JPH0362867A - Coating compound composition - Google Patents

Abstract

PURPOSE:To obtain a coating compound composition providing a coating film having excellent hardness, scratching resistance and stain resistance without damaging weather resistance and water resistance comprising a vinyl-based copolymer containing a specific amount of a polymerization unit of dicylohexyl fumarate and having a specific molecular weight. CONSTITUTION:The objective composition comprising a vinyl-based copolymer containing 5-50wt.% polymerization unit of dicylohexyl fumarate and having 1,000-50,000 average molecular weight. The composition preferably contains >=70 pst.wt. crosslinking agent (preferably polyisocyanate or amino resin) based on 100 pts.wt. copolymer.

Description

Detailed Description of the Invention <Field of Industrial Application> The present invention relates to a coating composition containing as a resin component a vinyl copolymer containing dicyclohexyl fumarate as a polymerized unit, and more specifically, it relates to a coating composition containing as a resin component a vinyl copolymer containing dicyclohexyl fumarate as a polymerized unit. The present invention relates to a coating composition that provides a coating film with excellent hardness, scratch resistance, and stain resistance without impairing the properties.

<Prior Art> Vinyl resins, especially acrylic resins, have traditionally been used in applications that require weather resistance, such as top coatings for automobiles. In recent years, quality requirements for paint films have become even more sophisticated, and in particular, for automobile parts made of plastic materials, improvements in paint film hardness, scratch resistance, stain resistance, etc., in addition to weather resistance, are desired.

Conventionally, in acrylic paint resins, in order to improve coating film hardness, scratch resistance, and stain resistance.

It was customary to increase the content of styrene and methyl methacrylate, which are hard components.

<Problems to be Solved by the Invention> However, increasing the styrene content as a resin component for paints causes a decrease in weather resistance, and increasing the methyl methacrylate content causes a decrease in water resistance. be.

An object of the present invention is to provide a coating composition that provides a coating film with excellent hardness, scratch resistance, and stain resistance without impairing weather resistance or water resistance.

<Means for Solving the Problems> According to the present invention, dicyclohexyl fumarate contains 5 to 50% by weight of polymerized units and has an average molecular weight of 1.

OOO~50. A coating composition characterized by containing a vinyl copolymer having O○○ is provided.

The present invention will be explained in more detail below.

The coating composition of the present invention contains, as a resin component, a vinyl copolymer containing dicyclohexyl fumarate as an essential component. The content of the dicyclohexyl fumarate is in the range of 5 to 50 percent by weight based on polymerized units of dicyclohexyl fumarate based on the entire vinyl copolymer.

In this case, if it is less than 5% by weight, the effect of improving the hardness, scratch resistance, and stain resistance obtained by dicyclohexyl fumarate is insufficient, and if it exceeds 50% by weight, flexibility decreases, which is not preferable. In the coating composition of the present invention, by using the dicyclohexyl fumarate, the glass transition point and thermal stability of the vinyl copolymer are improved. , scratch resistance, and stain resistance can be improved.

In the vinyl copolymer of the present invention, vinyl monomer components other than dicyclohexyl fumarate include methyl acrylate-1~, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate,
Acrylic monomers with no functional groups other than unsaturated double bonds, such as butyl methacrylate, octyl acrylate, octyl methacrylate, dodecyl acrylate, dodecyl methacrylate, octadecyl acrylate, octadecyl methacrylate; carboxyl groups such as acrylic acid and methacrylic acid an acrylic monomer having; 2-
Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, reaction product of 2-hydroxyethyl methacrylate and caprolactone (U
jProduct name "Plaxel FM Monomer" Daicel Industries, Ltd.
Acrylic monomers containing hydroxyl groups, such as those produced by the Company); acrylic monomers containing epoxy groups, such as glycidyl acrylate-1 and glycidyl methacrylate; esters of male 3-yic acid and m alcohols; styrene.

Other vinyl monomers such as α-methylstyrene, vinyl acetate, and vinyl chloride can be preferably used.

