JPS61130381A - Acrylic paint - Google Patents

Abstract

PURPOSE:To provide an acrylic paint having excellent resistance to wear, alcohols and plasticizer migration and workability, containing a mixture of a drying oil fatty acid-modified vinyl copolymer resin and a vinyl copolymer resin having a resin skeleton contg. no functional groups. CONSTITUTION:5-25wt% epoxy group-contg. monomer (a1), 40-95wt% methyl methacrylate (a2), 0-10wt% alkyd resin (a3) contg. copolymerizable unsaturated bonds and 0-50wt% other copolymerizable vinyl monomer (a4) are used in such a quantity that the combined quantity is 100wt%. They are divided into two groups, one group being 20-80wt% a2 alone, mixture of a2 and a4 and/or a3, or mixture of a2, a4 and a3 and the other being 80-20wt% of the combined quantity of a1, a2, a4 and a3. When 80-98% of the monomers of one of these groups is converted to polymer, another group is added and copolymerized. The titled paint contains a resin as a component obtd. by adding 5-60pts.wt. drying oil fatty acid having an iodine value of 100-200 to 100pts.wt. the resulting epoxy group-contg. vinyl copolymer resin.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a new and useful acrylic paint, and more specifically, the present invention relates to a new and useful acrylic paint, and more specifically, a specific drying oil fatty acid modified vinyl copolymer resin and a functional group in the resin skeleton. Comprising a mixture with a vinyl copolymer resin that does not contain (polar groups) as an essential component, it has excellent abrasion resistance, alcohol resistance, plasticizer migration resistance, and workability, and is especially suitable for various SF plastics. Regarding paints suitable for painting.

[Problems to be solved by conventional technology and invention]

Traditionally, this type of glass paint (hereinafter also referred to as plastic paint) has been divided into lacquer-based paints that do not participate in crosslinking and urethane-based paints that participate in crosslinking. is hardenable,
Although it has excellent coating film performance, it cannot be said to dry quickly on the negative side, and depending on the solvent used, it may corrode the plastic material and impair the painted appearance, which is undesirable.

On the other hand, lacquer-based paints harden quickly and are easy to use, but have the drawback of insufficient gloss, appearance, and coating performance.

Therefore, it is desired to develop a coating system that can complement the deficiencies of both the lacquer system and the urethane system.

Separately, a method of obtaining an air-curable resin by adding a drying oil fatty acid to an epoxy group-containing acrylic copolymer resin is disclosed, for example, in British Patent No. 767,476; In order to solve the problem that the resin obtained by this method lacks gloss due to insufficient moisture to the pigment, the following is proposed.
For example, JP-A-53-51232 and 53-9923
It can be said that this is an improved method as described in Publication No. 1.

However, all of these improvement methods involve adding the drying oil fatty acid to the epoxy group in the acrylic copolymer resin, and then esterifying it with dicardic anhydride such as tetrahydrophthalic anhydride. (1) Preparation of an acrylic resin as a paste resin, (2) Modification by addition of a drying oil fatty acid to this acrylic resin, and (3) Esterification of the thus obtained fatty acid-modified copolymer resin with dicarmenic anhydride. This method cannot be said to be a preferable method because it lengthens the total reaction time consisting of three steps, complicates reaction control, and increases production costs.

In addition, it cannot be said that a glass paint using such a drying oil-fatty acid-modified copolymer resin is a preferable method because of the selectivity of materials in terms of adhesion and the like.

As mentioned above, there are many problems with conventional paints that need to be improved and solved.

[Means for solving problems]

However, in view of the actual situation as described above, the present inventors have developed a method that can be obtained by a simpler method, has good wettability to pigments, has excellent gloss, and can be applied to plastics. It has abrasion resistance such that the base material is not easily exposed, even if there is one scratch during packaging, and even more so due to the transfer of plasticizer due to contact with the painted surface of polyvinyl chloride resin crack cord (PVC cord). The present invention was completed as a result of intensive research to obtain a paint for glass-based coatings that has excellent stain resistance and plasticizer migration resistance, which prevents contamination and softening of painted surfaces. .

That is, the present invention relates to an epoxy group-containing vinyl monomer.

