JP2853121B2 - Resin composition for paint - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel coating resin composition, and
Or isobornyl (meth) acrylate as an essential component
Acrylic copolymer and polyisocyanate
Dryness, hardness, sharpness, solubility, meat
Excellent holding feeling and recoatability.
Depending on the coating, it may have an adverse effect on old coatings or materials with poor solvent resistance.
For car repair, car parts, motorcycles that have no effect
For building, building exterior, roof, woodworking, general metal
It relates to a suitable coating resin composition. [Prior art] Until now, acrylic urethane paint has
Cars, motorcycles, buses,
Metal parts such as trucks, railcars and home appliances, plus
Industrial machinery, buildings, plans, including ticks
, Structures, wood products, plastic products, steel furniture
It is frequently used for painting and repair painting. But
However, conventional paints have poor drying properties, so
When repainting in parts, for example,
Paint and enamel paint, and clear the second coat
In the case of two-coat finish to paint, the first coat
Aluminum particles and enamel layer mixed in the second coat
(Return unevenness), lifting and other finishing
Dry for a long time or take a long time
It is necessary to slowly apply the second coat. Also, forced
Even if it is dry, if you try to repaint it, it will dry more than one night
Is required and primer surfacer or sandy
After coating and curing, the
Sanding can be done unless it takes a long time before starting the polishing process
The time is only short before sanding becomes possible
The development of is eagerly awaited. By the way, improve these disadvantages
Hardening accelerators such as dibutyltin dilaurate
Use nitrocellulose or cellulose acetate
Tobutyrate, vinyl chloride-vinyl acetate copolymer, etc.
It is well known that a large amount is added.
The pot life is shortened when using
Nitrocellulose in large quantities
Paints are prone to yellowing and cracking during outdoor exposure.
Paints with a large amount of rosin acetate butyrate
Drawbacks such as erosion, coating skin, and water resistance
Was. [Problems to be solved by the invention] As described above, as long as the conventional technology is followed,
Also dryness, solubility, hardness, recoatability and texture
It is especially good for materials with low solvent resistance.
Coatings that are extremely practical
It has been very difficult to provide a resin composition for foodstuffs. Therefore, the problem to be solved by the present invention is one of
Drying, solubility, hardness,
It has excellent resilience and texture, and is solvent resistant.
Extremely low impact on less sensitive materials
To provide a highly practical and practical coating resin composition.
You. <Means for Solving the Problems> In view of the situation described above, the present inventors considered that drying at room temperature
Quickly cures in forced drying and requires a long drying time
No need, even if repainting immediately, can be used for lifting and lifting
Does not occur, and the first coat
No uneven return of fine particles or enamel layer, and use
Depending on the solvent composition, old coatings or materials with poor solvent resistance may be used.
In addition to weathering, weather resistance, hardness, water resistance, gasoline resistance,
Chemical resistance, solubility in non-polar solvents, texture, sharpening, etc.
Excellent for automobile repair, building exterior, woodworking, plastic
The highest quality finishes for motorcycles, cars, motorcycles, etc.
Paint resin composition that enables painting that requires
As a result of intensive studies, isobornyl (meth)
An acrylic copolymer containing
Combine with Socyanate to achieve the above objectives
This led to the completion of the present invention. That is, the present invention basically relates to isobornyl (meth
(T) 2-95% by weight of acrylate (1) and containing hydroxyl group
Based on 1 to 50% by weight of the vinyl monomer (2),
10% by weight or less of carboxyl group-containing vinyl monomer
(3) and a resin having a copolymerizable unsaturated group content of 80% by weight or less
Either (4) or these (3) and
Each of the components (4) and each of the above (1) to (4)
Of other vinyl monomers (5) copolymerizable with the component
4 to 97% by weight, so that the total is 100% by weight
In, obtained by copolymerization in the presence of a radical generator,
Number average molecular weight (Mn) is 3,000-30,000 and weight
Average molecular weight (Mw) / number average molecular weight (Mn) 1.8 to 25
Acrylic copolymer (A) and polyisocyanate
(B) and an organic solvent (C).
Ryl copolymer (A) and polyisocyanate (B)
OH / NCO = 1 / (0.2-1.8)
Consisting of, inter alia, drying
Properties, hardness, sharpness, dissolvability, texture, and recoatability
To provide an excellent coating resin composition
It is. Isobornyl used as component (1) here
(Meth) acrylate is dry, hardness, weather resistant, soluble
(Solubility in non-polar organic solvents), sharpening, compatibility, face
Less than 2% by weight
Use of said isobornyl (meth) acrylate
The effect is getting harder to achieve, while 95% by weight
If it is too large, the brittleness of the coating etc.
In any case, it will be more noticeable
Absent. Therefore, the range of 2 to 95% by weight is appropriate.
Yes, especially within the range of 5 to 75% by weight. Next, the hydroxyl group-containing vinyl used as the component (2)
As the monomer, for example, 2-hydroxyethyl (meth)
(T) acrylate, 2-hydroxypropyl (meth) a
Acrylate, 3-hydroxypropyl (meth) acryle
, 2-hydroxybutyl (meth) acrylate, 3
-Hydroxybutyl (meth) acrylate, 4-hydro
Xybutyl (meth) acrylate, 3-chloro-2-hi
Droxypropyl (meth) acrylate, di-2-hydroxide
Roxyethyl fumarate, mono-2-hydroxyethyl
-Monobutyl fumarate or polypropylene glyco
Or polyethylene glycol coated mono (meth)
Relevant, and furthermore, attachment of these to ε-caprolactone.
Additive or “Placcel FM or FA monomer” [da
Caprolactone-added monomer manufactured by Isel Chemical Co., Ltd.]
Of α, β-ethylenically unsaturated carboxylic acids such as
Cycloalkyl esters; (meth) acrylic acid, croton
Acid, maleic acid, fumaric acid, itaconic acid or citrus
Rejects unsaturated mono- or dicarboxylic acids such as conic acid
Therefore, the monoester of these dicarboxylic acids and monohydric alcohols
Α, β-ethylenically unsaturated carboxylic acids such as steles
Or the aforementioned α, β-unsaturated carboxylic acid hydroxy
Alkyl esters and maleic acid, succinic acid, phthalate
Acid, hexahydrophthalic acid, tetrahydrophthalic acid,
Benzenetricarboxylic acid, benzenetetracarboxylic acid,
"Hymic acid" [product of Hitachi Chemical Co., Ltd.]
Polyols such as lorphthalic acid or dodecinyl succinic acid
Various unsaturated carbohydrates such as adducts of rubonic acid with anhydride
Acid and “Kajura E” (branch made by Shell, Netherlands)
Glycidyl esters of synthetic fatty acids), coconut oil fatty acids
Lysidyl ester or glycidyl octyl ester
Monoglycidyl esters of monovalent carboxylic acids such as
Is butyl glycidyl ether, ethylene oxide or
Is a bond with a monoepoxy compound such as propylene oxide.
