposed to a germicidal lamp for 10011 Th, and the difference Δb between the b value after exposure and the b value before exposure was expressed as Δb. put it here,
The larger the Δb value, the more significant the yellowing.

For comparison of "weather resistance", Parnock 0N-95 was added to 100 parts of the paint resin obtained in Example (3), Comparative Example g, and 1°.
When 0 is mixed in an amount that makes 011/NC0 = 1, four C
35% of Tybake CR-93, 40 parts of xylene/butyl acetate-501 part 0 mixed solvent as a thinner, 250 parts of glass peas were added, and the mixture was kneaded in a sand mill for 1 hour. An enamel base was prepared. Furthermore, Parnock D is added to the enamel base.
A predetermined amount of N-950 was blended to make a urethane paint. After painting it on a resin steel plate coated with a urethane-based primer, it was baked at 60°C for 60 minutes. After being left at room temperature for about a month, natural baking was performed in the suburbs of Miyazaki City. Color difference. (ΔF) indicates the color change between the initial stage and after the background coloring, and the larger the numerical value, the greater the color.

Application examples 10 to 14 Each component was blended into the ioo part of the resin solution obtained in Example 3 with the composition shown in Table 3. PWC = 40
%), knead and further xylene/butyl acetate 50
Enamel bases were prepared separately by diluting a mixed solvent of 150 (weight ratio) with Ford Cup No. 4 as a thinner to 12 seconds.

However, in Application Example 1, after kneading with only the resin solution and titanium oxide, a predetermined amount of [Parnock DN-950, 1
was mixed and then diluted.

Next, apply each enamel base to Bonderai 1~#
144 treated dull steel plates were spray coated separately to obtain cured coatings under the curing conditions C and C as shown in the same table.

Thereafter, various performance comparisons were made on the items shown in the table using conventional methods for each coating film.

These results are summarized in the same table.10 As shown in Tables 1 to 3, it can be seen that the resin composition for paint of the present invention has extremely excellent properties.

(The following is a blank space) [Effects of the present invention] The resin composition for coating film 31 of the present invention comprises a resin component prepared from a vinyl monomer having a specific functional group and an unsaturated bond-containing polyester resin, and a crosslinking agent component. The thing is
In particular, it has excellent pigment dispersibility, no amino odor, excellent weather resistance, and excellent resin coloring properties.

Thus, the resin composition of the present invention can be applied to a wide variety of profiteering applications and exhibit excellent effects.

Patent applicant, Nippon Ink Kagaku Ninigyo Co., Ltd. agent, patent attorney Yoshio Mizuno

Claims (1)

[Claims] 1. (A) (1) Copolymerizable unsaturated bond-containing polyester resin 0.1-20 wt% (2) Hydroxyl group-containing vinyl monomer 1-50 wt% (3) Carboxyl group-containing vinyl monomer 0.1 to 5 wt% (4) 0 to 5 wt% of a phosphorus atom-containing vinyl monomer (5) 20 to 98.8 wt% of a vinyl monomer copolymerizable with (1) to (4) as a radical generator. The number average molecular weight (@Mn@) obtained by copolymerization in the presence of is 4000 to 30
000, weight average molecular weight (@Mw@) / number average molecular weight (
@Mn@) = 2 to 25 acrylic copolymer and (B)
A resin composition for coating material with excellent pigment dispersibility, characterized by comprising a polyisocyanate and/or an amino resin as a crosslinking agent component. 2. Polyisocyanate as the crosslinking agent component (B),
OH/NCO=1/(0.5-1
．． 5) The resin composition for coating material with excellent pigment dispersibility according to claim 1, which is blended in the following ratio (equivalent). 3. The pigment dispersion according to claim 1, wherein the amino resin as the crosslinking agent component (B) is blended in a ratio of acrylic copolymer/amino resin = 60 to 90/10 to 40 (solid content ratio). A resin composition for paint with excellent properties.