5 to 25% by weight of mer (a-1), methyl methacrylate
) 40 to 95% by weight of (a-2), 0 to 10% by weight of alkyd resin (a-3) having a copolymerizable unsaturated bond, and a copolymerizable vinyl monomer (a-4)
0 to 50% by weight of monomer (a-2) and (a-4) are used so that the total amount is 100% by weight. / or a mixture in which the total amount of the above-mentioned alkyd resin (a-3) is 20 to 80% by weight of the total amount of these (a-2), (a-4), and (a-3), and the monomer (a-3); -1) and a system containing monomer (a-1) consisting of these (a-1);
-2), (a-4), and (a-4) total amount is 80~2
0% by weight of monomer (a-2) alone or entirely of monomer (a-1) consisting of monomer (a-2) and (凰-4) and/or alkyd resin (a-3).
1. When the polymerization rate of one of the systems reaches 80 to 98%,
The other system is also copolymerized, and then 5 to 6 parts of drying oil fatty acid having an iodine value of 100 to 200 is added to 100 parts by weight of the epoxy group-containing vinyl copolymer thus obtained.
For cellulose compounds, dryers, pigments and/or paints, which contain as an essential component a drying oil-fatty acid-modified vinyl copolymer resin obtained by addition reaction in a proportion of 0 parts by weight. The object of the present invention is to provide an acrylic paint which also contains additives and has particularly excellent abrasion resistance, alcohol resistance, plasticizer migration resistance, and workability.

Here, typical drying oil fatty acids with an iodine value of 100 to 200 include natural fats and oils such as cottonseed oil, soybean oil, rice bran oil, dehydrated castor oil, linseed oil, tall oil, and Chinese tung oil. Fatty acids, ``Hydien'', ``Hydwen H'', ``Hytzen S'', rsK conjugated fatty acids 20'' [all Soken Chemical products] or ``PAMOLYN 200 or 300''
(synthetic drying oil fatty acids such as (produced by Herki Tameshisu Co., Ltd., USA))
However, in order to adjust the iodine value of such fatty acids, in some cases, coconut oil fatty acids, castor oil fatty acids, octylic acid, diuric acid, "parsatic acid" (synthetic drying oil fatty acids) or other saturated or unsaturated fatty acids with an iodine value of less than 100, such as stearic acid, in an amount within a range that does not impair the air drying properties of the resulting modified vinyl copolymer resin, as listed above. Can be used in combination with various drying oil fatty acids.
The appropriate amount of each of the above-mentioned drying fatty acids to be used is 5 to 60 parts by weight, preferably 110 to 50 parts by weight, based on 100 parts by weight of the epoxy group-containing vinyl copolymer.
This is in parts by weight.

If the amount is less than 5 parts by weight, the resulting modified copolymer resin will have poor air curability, and the coating film will have a sufficient three-dimensional structure, resulting in Ic<<, resulting in poor physical properties and resistance. Solvent properties deteriorate, and conversely, if it exceeds 60 parts by weight, the coating film tends to yellow, weather resistance decreases, and crosslinking of the coating film progresses too much. In either case, the coating film becomes brittle due to loss of flexibility and cannot be put to practical use.

Next, the above-mentioned epoxy group-containing vinyl monomer (a-1
) are typically glycidyl (meth)acrylate or β-methylglycidyl (meth)acrylate, but (meth)allyl glycidyl ether can also be used.

These may be used alone or in combination of two or more.

And the epoxy group-containing vinyl monomer (a-1)
is used within a range of 5 to 25% by weight, but since the epoxy group in the monomer participates in the reaction with various drying oil fatty acids as mentioned above, the monomer (a
It goes without saying that the appropriate amount of -1) to be used should be determined mainly depending on the amount of the drying oil fatty acid used, and usually, 91.0 It is preferable to use the epoxy group in a proportion of 1.25 to 1.25 equivalents from the viewpoint of reaction rate and prevention of adverse effects of residual carxyl groups on the coating film.

In addition, the alkyd resin (a-3) having a copolymerizable unsaturated bond can be used not only for pigments with low oil absorption such as titanium oxide and Bengara, but also for quinacridone,
7 Talocyanin series, a! organic pigments such as
- It is used when it is desired to improve the dispersibility of pigments that have poor dispersibility and relatively large oil absorption, such as pigments, and in that sense, the alkyd resin has poor membrane performance itself. It can be said that there is no further involvement.