Adducts or adducts thereof with ε-caprolactone:
And hydroxyethyl vinyl ether. These are used in the resulting acrylic copolymer (A).
Used to impart a function as a crosslinking point
In the range of 1 to 50% by weight, especially 5 to 40% by weight
It is. If the amount used is 1% by weight or less, a sufficient cross-linking point is selected.
Not more than 50% by weight, too many crosslinking points
The strain stress at the time of curing increases, and on the contrary
It becomes easy to melt and separates when it becomes a solvent system with weak dissolving power.
Or cloudy, which is not preferable. Next, the carboxyl group-containing vial used as the component (3)
Examples of the phenyl-based monomer include (meth) acrylic
Acid, crotonic, maleic, fumaric, itaconic
Or unsaturated mono- or dicals such as citraconic acid
Including boric acid, these dicarboxylic acids and monovalent alcohols
Α, β-ethylenically unsaturated such as monoesters with
Carboxylic acids; 2-hydroxyethyl (meth) acrylate
G, 2-hydroxypropyl (meth) acrylate, 3
-Hydroxypropyl (meth) acrylate, 2-hydr
Roxybutyl (meth) acrylate, 3-hydroxybutyrate
Tyl (meth) acrylate, 4-hydroxybutyl (meth
TA) acrylate, 3-chloro-2-hydroxypropyl
(Meth) acrylate, di-2-hydroxyethyl ester
Malate, mono-2-hydroxyethyl-monobutyl
Malate or polyethylene glycol mono (meth) a
Α, β-unsaturated carboxylic acid hydroalyl such as acrylate
Kill esters and maleic acid, succinic acid, phthalic acid,
Xahydrophthalic acid, tetrahydrophthalic acid, benzene
Tricarboxylic acid, benzenetetracarboxylic acid,
Acid] [product of Hitachi Chemical Co., Ltd.], Tetrachlorf
Polycarboxylic acids, such as tallic acid or dodecinyl succinic acid
There are adducts with acid anhydrides. The carboxyl group-containing vinyl monomer (3) is
A polyisocyanate component, which is a component (B) described later, is added.
When combined, they often exhibit internal catalysis,
Use these because their stability is shorter
In some cases, it is necessary to improve the adhesion to the material and the compatibility with other resins.
Depending on the effect, the amount used is 0 to 10% by weight.
Medium, preferably in the range of 0.2-5% by weight
No. Next, the copolymerizable unsaturated group used as the component (4)
The contained resin is the obtained acrylic copolymer (A) component
And, in particular, improved pigment dispersibility
Increase the amount of non-volatile components during coating, and
Its main purpose is to improve solubility.
That is, as the copolymerizable unsaturated group-containing resin
In particular, if only representative examples are given,
Steal resin, acrylic copolymer, petroleum resin, logistics
Ester-based or polyether-based
In the case of the invention, the polyester-based resin (oil
Includes gender type. ) Or acrylic copolymer
It is desirable to use, among others, considering the various physical properties of the cured coating film
In such a case, the copolymerizable unsaturated group-containing resin itself
In addition to unsaturated groups, the hydroxyl group
Is also more desirable
The result is that you get it. Such polyester resin or acrylic copolymer
Japanese Patent Publication Nos. 45-22011, 46-20502, 44
JP-A-7134, JP-A-48-78233, JP-A-50-58123
Raw materials having copolymerizable unsaturated groups as known in
Required by reacting with other raw material components.
Having a copolymerizable unsaturated group in the resin skeleton,
Alternatively, Japanese Patent Publication Nos. 49-47916 and 50-6223
First, a saturated polyester with no copolymerizable unsaturated groups
After obtaining the hydroxyl group in the saturated polyester
Functional groups such as groups or carboxyl groups, or even di-
Epoxy groups introduced by reacting epoxy compounds
Utilize a functional group reactive with these functional groups
Compounds having a hydroxyl group, for example, (meth) acrylic acid
It has acid chloride group and vinyl group like Ride
Epoxy groups such as glycidyl (meth) acrylate
And those having a vinyl group, vinylmethoxysilane,
Ta) Alkyls such as acryloxyethyltrimethoxysilane
Having a coxysilanol group and a vinyl group, anhydrous maleic
Acid anhydrides such as tetrahydrophthalic anhydride and vinyl acid
Having a hydroxyl group, fumaric acid, (meth) acrylic acid, etc.
Having a carboxyl group and a vinyl group, 2-hydro
Xypropyl (meth) acrylate to hexamethylenedi
Isocyanate equimolar adducts, isocyanate ethyl
Has an isocyanate group such as acrylate and a vinyl group
Vinyl monomers such as
Having a hydroxyl group and a copolymerizable unsaturated group
Such as a hydroxyl group, carboxyl group, epoxy group
Vinyl monomer having a functional group such as
Acrylic copolymers with these functional groups
Copolymerizable unsaturated polyester to the above-mentioned saturated polyester
As in the case of introducing the group, contained in the acrylic copolymer
Functional groups and vinyl groups that are reactive with the functional groups
Compounds, such as (meth) acrylic acid chloride
Having acid chloride groups and vinyl groups such as
Epoxy and vinyl groups such as zir (meth) acrylate
Having vinyl methoxysilane, (meth) acrylic
Alkoxysila such as roxyethyltrimethoxysilane
Having a phenolic group and a vinyl group, maleic anhydride,
It has acid anhydride groups such as trahydrophthalic anhydride and vinyl groups.
And carbohydrates such as fumaric acid and (meth) acrylic acid
Having a xyl group and a vinyl group, 2-hydroxypro
Pill (meth) acrylate-hexamethylene diisocyanate
Nitrate equimolar adduct, isocyanate ethyl methacrylate
It has an isocyanate group and a vinyl group.
Which vinyl monomer is added to the acrylic copolymer
Those having a hydroxyl group and a copolymerizable unsaturated group
Appropriate. Such polyester resins are octylic acid, lauryl
Acid, stearic acid or “versatic acid”
Oleic acid, such as saturated fatty acids such as
Linoleic acid, linoleic acid, eleostearic acid or
Is an unsaturated fatty acid such as ricinoleic acid;
Or 300 ”(a synthetic dry fat manufactured by Hercules, USA)
Acid), Chinese oil (fatty acid), linseed oil (fatty acid), dehydration
Castor oil (fatty acids), tall oil (fatty acids) or cottonseed
Oil (fatty acids), soybean oil (fatty acids), olive oil (fats)
Acid), safflower oil (fatty acid), castor oil (fatty acid)
Or semi-dry oil (fat) such as rice sugar oil (fatty acid)
Acid); or hydrogenated coconut oil fatty acid, coconut oil fatty acid or
Oils such as non-drying oils (fatty acids) such as palm oil fatty acids or
Use one or a mixture of two or more selected from fatty acids
With or without ethylene glycol, pro
Pyrene glycol, glycerin, trimethylol eta
, Trimethymerol propane, neopentyl glycol
, 1,6-hexanediol, 1,2,6-hexanetrito
Pentaerythritol or sorbitol
One or more alcohols, and benzoic acid, p-
t-butylbenzoic acid, (phthalic anhydride), hexahydro
(Anhydride) phthalic acid, tetrahydro (anhydride) phthalic acid,
Trachloro (anhydride) phthalic acid, hexachloro (anhydride) phthalic acid
Talic acid, tetrabromo (anhydride) phthalic acid, trimellit
Acid, “hymic acid”, (anhydrous) succinic acid, (anhydrous)
Oleic acid, fumaric acid, (anhydrous) itaconic acid, adipine
One kind of carboxylic acid such as acid, sebacic acid or oxalic acid
Or two or more kinds in a conventional manner, and if necessary,
Toray Silicone SH-6018 [Toray Silicone Co., Ltd.