The resin (a-3) may be one modified with oil or fatty acid, or a so-called oil-free alkyd resin that is not modified with these. In the present invention, each of these alkyd resins is used. Among these, those having an unsaturated bond copolymerizable with the six vinyl monomers are particularly suitable. - Typical examples of such alkyd resins include saturated fatty acids such as octylic acid, lauric acid, stearic acid or "persatic acid"; unsaturated fatty acids such as oleic acid, linoleic acid, lyluic acid, eriostearic acid or ricinoleic acid. Fatty acids: Chinese tung oil, linseed oil, dehydrated castor oil,
Oils or oils such as tall oil, cottonseed oil, bean oil, olive oil, safflower oil, castor oil, or semi-drying oils such as rice bran oil, or non-drying oils such as hydrogenated coconut oil or 4-mu oil. -tylene glyconyl, clopylene glycol, neopentyl glycol, with or without the use of one or a mixture of two or more of these fatty acids;
1.6-hexanediol, glycerin, trimethylolethane, trimethylo-/I/glo/47,1,2.6
- One or more of various polyhydric alcohols such as hexaztriol, pentaerythritol or nrubitol with benzoic acid, p-t@rt-butylbenzoic acid, phthalic acid (anhydride), λ xahydro (anhydride) Phthalic acid, tetrahydro-phthalic acid, tetrachloro-phthalic acid, hexachloro-7thalic acid, tetrabromo-phthalic acid, phthalic acid, trimellitic acid,
One or more of various carboxylic acids such as (anhydrous) succinic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, fumaric acid, adipic acid or sepacic acid are further added as necessary by a conventional method. Accordingly, monoepoxy compounds such as glycidyl esters of fatty acids such as Gardura EJ (a product of Shell Company), polyepoxy compounds such as [Epoxy resins such as Epiclon 200, 400, 850 or 1050J [epoxy resin manufactured by Inu Nippon Ink Chemical Co., Ltd.]] or tolylene diisocyanate, hexamethylene diincyanate or 4.4'-
Diincyanates such as methylene bis(cyclohexyl incyanate), polyinocyanates obtained by the addition reaction of these various diincyanates with polyhydric alcohols such as dehydrated water, and twin cyanates (co-inocyanates). ) One or more polyincyanates having an incyanuric ring obtained by a polymerization reaction are substituted for a part of the suspended polyhydric alcohols and carboxylic acids, and the resulting polyinsyanuric acid is reacted in a conventional manner. In this case, the alkyd resin should be one that does not have copolymerizable unsaturated bonds, or one that has been modified with a small amount of saturated fatty acid or non-drying oil (fatty acid). Or an oil-free alkyd tree that has not been modified in any way with oil or fatty acids.
In particular, other vinyl monomers, namely monomers (a-1) listed above.

(a-2) and (a-4) In order to introduce copolymerizable unsaturated bonds that will serve as grafting points, pre-treatment using an unsaturated carboxylic acid such as (anhydrous) maleic acid or fumaric acid. is necessary.

And the alkyd resin obtained in this way (a-
3) is used in a range of 0 to 10% by weight, but if it is used in a large amount exceeding 10% by weight, solvent resistance and stain resistance become inferior, and □Moreover, during polymerization, the alkyd resin This is not preferable since the carfoxyl groups therein and the epoxy groups in the epoxy group-containing vinyl monomer (a-1) tend to react and form into glues, which is not preferable.