Products), X-22-160AS, KR-212,213 [Shin-Etsu Chemical Co., Ltd. products]
Such as reactive silicone resin, "Kajura E"
Monoepoxy compounds such as glycidyl esters of fatty acids
Thing, "Epiclon 200 or 400""Epicoat828"
Or a polyepoxy compound such as 1001
Rylene diisocyanate, hexamethylene diisocyanate
Or isophorone diisocyanate or 4,4'-meth
Diethylene bis (cyclohexyl isocyanate)
Isocyanates, these diisocyanates and the above
Polyyl obtained by the addition reaction with polyhydric alcohol and water
Socyanates or diisocyanates
Poly (isocyanurate) -bearing poly obtained by (co) polymerization
One or more of isocyanates,
By replacing some of the coal and carboxylic acids,
What is obtained by reaction is suitable. In addition, the copolymerizable unsaturated group-containing acrylic copolymer described above
As a body, the vinyl type mentioned above or later
From the monomers, an appropriate monomer is selected to obtain a desired model.
It can be obtained by copolymerization using a normal method with a nomer composition
Things are appropriate. The polyester resin and the acrylic copolymer,
Each may be used alone or in combination of two or more
Is, of course. Components of these copolymerizable unsaturated group-containing resins (4)
Is used within a range not exceeding 80% by weight
However, as long as the amount used is about 1% by weight or more,
The effect of the component is expressed, preferably
Is suitably in the range of 1 to 70% by weight. Of course, another component is a carboxyl group-containing vinyl
If there is no use of the mer (3),
When the amount of the component (4) is less than about 1% by weight,
In short, if you do not use it at all,
Is not able to exhibit the effect of
What if you get too much over weight percent?
Gelation during the reaction, especially weather resistance
Is likely to decrease, so in any case
Is also not preferred. (5) Each component of (1) to (4) used as a component
Examples of copolymerizable vinyl monomers include (a): styrene, α-methylstyrene, pt-butyl
Aromatic vinyls such as styrene and vinyltoluene
Monomer, (b): methyl (meth) acrylate, ethyl (meth)
TA) acrylate, n-propyl (meth) acrylate
G, i-propyl (meth) acrylate, n-butyl
(Meth) acrylate, i-butyl (meth) acrylate
G, t-butyl (meth) acrylate, 2-ethylhexyl
Sil (meth) acrylate, lauryl (meth) acryle
, Cyclohexyl (meth) acrylate, benzyl
(Meth) acrylate, dibromopropyl (meth) ac
Acrylate, tribromophenyl (meth) acrylate
Or alkoxyalkyl (meth) acrylate
(Meth) acrylates; maleic acid, fumaric acid or
Is an unsaturated dicarboxylic acid such as itaconic acid and a monovalent alcohol
Diesters with vinyl; vinyl acetate, vinyl benzoate,
Vinyl such as "Veoba" (Ciel vinyl ester)
Esters: "Biscoat 8F, 8FM, 17FM, 3F or 3F
M "[Fluorine-containing acrylic monomer manufactured by Osaka Organic Chemical Co., Ltd.
ー], perfluorocyclohexyl (meth) aclayre
G, di-perfluorocyclohexyl fumarate or
Ni-propyl perfluorooctanesulfonamide
(Per) fluoroa, such as ethyl (meth) acrylate
Vinyl group-containing vinyl esters, vinyl ethers,
(Meth) acrylates or unsaturated polycarboxylic acids
Fluorinated polymerizable compounds such as esters;
TA) acrylonitrile, vinyl chloride, vinylidene chloride,
Olefins such as vinyl fluoride or vinylidene fluoride
Vinyl monomers that do not have functional groups such as
You. Other materials that can be used include (c): (meth) acrylamide, dimethyl (meth)
Acrylamide, N-tert-butyl (meth) acrylamide
, N-octyl (meth) acrylamide, diacetone
Acrylamide, dimethylaminopropylacrylamid
, Alkoxylated N-methylolated (meth) acrylic acid
Amide bond-containing vinyl monomers such as amides, (d): dialkyl [(meth) acryloyloxyal
Kill] phosphates or (meth) acryloyl
Silalkyl acid phosphates, dialkyl [(me
(T) Acryloyloxyalkyl] phosphites
Is (meth) acryloyloxyalkyl acid phosphor
And the above (meth) acryloyl
Iroxyalkyl acid phosphates or acid
Alkylene oxide adducts of phosphites
Jill (meth) acrylate and methyl glycidyl (meth)
With epoxy-containing vinyl monomers such as acrylates
Acid or phosphorous acid or their acid esters
Ester compound, 3-chloro-2-acidphosphoxy
Phosphorus atom-containing vinyl such as propyl (meth) acrylate
-Based monomers, (e): dimethylaminoethyl (meth) acrylate
G, diethylaminoethyl (meth) acrylate
Dialkylaminoalkyl (meth) acrylates
You. The amide bond-containing vinyl monomers (c),
Atom-containing vinyl monomers (d), dialkylamido
No alkyl (meth) acrylates (e)
Of acrylic copolymers with internal catalyst
Improves adhesion, compatibility with other resins, pigment dispersibility, etc.
These are used when you want to use them alone or in combination.
It is possible to use
From the viewpoint, the phosphorus-containing vinyl monomer is 0.05 to 5% by weight.
%, Amide bond-containing vinyl monomer and dialkyl alcohol
Minoalkyl (meth) acrylates 0.05 to 10% by weight
It may be used within the range. Further, other vinyl resins used as the component (5)
As the monomers, (f): glycidyl (meth) acrylate, (β-meth
Chill) glycidyl (meth) acrylate, (meth) ant
Luglycidyl ether or α, β-ethylenically unsaturated
Carboxylic acids or mono-2- (meth) acryloyl
Hydroxyl-containing vinyl monomers such as oxymonoethyl phthalate
Of an equimolar adduct of the
Various unsaturated carboxylic acids such as "Epiclon 200, 400,
441,850 or 1050 "[Dainippon Ink and Chemicals, Inc.