Therefore, the amount of the alkyd resin (a-3) to be used should be within the range mentioned above, and the acid value and oil of the alkyd resin should be adjusted to prevent gluing from occurring due to the reaction between these carmexyl groups and epoxy groups. It goes without saying that it should be determined in consideration of the length, amount of copolymerizable unsaturated bonds, molecular weight of the resin (a-3), and molecular weight of the resulting epoxy group-containing vinyl copolymer. , other copolymerizable vinyl monomers (
Typical examples of JL-4) include methyl acrylate, ethyl (meth)acrylate, and n-furovir (meth).
acrylate, penta-furovir (meth)acrylate, n
-butyl (meth)acrylate, l-butyl (meth)acrylate, tart-butyl (meth)acrylate,
2-ethylhexyl (meth)acrylate, lauryl (
Methyl methacrylate (a-2) as described above, such as meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, nopromoprobil (meth)acrylate or tribromophenyl (meth)acrylate various (meth)acrylates except diesters of monohydric alcohols with unsaturated dicarboxylic acids such as maleic, fumaric or itaconic acids; vinyl acetate, vinyl benzoate or "peopa" (vinyl esters of Shell) )
Vinyl esters such as ``Visco-'' 8 F,
8 FM.

3F or 3FMJ (fluorine-containing acrylic monomer from Osaka Organic Chemicals), 2-fluorocyclohexyl (
Vinyl esters containing a (bar)fluoroalkyl group, such as meth)acrylate, non-perfluorocyclohexyl fumarate, or N-1-f ropyrnothous-fluorooctasulfonamide ethyl (meth)acrylate;
Vinyl ethers, (meth)acrylates or unsaturated cals? Fluorine-containing compounds such as phosphoric acids; styrene, α-
Aromatic vinyl compounds such as methylstyrene, p-tart-butylstyrene or vinyltoluene; or vinyl chloride, vinyl fluoride, chloride? Examples include olefins such as nylidene, vinylidene buttoxide, and (meth)acrylonitrile.

Therefore, (a-1) and (a-2) listed above.

Various monomers and alkyd resins (a-4) and alkyd resins (a-4)
-3) using the epoxy group-containing vinyl co-electro-coupled t
- The preparation method is not particularly limited, and various known and commonly used methods such as solution polymerization and bulk polymerization may be used;
Moreover, it is most preferable to use solution polymerization because the molecular weight can be easily controlled.

The epoxy group-containing vinyl copolymer obtained by smelting is further subjected to an addition reaction with the above-mentioned drying oil fatty acid to give the desired drying oil fatty acid modified vinyl copolymer resin. It is composed of one part of the polymer having oil-fatty acid gold pendants, and one part of the polymer that does not contain the fatty acid at all.
Vinyl monomers other than >, that is, the monomers mentioned above (
a-2) alone, or a mixture of monomer (a-4) and/or alkyd resin (a-3), monomer (a-2), monomer (a-4), and alkyd resin (a-2). 20-80 weight ts of total amount with 3,).

Preferably, the monomer (a-1), monomer (a-2), and monomer (
a-4) and/or a mixture with alkyd tree 111 (a-3), and on the other hand, a system containing no monomer (a-1) at all, a system containing the monomer (a-1) a-2) and a system consisting of a mixture of monomer (a-4) and/l or alkyd resin (a,-3), and the polymerization rate of any one of the systems is 8.
When it reaches 0 to 91%, the remaining system is also copolymerized, and then the epoxy group-containing vinyl copolymer thus obtained is reacted with a drying oil fatty acid as mentioned above in a predetermined ratio. At this time, at the same time, a part of the polymer that does not contain the fatty acid at all can be obtained corresponding to the system that does not contain the monomer (a-1) tl'' at all among the two monomer systems that have been divided as described above. In the invention, this epoxy group-containing vinyl copolymer contains epoxy groups, i?IJ ma-min, a part of the polymer with the corresponding drying oil fatty acids pendant, and a part of the polymer that does not contain any epoxy groups, thus A portion of the polymer that does not contain any drying oil fatty acids will exist in opposition, but in the case of "epoxy group-containing vinyl copolymer" and "drying oil fatty acid modified vinyl copolymer resin", respectively, It shall mean a mixture of these two opposing components (one part of the polymer).

Here, monomer (a-2) alone or a mixture of monomer (a-2) and monomer (a-4) and/or alkyd resin (a-3) is used. ), monomer (a-4), and alkyd resin (a-3) are less than 20% by weight of the total amount, that is, the amount of monomer (a-1) involved is small, and the modification with drying oil fatty acids is The solvent resistance and abrasion resistance of the coating film, which should be said to be a feature of this, decrease, and on the other hand, if it exceeds 80% by weight.

In other words, since the portion of monomer (a-1) that does not participate at all decreases, the adhesion to the plastic material becomes poor, and in this case, the purpose of the present invention cannot be met. Undesirable.

The drying oil-fatty acid-modified vinyl copolymer resin thus obtained, which is an essential component of the paint of the present invention, satisfies the objectives of the present invention by itself and can be made into a good rear paint. In addition, if necessary, cellulose derivatives such as nitrified cotton or striped cellulose acetate zotylate, dryers, pigments, and paint additives are also mixed into the drying oil-fatty acid-modified vinyl copolymer resin. At least it can be done with the paint of the present invention.

At this time, in order to improve the thinner resistance, dry VK hardness, flexibility, etc. of the paint of the present invention, various cellulose derivatives such as the above are added to the paint of the present invention, and to improve the mechanical properties of the paint of the present invention. 1) Add plasticizer or polyester resin, and if you want to further improve "knock-on" prevention, weather resistance, and leveling properties, use antifoaming agents, leveling agents, ultraviolet absorbers, antioxidants, etc. Using each of the 81 known and commonly used paint additives in conventional amounts (
・It's fine.

Here, the above-mentioned dryer may be any of those commonly used for paints, but the most representative ones include cobalt, vanadium, manganese, cerium, lead, iron, calcium, zinc,
Naphthenates, octylates, or resinates such as zirconium, cerium, nickel, or tin may be used, but the amount used in such a dryer depends on the type of dryer, the composition ratio of each other component, and the required performance. You should select the appropriate one by fishing on a boat.

At that time, penzoyl oxide, methyl ethyl ketone peroxide or t@rt-butyl 9-
A small amount of an organic peroxide such as benzoate may also be used in combination to further enhance the effectiveness of the dryer.

Furthermore, since hydroxyl groups generated by the reaction between fatty acids and epoxy groups are already present in the drying oil-fatty acid-modified vinyl copolymer resin, which is an essential component of the paint of the present invention, The coating composition of the present invention can also be crosslinked and cured by incorporating a conventional curing agent component such as dlJmer.

To apply the paint of the present invention thus obtained.

Known and commonly used coating methods such as brush coating, spray coating, or roll coating can be employed, and the materials or base materials to which the paint of the present invention can be applied are mainly ABS, "Noryl", polycarbonate, melamine resin, polystyrene, Urea resin, /IJ ester resin, Boripropylene or RIM
, urethane, etc., to mixed systems or composite systems composed of multiple components (
Various / Including IJ Mama Alloy. ), or F'
A wide range of so-called composite materials such as RP, FRTP or FR-RIM can be used.

〔Effect of the invention〕

Since the paint of the present invention uses a drying oil fatty acid modified vinyl copolymer resin obtained by a -casting method as its essential component,
For example, a two-step method in which an epoxy group-containing vinyl copolymer is first prepared using a vinyl monomer containing an I-oxy group and an alkyd resin having a copolymerizable unsaturated bond as the main raw materials, and then a drying oil fatty acid is added. It has the advantage of superior moisture resistance and adhesion compared to similar resins obtained by.

When compared with conventional acrylic lacquers, the paints of the present invention are significantly superior in gloss, alcohol resistance, abrasion resistance, adhesion and plastic migration resistance.

〔Example〕

Next, the present invention will be specifically explained with reference to Reference Examples, Examples, and Comparative Examples. In the following, all parts and parts are based on weight unless otherwise specified.