Epoxy resin 828, 1001 or 100
4] (Ciel epoxy resin), "Araldite 6071
Or 6084 "(epoxy manufactured by Ciba Geigy, Switzerland)
Resin), “Chissonox 221” [Epo manufactured by Chisso Corporation
Compound) or "Denacol EX-611" (Nagase & Co., Ltd.)
At least in one molecule such as an epoxy compound manufactured by
Various polyepoxy compounds having two epoxy groups
Epoxy group-containing polymerization obtained by addition reaction at equimolar ratio
Or (g): vinylethoxysilane, α-methacryloxy
Propyltrimethoxysilane, trimethylsiloxyethyl
(Meth) acrylate, KR-215, X-22-5002 [Shin-Etsu
Products) and other silicon-based monomers.
You. Also, for the purpose of further improving the weather resistance, for example, T-37, LA-
Polymerizable purple such as 82 [Adeka Argus Chemical Co., Ltd. product]
An external light absorber or a light stabilizer can be copolymerized. Various monomers as the component (5) include (1)
~ (4) Combination with components, copolymerizability, painting work
Properties, gloss, hardness, flexibility, weather resistance, drying properties, solvent resistance,
In terms of compatibility, dilutability, solubility, pot life, etc.
The amount of the monomer component used and its combination should be 4 to 97% by weight.
The range may be determined. Especially styrene, vinyl toluene
Aromatic vinyl monomers such as are resistant to weathering and yellowing
Is required, use less than 40% by weight.
In particular, it is more preferable to keep the content at 35% by weight or less. Vinyl ethoxy having a hydrolyzable alkoxy group;
In the case of silicon-based monomers such as silane, too much
Use of such monomers may cause gelation when used.
-If you use, the amount used is 10% by weight or less,
It is preferable to keep the content to 5% by weight or less. Production of the acrylic copolymer (A) component used in the present invention
Is known using each of the above-mentioned raw materials (1) to (5).
Drive conventional copolymerization or graft copolymerization
Azobisisobut
Tyronitrile (AIBN), benzoyl peroxide (BP
O), t-butyl perbenzoate (TBPB), t-butyl
Hydroperoxide, di-t-butyl peroxide
(DTBPO), cumene hydroperoxide (CHP)
Use a radical-generating polymerization catalyst alone or as a mixture of several types
I do. As the organic solvent (C) used in the present invention, aniline
The point or mixed aniline point is in the range of 7 to 70 ° C, especially 8 to 65 ° C.
Non-polar organic solvents in the box are preferred, and typical examples thereof
For example, toluene (mixed aniline point 8.8 ° C), xylene
(Mixed aniline point 10.8 ° C), sorbetso 100 (mixed aniline
Phosphorus point 13.5 ℃: Exxon chemical products), Sorbetso 150
(Mixed aniline point 16 ° C: same) swazole 100 (mixed aniline
Phosphorus point 24.6 ° C: Maruzen Petroleum Products, Swasol 200 (mixed)
Aniline point 29.4 ° C: same), Swazole 310 (mixed anili)
Temperature 43.6 ° C: same), Swazole 1000 (mixed aniline point 1)
2.7 ° C: same), Swazole 1500 (mixed aniline point 16.5)
° C: same), Essonafusa No.3 (aniline point 58 ° C: exo)
No. 5 (aniline point 55 ℃)
Esonaphtha No.6 (aniline point 43 ° C: same), Howe
(Aniline point 15 ° C: shell chemical product), Loose (aniline point
Phosphorus point 44 ° C: same), Pegasol ARO-80 (mixed aniline point
25 ℃: Mobil Petroleum Products, Pegasol R-100 (mixed
Niline point 14 ° C: same), Pegasol R-150 (mixed aniline)
Point 16 ° C: same), Pegasol 1725N (aniline point 56 ° C:
Pegasol 3040 (aniline point 56 ° C: same), Pegaso
AN-45 (aniline point 44 ° C: same), Pegasol 1725
(Aniline point 56 ° C: same), methylcyclohexane (aniline
Phosphorus point 40 ° C), ethylcyclohexane (aniline point 44
° C) and other non-polar aromatic hydrocarbons with relatively low dissolving power
Organic solvents based on aliphatic aliphatic hydrocarbons and naphthenic hydrocarbons
Is mentioned. One or more of these
May be used in combination. Further, in the present invention, the non-polar organic solvent and the polar organic solvent
Typical examples of polar organic solvents that can be used together
Are ethyl acetate, butyl acetate, isobutyl acetate, celloso
Rubu acetate, propylene glycol methyl ether
S, such as acetate and 3-methoxybutyl acetate
Ter solvents, ether ester solvents, acetone,
Methyl ethyl ketone, methyl isobutyl ketone, cyclo
Isocyanate groups such as ketone solvents such as hexanone
A strong solvent that does not have a functional group that reacts with
No. The mixing ratio of the non-polar organic solvent and the polar organic solvent,
Drying property, coating workability, strength of solvent resistance of coated material, finish
Required for paints such as appearance, coating viscosity, and intended use
Depends on performance requirements,
Polar organic solvent / polar organic solvent = 100/0-40/60 (weight ratio)
May be selected as appropriate within the range. In this case, the solvent system
Acrylic copolymers made with only non-polar organic solvents
Use a non-polar organic solvent as a dilution thinner in the body solution.
It may be diluted and made into a paint by using
It may be diluted with a polar organic solvent and made into a paint to fall within the range.
No. Conversely, acrylic copolymers produced using only polar organic solvents
Diluted thinner so that the above-mentioned compounding ratio is added to the polymer solution
Diluted with non-polar organic solvent as paint
Good, and in a combined system of non-polar organic solvent and polar organic solvent
Produce an acrylic copolymer solution and adjust it to the blending ratio described above.
Rare in non-polar organic solvents and / or polar organic solvents
It may be made into a paint. Number average molecular weight of the obtained acrylic polymer (A) (▲
If ▼) is less than 300, weather resistance, dryness, hardness, solvent resistance
The coating properties such as the properties are inferior, and said above 30,000
Such film properties are good, but solubility in non-polar solvents,
As the feeling of meat, finished appearance, leveling property, etc. will deteriorate
Not preferred. Therefore, ▲ ▼ = 3000-30000, especially 5
It is preferably in the range of about 000 to 20,000. Also, weight flat
Average molecular weight (▲ ▼) / number average molecular weight (▲ ▼) 1.8
If less than, weather resistance, drying property, solvent resistance, flexibility, pigment
Dispersibility is poor, and if it exceeds 25, pigment dispersibility is not good.
Even painting workability, dilutability, non-volatile content during painting, potra
Both are preferred as inconveniences are more likely to occur with if, etc.
Absent. Therefore, ▲ ▼ / ▲ ▼ is 1.8-25, more
3 to 20 if the layer and the pigment dispersibility are desired to be good.
Range is appropriate. Polyisocyanate used as a curing agent in the present invention
As the nate (B), tolylene diisocyanate, di
Aromatic diiso such as phenylmethane diisocyanate
Cyanate; hexamethylene diisocyanate, trime
Aliphatic diisocyanates such as tylhexane diisocyanate
Anate; isophorone diisocyanate, methylcyclo
Hexane-2,4 (or 2,6) -diisocyanate, 4,
4'-methylenebis (cyclohexyl isocyanate
G), 1,3- (isocyanatomethyl) cyclohexane
Alicyclic diisocyanates such as
Isocyanate and ethylene glycol, polyether poly
Riol (polyethylene glycol, polypropylene
Recall, polycaprolactone polyol, etc.)
Polyvalent alcohols such as tylolethane and trimethylolpropane
Has a functional group that reacts with alcohol and isocyanate groups
Low molecular weight polyester resin (including oil-modified type)
Additives or bures with acrylic copolymers, water, etc.
Copolymer; copolymer of diisocyanate (oligomer)
ー); or 2-hydroxypropyl (meth) acryl
Rate to hexamethylene diisocyanate equimolar addition
Substances, isocyanate ethyl methacrylate, etc.
Vinyl monomers having anate groups and copolymerizable unsaturated groups
-Copolymer having essential component; Japanese Patent Application Laid-Open No. 61-72013
C as disclosed _Two ~ C ₈ Alkylene, cycloalkyl
Len and aralkylenediisocyanates and C _Ten ~ C ₄₀ of
The diol is reacted in the presence of an isocyanuration catalyst.
Non-polar organic solvent with isocyanurate ring
And polyisocyanates soluble in the agent.
So-called weak solvent type paint system that uses a large amount of polar organic solvent
In Japanese Patent Application Laid-Open No. 61-72013,
When using polyisocyanates soluble in polar organic solvents
More favorable results are obtained. The acrylic copolymer of component (A) and the component (B)
The mixing ratio with polyisocyanate is OH
/ NCO = 1 / 0.2 to 1 / 1.8 (equivalent ratio), especially 1 / (0.5 to 1.5)
It is preferable to mix them. NCO per equivalent of OH
Less than 0.2 equivalent does not give the desired coating film properties, 1.8
Exceeding the equivalent will provide sufficient coating properties, but will not occur under high humidity.
There is a possibility of foaming, and this is not preferable in terms of paint price. The resin composition for paints of the present invention is used for repairing automobiles,
For coatings that are easily damaged by polar solvents such as
When repainting or repairing finished materials, polar
If you use less or no solvent, polar solvents
Lifting observed when applying paint containing
No), gives a smooth and good coating with high commercial value
Ele, sanding sealer and primer surf
Excellent sharpening ability for sanders and sanding time
Polycarbonate that is shortened and easily exposed to polar solvents
Solvent for plastics materials with poor solvent resistance, such as
Troubles such as occurrence of cracks are less likely to occur.
In addition, two-tone finishing and repair of cars, motorcycles, etc.
The repainting interval is very short in
Use polar organic solvents that are photochemically inert and have low toxicity
If compared with the case of using a conventional highly toxic polar solvent,
Work environment has been significantly improved, pollution has been reduced,
Significant improvements in performance are also possible. In the present invention, room temperature drying, forced drying,
Curing in the flow or vapor cure system or VIC
It can be applied under any curing conditions, such as system
Dispersant, leveling agent, UV absorber, curing accelerator
Etc., which are commonly used in the art.
Needless to say that the dose can be used
If it is compatible with and soluble in the resin composition for coatings of the invention
Plasticizers and other resins, such as accelerators, may be used to improve performance.
Ryl copolymer, cellulose compound, acrylated alkyd
Resin, alkyd resin, silicone resin, fluororesin, epoxy
Xy resin etc. can be used together as appropriate, or
As enamel paint, do not mix with clear paint
Can be used. Painting can be spray or roller
Can be carried out in any known and customary manner.
You. [Effects of the Invention] The resin composition for paints of the present invention has, among others,
Excellent resolving power, hardness, recoatability, and feeling of holding
And the shadow on materials with poor solvent resistance
It is extremely practical, with little resonance.
You. Therefore, the coating resin composition of the present invention is as described above.
It can be applied and used for such a wide range of uses. [Examples] Next, the present invention will be specifically described with reference to Examples. still,
All parts and percentages in the examples are on a weight basis. Production Example 1 [Synthesis of copolymerizable unsaturated bond-containing resin (4)] Stirrer, thermometer, reaction product water removing device, N _Two Gas introduction
513 parts of isophthalic acid in a four-necked flask equipped with a tube, anhydrous
19 parts of maleic acid, 106 parts of adipic acid, neopentyl gly
Cole 391 parts, trimethylolpropane 83 parts, Pentae
Charge risuritol 30 parts and defoamer 0.005 parts and raise to 180 ° C
After warming and maintaining at the same temperature for 2 hours, 220
Temperature to ℃ _Two Under an atmosphere of gas, until the acid value becomes 9 or less.
After maintaining at the same temperature, the non-volatile content becomes about 60%
Diluted with toluene / butyl acetate = 85/15 (weight ratio)
Unsaturated bond with 60% non-volatile content, viscosity U, acid value 5.0, OH value 72
The obtained polyester resin (4-1) was obtained. Production Example 2 [Same as above] 382 parts of dehydrated castor oil fatty acid, 5 parts of maleic anhydride, none
Water phthalic acid 349 parts, neopentyl glycol 134 parts, tri
98 parts of methylol propane, 100 parts of Penta Eristol
Parts, defoamer 0.005 part, swallow 310
The same procedure as in Preparation Example 1 was carried out except that the nonvolatile content was 60%,
Modified dehydrated castor oil with viscosity U, acid value 3.6, OH value 54, oil length 40%
Unsaturated unsaturated bond-containing polyester resin (4-2)
Was. Production Example 3 [Same as above] Stirrer, thermometer, N _Two Four-hole hula with gas inlet tube
Charge 300 parts of toluene and 500 parts of butyl acetate into 115
Temperature, and 200 parts of styrene, methyl methacrylate
300 parts, butyl methacrylate 417 parts, β-hydroxy
58 parts of ethyl acrylate, 200 parts of toluene, t-butyl
Luper octoate 30 parts, di-t-butyl peroxide
The mixture of 5 parts is added dropwise over 4 hours, about 15 hours,
After maintaining at 115 ° C, 25 parts of maleic anhydride was added.
And further maintained at 115 ° C. until the acid value is about 7,
Unsaturated group-containing acrylic having a non-volatile content of 50%, a viscosity of Y and an acid value of 7.5.
A copolymer (4-3) was obtained. Production Example 4 [Same as above] In a four-necked flask similar to that used in Production Example 3,
300 parts of ene and 500 parts of butyl acetate were charged and the temperature was raised to 115 ° C.