Reference Example 1 (Example of Preparation of Drying Oil Fatty Acid Modified Vinyl Copolymer Resin) 300 parts of toluene, 179 parts of xylene, and 250 parts were placed in a four-way flask equipped with a thermometer, reflux condenser, stirrer, and nitrogen gas inlet tube. butyl acetate, ``Heccosol''
P-470 = 71 parts of 70 J (long oil alkyd resin manufactured by Dainippon Inya Chemical Industry Co., Ltd.) and G-tert
2 parts of -butyl-butyronitrile (DTBPO) were charged and the temperature was raised to 120°C. When the temperature reached the same temperature, 180 parts of methyl methacrylate (MMA) and azobisisobutyronitrile (AIBN) were added. ) and 1 part of tert-butylbenzoate (TBPB) were added dropwise over 1 hour and reacted at the same temperature for 1.5 hours. At this point, the polymerization rate was 93%. That was it, MM
A mixture of 470 parts of A, 100 parts of glycidyl methacrylate (GMA), 8 parts of AIBN, and 3 parts of TBPB was added dropwise over 3 hours, and after the addition was completed, the mixture was kept at the same temperature for 10 hours to react. The non-volatile content (NV
) was 51.6%, then 150 parts of soybean oil fatty acid, 50 parts of linseed oil fatty acid, and 0.2 part of 2-methylimidazole (2-MIZ) were added and heated at the same temperature. The reaction was carried out until the acid value reached around 2.
Add 50 parts of n-butanol to obtain a transparent solution of the target resin with a W of 50.61, a donor viscosity of 2° at 25°C (the same applies hereinafter), and an acid value of 1.7. Ta.

Hereinafter, this will be abbreviated as resin solution (1).

Reference Example 2 (Same as above) First, a monomer mixture consisting of 100 parts of styrene (ST) and 630 parts of styrene (ST) was prepared, and 300 parts of toluene, 187 parts of xylene, and acetic acid were added to the same reactor as in Reference Example 1. 250 parts of butyl, “Peccosol P-470-
Prepare 430 parts of 70J and 2 parts of DTBPO to make 1
The temperature was raised to 20°C, and when the temperature reached the same temperature, 530 parts of the previous monomer mixture, 80 parts of GMA, and AI were added.
3 parts of a mixture of 7 parts of BN and 3 parts of TBPH
The mixture was added dropwise over time and kept at the same temperature for an additional 2 hours for reaction. At this point, the polymerization rate was 97.

Subsequently, a mixture consisting of the remaining 200 parts of the previous monomer mixture, 2 parts of AIBN, and 1 part of TBPB was added dropwise over 1 hour, and after the addition was completed, the mixture was kept at the same temperature for 12 hours.
The reaction was continued for a certain period of time, and after confirming that NY was 52.8%, 100 parts of soybean oil fatty acid, 60 parts of linseed oil fatty acid and 0.2 part of 2-MIZ were added and the same amount was added. After reacting at a temperature of 250 ml until the acid value is around 2,
1-butanol was added to obtain a transparent solution of the desired resin having a W of 5r.01, a viscosity of 2, and an acid value of 1.8. Hereinafter, this will be abbreviated as resin solution (2).

Reference Example 3 (Same as above) In a reactor similar to Reference Example 1, 300 parts of toluene, 183 parts of xylene, 250 parts of butyl acetate, 57 parts of Beccosol P-470-70J, and 2 parts of DTBPO were added.
When the temperature reached the same temperature, 200 parts of ST, 460 parts of 1st grade, 100 parts of GMA,
A mixture of 10 parts of AIBN and 4 parts of TBPH was added dropwise over 4 hours, and the reaction was further continued at the same temperature for 10 hours. After confirming that the ratio was 51.6%, soybean oil fatty acid was added. 100 parts of linseed oil fatty acid, 100 parts of linseed oil fatty acid, and 0.2 part of 2-MIZ were added and reacted at the same temperature until the acid value reached around 2. Then, 250 parts of l-butanol was added and mushrooms were grown. 50.5, a viscosity of Y-2, and an acid value of 1.8, a transparent solution of the target resin was obtained. Hereinafter, this will be abbreviated as resin solution (3).

Reference Example 4 (Same as above) A monomer mixture consisting of 300 parts of 5T0 and 350 parts of 71 parts of 704 and 2 parts of DTBPO were charged and the temperature was raised to 120°C. When this temperature was reached, 400 parts of the previous monomer mixture and AIBN were added.
A mixture consisting of 5 parts of DBPH and 2 parts of DBPH was added dropwise over t-2 hours, and even after the addition was completed, the mixture was kept at 120°C for 2 hours.