At 15 ° C, 460 parts of butyl methacrylate
300 parts of acrylate, β-hydroxyethyl methacrylate 1
40 parts, methacrylic acid 20 parts, butyl acrylate 80 parts,
233 parts of ruene, 30 parts of t-butyl peroctoate, t-
Mix the mixture of 5 parts of butyl perbenzoate for 4 hours
After holding at 115 ° C for about 15 hours,
The temperature was lowered to ° C. Next, 0.03 parts of hydroquinone,
Methacrylate 33 parts, 2-methylimidazole 0.1 part
And kept at 90 ° C until the acid value is 1 or less.
Unsaturated group with 50% volatile, viscosity U, acid value 0.9 and OH value 35
Acrylic copolymer (4-4) was obtained. Production Example 5 [Synthesis of acrylic copolymer (A)] Stirrer, thermometer, inert gas inlet, condenser
In a four-necked flask equipped with
To 120 ° C., 150 parts of styrene, 8 parts of methacrylic acid,
21 parts of methyl methacrylate, β-hydroxyethyl meth
Acrylate 140 parts, n-butyl methacrylate 200 parts, a
Sobornyl methacrylate 481 parts, house 300 parts, t-butyl
10 parts of tilperbenzoate, di-t-butylperoxy
5 parts, 30 parts t-butyl peroctoate
Drop the product over 4 hours, and after the dripping is complete,
While maintaining the temperature at 120 ° C., the nonvolatile content was 50%, the viscosity was U, and the acid value was 3.
Acrylic copolymer with 0, OH value 30, ▲ ▼ / ▲ ▼ = 2.0
A combination (A-1) was obtained. Production Example 6 (same as above) In the same reaction vessel as in Production Example 5, an unsaturated bond-containing polymer
34 parts of stell resin (4-1), 400 parts of xylene and
400 parts of isobutyl acetate and t-butyl peroctoate
And 5 parts of β-hydroxyethyl acrylate
4.0 parts, 10 parts of acrylic acid, 150 of methyl methacrylate
Parts, 20 parts of styrene, 310 parts of ethyl methacrylate,
100 parts of t-butyl methacrylate, isobutyl acryl
200 parts of acrylate and 50 parts of isobornyl methacrylate
150 parts of the monomer mixture consisting of
Temperature. Then, hold at the same temperature for 30 minutes, then
In minutes, the temperature was raised to 115 ° C. When it reaches 115 ° C, the remaining 830 parts of the monomer mixture and
186 parts of toluene and 20 parts of t-butyl peroctoate
Part, 5 parts of azobisisobutyronitrile and t-butyl
A mixture of 5 parts of luper benzoate for 4 hours
It dripped over. After dropping, keep at the same temperature of 115 ° C for about 10 hours
By retaining, non-volatile content is 50%, viscosity
Is Y, the acid value is 4.0, the OH value is 35, and Mw / Mn = 4.9
Acrylic copolymer (A-2) was obtained. Production Example 7 (same as above) In the same reaction vessel as in Production Example 5, an unsaturated bond-containing polymer
333 parts of the polyester resin (4-1) and an unsaturated bond-containing resin
500 parts of the ester resin (4-2) and t-butyl par
5 parts of octoate, 2 parts of fumaric acid and 36 parts of house
7 parts, and as a vinyl monomer,
In each case, 10 parts of β-hydroxyethyl acrylate,
8 parts of methacrylic acid, 100 parts of styrene, n-butyl
180 parts of acrylate, 100 parts of i-butyl methacrylate
Parts and 100 parts of isobornyl methacrylate,
As the remaining solvent, polymerization of 300 parts of SWASOL 310 was started.
Using 15 parts of t-butyl peroctoate as an agent
Except for the change, the same as in Production Example 6,
Non-volatile content is 50%, viscosity is W, acid value is 4.8, OH value is 28
And an acrylic copolymer having Mw / Mn = 9.0 (A-
3) was obtained. Production Example 8 [Same as above] In the same four-necked flask as used in Production Example 5,
700 parts of toluene were charged, and as a vinyl monomer, β
-Hydroxyethyl methacrylate 100 parts, β-hydro
50 parts of xyethyl acrylate, 20 parts of methacrylic acid, methyl
Methacrylate 230 parts, n-butyl methacrylate 200
Parts, i-butyl methacrylate 200 parts, isobornyl
Use 200 parts of acrylate and 300 parts of toluene as the remaining solvent.
The same procedure as in Production Example 5 was carried out except that a non-volatile part was 50%,
Degree W, acid value 6.5, OH value 34, ▲ ▼ / ▲ ▼ = 2.3
A cryl copolymer (A-4) was obtained. Production Example 9 [Same as above] In the same four-necked flask as used in Production Example 5,
1083 parts of an unsaturated bond-containing polyester resin (4-2), t
-8 parts butyl peroctoate and 267 parts roast
Ethyl methacrylate 100 as vinyl monomer
Parts, n-butyl methacrylate 110 parts, β-hydroxy
90 parts of ethyl methacrylate, isobornyl acrylate
Using 50 parts, 200 parts of loin as the remaining solvent, butyric acetate
100 parts, t-butyl perbenzoe as a polymerization initiator
15 parts, di-t-butyl peroxide 5 parts, t-butyl
Same as Production Example 6 except that 20 parts of Luper Octoate were used
And the non-volatile content 50%, viscosity V, acid value 2.0, OH value 50, ▲
▼ / ▲ ▼ = 15 acrylic copolymer (A-5)
Obtained. Production Example 10 [Same as above] In the same four-necked flask as used in Production Example 5,
250 parts of unsaturated bond-containing acrylic resin (4-1), xylene
475 parts, butyl acetate 100 parts, vinyl monomer
310 parts of β-hydroxyethyl acrylate,
9 parts of lylic acid, 170 parts of methyl methacrylate, cyclohexyl
Silmethacrylate 100 parts, butyl acrylate 86 parts,
Using 200 parts of isobornyl acrylate, the remaining solvent
And the same procedure as in Production Example 6 except that 300 parts of xylene was used.
, Nonvolatile content 50%, viscosity Z, acid value 4.5, OH value 75, ▲
▼ / ▲ ▼ = 3.0 acrylic copolymer (A-6)
Obtained. Production Example 11 [Same as above] In the same four-necked flask as used in Production Example 5,
400 parts of unsaturated bond-containing acrylic resin (4-2), toluene
300 parts and 200 parts of Naphtha 3
As ethyl methacrylate 50 parts, Praxel F _M -1
[Lactone-added hydroxyl-containing monomer: Daicel Chemical
287 parts, n-butyl methacrylate 73 parts, iso-
100 parts of bornyl acrylate, isobornyl methacrylate
200 parts of 2-ethylhexyl methacrylate
Used, 300 parts of toluene as the remaining solvent, and a polymerization initiator
15 parts of t-butyl perbenzoate, di-t-butyl
Luperoxide 5 parts, t-butyl peroctoate 25 parts
In the same manner as in Production Example 6 except that
Degree W, acid value 0.9, OH value 40, ▲ ▼ / ▲ ▼ = 3.4
A cryl copolymer (A-7) was obtained. Production Example 12 [Same as above] In the same four-flask used in Production Example 5,
34 parts of saturated bond-containing polyester resin (4-1), unsaturated
200 parts of bond-containing acrylic resin (4-2), 586 parts of house
T-37 (UV absorbing monomer)
ー: Adeka Argus Chemical Co., Ltd. products] 10 parts, LA-82
(Same as above) 10 parts, methacrylic acid 8 parts, β-hydroxyethyl
22 parts of acrylate, 210 parts of n-butyl acrylate,
110 parts of sobornyl methacrylate, isobornyl acryl
Rate 510 parts, and the remaining solvent is swazole 310 3
00 parts, t-butyl perbenzoate 15 as a polymerization initiator
Parts, di-t-butyl peroxide 10 parts, t-butyl peroxide
Except for using 35 parts of octoate, the same as in Production Example 6,
Non-volatile content 50%, viscosity W, acid value 4.6, OH value, 20, and ▲
▼ / ▲ ▼ = 6.2 acrylic copolymer (A-
8) was obtained. Production Example 13 [Same as above] In the same four-necked flask as used in Production Example 5,
Charge 500 parts of toluene and 200 parts of Naphtha 3 and raise to 100 ° C
Heated at 100 ° C, 150 parts of styrene, 8 parts of methacrylic acid, 2-
200 parts of ethylhexyl acrylate, β-hydroxy
140 parts of tyl methacrylate, n-butyl methacrylate 1
00 parts, 402 parts of isobornyl methacrylate, Naphtha 3
00 parts, t-butyl perbenzoate 10 parts, di-t-butyl
Luper oxide 5 parts, t-butyl peroctoate 30 parts
Was added dropwise over 4 hours, and the addition was completed.
After that, it is kept at 100 ℃ for about 15 hours.
U, acid value 3.0, OH value 30, ▲ ▼ / ▲ ▼ = 2.1
A lylic copolymer (A-9) was obtained. Production Example 14 (according to the method disclosed in JP-A-61-72013)
Synthesis of polyisocyanate (B)) equipped with a stirrer, nitrogen gas inlet tube, air cooling tube and thermometer
In a 5 l glass four-necked flask with a nitrogen gas atmosphere
Below, hexamethylene diisocyanate (manufactured by Bayer AG)
Product, trade name Desmodur H) 3500 parts and 12-hydro
Kistearyl alcohol (produced by Henkel, trade name Loku
(Sanol, about 80% purity) 716.3 parts were charged. Next, attach an oil bath to the flask and raise the temperature to 65 ° C while stirring.
Upon warming, the contents of the flask became a homogeneous liquid. Pull
Continue to maintain the same temperature for 2 hours, then cool to 55 ° C
did. N, N, N-trimethyl as an isocyanuration catalyst
Ru-N-2-hydroxypropylammonium pt-
3.4 of a 20% butyl cellosolve solution of butyl benzoate
Add the parts in portions, followed by 60 hours at any temperature for 3 hours
After allowing the reaction to continue during
Isocyanurate by adding 3.4 parts of a 3% xylene solution
Deactivates the catalyst, thereby reducing isocyanuration
Response has ended. After cooling the reaction mixture to room temperature, 1000 parts of
Has an isocyanurate ring as a distillation residue
549.4 parts of polyisocyanate (conversion rate 55.0%) and distillate
450.0 parts of hexamethylene diisocyanate (recovered
Rate of 45.0%). Polyisocyanate having isocyanurate ring obtained
Is converted to non-polar solvent, House (Shell Chemical
Diluted to 75% concentration with a hydride solvent, aniline point 15 ° C)
732.2 parts of a clear polyisocyanate solution (B) were obtained. The polyisocyanate solution (B) thus obtained is
Non-volatile content 75.1%, Gardner color number 1 or less, Gardner viscosity
Degree EF, isocyanate content 11.2%, molecular weight 953
Yes, the dilution ratio for the dilution solvent house is 1000% or more.
Was. Examples 1 to 9 and Comparative Examples 1 to 4 Copolymers (A-1) to (A-
Regarding 9), coating was performed with the composition shown in Table 1.
The coating was made with a sand mill for 60 minutes. About the paint obtained in this way,
In Examples 1 to 9, house / xylene / naphtha 3 =
50/40/10 (weight ratio) solvent, and in Comparative Examples 1-4
Xylene / butyl acetate = 50/50 (weight ratio) solvent used
And dilute it with a Ford Cup in 12-13 seconds.
Lay painted, baked at 60 ℃ for 40 minutes, cured at room temperature for 7 days
The following tests were performed on the coated film, and the physical properties were evaluated.
Was. Test items (1) to (4) and (7)
Has a dry coating of 40μm on a dull steel sheet treated with Bonde # 144.
After baking at 60 ℃ for 40 minutes, leave it at room temperature for 7 days.
The coated plate was evaluated. Table 2 shows the results. (Test items) (1) Gloss: 60 ° gloss. (2) Hardness: Hardness due to scratching with a pencil. (3) Adhesion: 240 in a blister box of 50 ° C x 98% RH
Secondary adhesion after time exposure (cross-cut adhesion). (4) Gasoline resistance: Nisseki regular gasoline at room temperature
The coated surface condition after immersion for 2 hours was determined. (5) Lifting property: Case of: Coating A / Coating B / Coating C / Steel A → New Repair Coating → Examples (1) to (9), Comparative Example
(1) to (4) correspond. B → Lacquer type primer surfacer ⇒ In this case
This is where the lifting takes place. C → Crosslinked old coating film (urethane, thermosetting acrylic,
In this case, after painting B on top of C, 60 ℃ × 40
Forcibly dry in minutes, and after one day, polished with # 400 waterproof paper
When I paint on the degreased thing, ro is lifty
Wake up. In this case, a new one coat (b)
Sam Paint Co., Ltd. product] was used. Case: Coating A / Coating B / Coating C / Steel A → New Repair Coating → Examples (1) to (9), Comparative Example
(1) to (4) are applicable. B → Crosslinked primer surfacer → Lacquer old paint film (NC lacquer, modified acrylic lacquer)
Car, straight acrylic lacquer, high solid lacquer
Car, etc.) ⇒ In this case, lifting occurs
You. In this case, after painting b on top of ha, 60 ° C x 40
Forcibly dry in minutes, and after one day, polished with # 400 waterproof paper
When I paint on the degreased thing, ha will lift
Wake up. In this case, as B, "Hypersurf 2
C "(a product of Isamu Paint Co., Ltd.). Case: Coating A / Coating A / Coating B / Sleigh
Toe board A → Top coat (2nd coat) → Apply 1st coat
After mounting, leave it at 30 ° C for about 6 hours, then coat it with 2 coats of the same
Paint as eyes. ⇒ Examples (1) to (9), Comparative Example
(1) to (4) correspond. A- → Top coat (first coat) ⇒ In this case
This is where the lifting takes place. B → Mastic paint layer (mixture of mastic paint) NS-100 [Calcium carbonate, Nitto Powder Co., Ltd. product] 144 parts Taipek R-550 [Titanium oxide, Ishihara Sangyo Co., Ltd. product]
1.5 parts Demol EP [Dispersant, Kao Corporation product] 3 parts Neugen EA-120 [Emulsifier, Daiichi Kogyo Co., Ltd. product] 1.5 parts Ethylene glycol 3 parts SN Deformer 154 [Defoamer, Sannopco Corporation] Product)
1.5 parts 28% ammonia water 1 part Water 24 parts 2% High Metrolose 90 SH-15000 [Thickener, Shin-Etsu Chemical
18.6 parts Boncoat 3650 [Acryl manufactured by Dainippon Ink and Chemicals, Inc.]