Subsequently, with the remaining 250 parts of the above seven i-mixtures,
A mixture of 100 parts of GMA, 5 parts of AIBN, and 2 parts of TBPH was added dropwise over a period of 2 hours, and an additional 1 part of
The reaction was continued by keeping at the same temperature for 0 hours, and W was 51.6.
After confirming that it is 100% of soybean oil fatty acid
parts, 100 parts of linseed oil fatty acids and 0 parts of 2-MIZ
．． 2 parts were added and reacted at the same temperature until the acid value exhibited a value around 2. When 250 parts of n-butanol was added thereto, M' was 50.7%, the viscosity was 2, and the acid value was around 2. Value is 1.6
A transparent resin solution was obtained. Hereinafter, this will be abbreviated as resin solution (4).

Examples 1 to 4 and Comparative Examples 1 and 2 Using each resin solution obtained in Reference Examples 1 to 4, 1 part 4 seconds with an NV of 20% was prepared according to the blending ratio shown in Table 1. All formulations were prepared with or without nitrified cotton methyl ethyl ketone solution and with cobalt 6-thinaphthenate, and then titanium oxide was prepared at a PWC of 40% for each formulation and commercially available acrylic lacquer.
%, and then kneaded in a mint mill for 1 hour to prepare white enamel.

Next, each white enamel was diluted with a thinner consisting of ethyl acetate/1-butanol/Gutilce a Solde (manufactured by Union Ki Carbide Co., USA) = 40/40/20 (by weight/1 ratio) to reduce the dry film thickness. AES, P as shown in the table with air spray so that the thickness is 15 μm.
S, rNoryl" [polyphenylene oxide made by Nippon Engineering Plastics Co., Ltd.] and Dillon [polyphenylene ether made by Asahi Kasei Co., Ltd.] were coated on various materials, baked at 60C for 30 minutes, and then heated to room temperature. Each cured coating film was obtained by leaving it to stand for 3 days.

Thereafter, the performance evaluations for each of these coating films are summarized in the same table, and each performance evaluation was performed in the following manner.

Gloss...Displayed using 60 degree specular reflectance (equity).

Abrasion resistance...Norman Tool and Meta/USA
The test was carried out using an RCA type abrasion resistance tester manufactured by Ping Co., Ltd.

Adhesion: After cutting the goblets at room temperature, that is, making cross cuts, and then removing the cellophane tape, the number of remaining goblets rA/100j (A:
Measured number of remaining gopans) Only tA was used.

Moisture resistant adhesion...AES material at 50℃, 984R,
The same procedure as above for "adhesion" was carried out except that the test was held under H.H. for 72 hours.

Resistance to plasticizer transfer...The state of change in the coating after placing an electric wire at 600 on a PVC cord and then applying a load of 500.9, mainly depends on whether or not the mold of the electric wire is attached or not. Evaluation was made on four levels: "excellent", "good", "fair" and "poor".

Excellent...Good with no change at all...Minor changes possible...Significant changes not possible...Significant changes Solvent resistance...Rubbing test using ethanol The number of times of rubbing is indicated by □.

Claims (1)

[Scope of Claims] (A) 5 to 5 of the epoxy group-containing vinyl monomer (a-1)
25% by weight, 40-95% by weight of methyl methacrylate (a-2), alkyd resin having copolymerizable unsaturated bonds (a-3)
) and 0 to 50% by weight of other copolymerizable vinyl monomer (a-4)
% by weight is used so that the total amount is 100% by weight, and the above-mentioned monomer (a-2) alone, or this monomer (a-2) and (a-4) and/or the above-mentioned alkyd resin (a-3) and the total amount of these (a
-20 to 8 of the total amount of (a-4) and (a-3)
A system containing monomer (a-1) consisting of a mixture of 0% by weight and monomer (a-1), these (a-2) and (
Monomer (a-2) alone, or monomers (a-2) and (a-4) and/or alkyd resin, comprising 80 to 20% by weight of the total amount of a-4) and (a-3). (
a-3) and a system containing no monomer (a-1) at all, and first, when the polymerization rate of one of the systems reaches 80 to 98%, the other system is divided into two. system was also copolymerized, and then a drying oil fatty acid having an iodine value of 100 to 200 was added to 100 parts by weight of the epoxy group-containing vinyl copolymer thus obtained in a proportion of 5 to 60 parts by weight. An acrylic paint comprising the obtained drying oil-fatty acid modified vinyl copolymer resin as an essential component, and further comprising a cellulose compound, a dryer, a pigment and/or a paint additive if necessary.