Emulsion] 104.6 parts Celltop HP-103 [Thickener, product of Kojin Co., Ltd.] 1.1 parts (6) Influence of solvent used in paint on coated material: Solve
The degree of occurrence of contact cracks is visually evaluated and determined.
You. (7) Weather resistance: gloss retention after one year exposure in Miyazaki. (8) Repairability: Paint in Table 1 on ABS resin plate
Spray painting by spray painting so that it becomes 10-60 μm,
Bake at 60 ℃ for 40 minutes. Then leave at room temperature for 30-40 minutes
Then, dry film thickness of the same paint on the coating film is 40μm
Spray-painted, baked at 60 ° C for 40 minutes, and dried
The state is visually determined. (9) Metal return unevenness: Acrydic 47-567 [Dainichi
Acrylic polyol manufactured by Hon Ink Chemical Industry Co., Ltd., nonvolatile
50%, OH value 30] / Barnock DN-950 series metallic base
[Aluminum paste made by Toyo Aluminum Co., Ltd.
Paste 1700NL mixed with PWC 10%)
Was spray painted on a tin plate and left at room temperature for 40 minutes.
In addition, the paint formulation shown in Table 1 (however,
The use of clear paint that lacks the use of clear paint
Was. ) And spray viscosity with the specified thinner.
Paint is diluted to a part of the metal plate and cured.
After that, the flow state of the aluminum particles is visually determined. (10) Drying: Dry to the touch (on glass plate). (11) Solid for painting: Ford using the specified thinner
This is the solids content when diluted to 11-12 seconds with cup No. 4.
The higher the value, the higher the feeling of meat retention and the better the dilutability to the solvent.
Indicates that (12) Acrylic copolymer (A) Swazole 310
Tolerance: 1 g of acrylic copolymer (A)
It is expressed as dilution ratio (%). (13) Pigment dispersibility: carbon black ... Mitsubishi Carbon MA-100 [Mitsubishi Chemical
[Products] PWC 3% Quinacridone Red ... First Gen Super Red YE
[Products of Dainippon Ink and Chemicals, Inc.] PWC 10% phthalocyanine blue ... Fast Gen Blue NK [Dainichi
The product of the Ink and Chemicals Co., Ltd.] PWC10% Kneading with the above PWC using a sand mill with the above pigment for 60 minutes
Meat primary color enamel base and white ena with blended meat of Table-1
Mel and TiO _Two / Carbon black = 98/2 (weight ratio), Ti
O _Two / Quinacridone red or phthalocyanine blue = 95
/ 5 (weight ratio)
-980 [Polyisocyanate manufactured by Dainippon Ink and Chemicals, Inc.
Details will be described later. ] And silicone
Oil KF-69 (product of Shin-Etsu Chemical Co., Ltd.)
Xylene / butyl acetate = 50/50 (weight ratio) solvent
Dilute to play viscosity, spray paint, touch dry,
Spray the same paint on a part of it and cure it by spraying.
The determination was made by comparing the color difference between the part and the flow-coated part. * 1) Acrydic A-801-P: Dainippon Ink and Chemicals
Acrylic polyol manufactured by Co., Ltd., nonvolatile content 50%, OH value 50,
Solvent toluene / butyl acetate * 2) Acrydic 52-614: Dainippon Ink and Chemicals
Acrylic polyol, 50% non-volatile content, OH value 17.
5. Solvent xylene / butyl acetate * 3) Acridic A-808: Dainippon Ink and Chemicals
Acrylic polyol manufactured by Co., Ltd., nonvolatile content 50%, OH value 20,
Solvent xylene / butyl acetate * 4) Taipaque CR-93: Titanium oxide manufactured by Ishihara Sangyo * 5) Tinuvin 328: UV absorber manufactured by Ciba-Geigy * 6) Tinuvin 770: Light stabilizer manufactured by Ciba-Geigy * 7) Thinner: house / xylene / naphtha 3 = 50
/ 40/10 (weight ratio) solvent * 8) Thinner: xylene / butyl acetate = 50/50 (weight
Solvent) * 9) Vernock DN-950: Dainippon Ink and Chemicals, Inc.
Hexamethylene diisocyanate-trimethylolp
Lopan addition polyisocyanate, nonvolatile content 75%, NCO12.
5% * 10) Burnock DN-980: Dainippon Ink and Chemicals, Inc.
Hexamethylene diisocyanate isocyanurate
Polyisocyanate, non-volatile content 75%, NCO 15%

Claims (1)

(57) [Claims] 2-95 of isobornyl (meth) acrylate (1)
% By weight and 1 to 50 of the hydroxyl group-containing vinyl monomer (2).
% Of carboxyl group-containing vinyl monomer (3) and 10% or less of copolymerizable unsaturated group-containing resin (4) by weight or less. ) And (4), and the above (1)
4 to 97% by weight of the other vinyl monomer (5) copolymerizable with each of the components (4) to (4) is selected so as to be 100% by weight in total, and is copolymerized in the presence of a radical generator. Number average molecular weight (Mn) obtained by polymerization is 3,000 to 30,000
And the weight average molecular weight is (Mw) / number average molecular weight (M
n) is composed of an acrylic copolymer (A) having 1.8 to 25, a polyisocyanate (B), and an organic solvent (C), and the acrylic copolymer (A) and the polyisocyanate (B) ) / OH / NCO = 1 /
(0.2 to 1.8). 2. The organic solvent (C) is a nonpolar organic solvent having an aniline point or a mixed aniline point at 7 to 70 ° C. and a polar organic solvent in a weight ratio of the nonpolar organic solvent / the polar organic solvent = The coating resin composition according to claim 1, wherein the composition is blended so as to be 100/0 to 40/60.