The vinyl copolymer of the present invention can be produced by a solution polymerization method by dissolving the above-mentioned vinyl monomer and dicyclohexyl fumarate in an organic solvent and heating the solution in the presence of a radical polymerization initiator to cause a polymerization reaction. Examples of organic solvents include toluene, xylene, aromatic hydrocarbon solvents such as the trade name "Turupetz #100J" (manufactured by Exxon Chemical Co., Ltd.); ethyl acetate, butyl acetate, ethylene glycol monoethyl acetate, propylene glycol monomethyl ether acetate. Ester solvents such as; ketone solvents such as methyl isobutyl ketone and methyl amyl ketone; alcohol solvents such as butyl alcohol and amyl alcohol; and ether alcohol solvents such as ethylene glycol monobutyl ether can be used. , benzoyl peroxide, lauroyl peroxide, t-butylperoxybenzoate-1-, azobisisobutyronitrile, and the like can be used.

The vinyl copolymer contained in the coating composition of the present invention is
It has an average molecular weight of 1,000 to 50,000. If the average molecular weight is less than 1,000, the weather resistance, water resistance,
Flexibility, stain resistance, etc. are poor, and if it exceeds 50.00, painting workability will be poor.

A crosslinking agent may be added to the coating composition of the present invention in an amount of 70 parts by weight or less, preferably 20 to 50 parts by weight, based on 100 parts by weight of the vinyl copolymer. If the amount of the crosslinking agent exceeds 70 parts by weight, the weather resistance and water resistance of the coating film will deteriorate, which is not preferable. When using an acrylic monomer having a hydroxyl group as the vinyl copolymer used in the present invention, polyisocyanates and amino resins are suitable as the crosslinking agent. Examples of such polyisocyanates include hexamethylene diisocyanate, inphorone diisocyanate, methylcyclohexane-2,4-(or 2,6-)
-) Diisocyanate, 4,4 methylene bis(cyclohexyl isocyanate), adducts of each of these diisocyanates with polyhydric alcohols such as ethylene glycol and trimethylolpropane, biuret forms added with water, and these diisocyanates with each other Further, blocked isocyanate compounds obtained by blocking each of the above-mentioned polyisocyanate compounds with a lower monohydric alcohol, ε-caprolactam, or the like can be mentioned. Further, examples of the amino resin include those obtained by adding formaldehyde to melamine, benzoguanamine, etc., and then etherifying it with a monohydric alcohol of 01 to C4. These amino resins may be used as a mixture of two or more. Furthermore, when an acrylic monomer having a carboxyl group is used as the vinyl copolymer of the present invention, a polyvalent epoxy compound can be used as a crosslinking agent. When using an acrylic monomer having the following, a polyhydric carboxylic acid compound can be used as a crosslinking agent.

7- Solvents, pigments, and additives can be added to the coating composition of the present invention as necessary. Further, other resins such as acrylic resins having compatibility may be added within a range that does not adversely affect the effects of the present invention.

The coating composition of the present invention can be used as a lacquer-type coating that does not contain a crosslinking agent or as a clear coating that does not contain a pigment.

The coating composition of the present invention includes metal 1 synthetic resin, wood, glass,
It can be coated on various materials such as concrete, and can be used for a wide variety of applications such as automobiles, home appliances, building materials, and pre-coating metals.

<Effects of the Invention> The coating composition of the present invention exhibits excellent coating film hardness, scratch resistance, and stain resistance without impairing weather resistance and water resistance.
Can be used for a variety of painting purposes.

<Example> Next, the present invention will be specifically explained using synthetic leather examples, examples, and comparative examples. All parts and percentages hereinafter are based on weight unless otherwise specified.

The sacrificial material is a 4L flask equipped with a stirrer, a reflux condenser, and a thermometer.
Based on the formulation of Synthetic Leather Example 1 in Table 1, xylene 80.0
The temperature was raised to 140°C.

Next, based on the formulation shown in Table 1, the following monomers and polymerization initiators were added dropwise at 140°C over 3 hours.

Dicyclohexylmaleimide 20.0 parts Styrene 30.0 parts Dodecyl methacrylate-1-10.0 parts Plaxel FM-2*) 40.0 parts t-
Butyl peroxybenzoate 1.8 parts*) Manufactured by Daicel Chemical Industries, Ltd., trade name, reaction product of 2-hydroxyethyl methacrylate emole and caprolactone 2 moles.

Next, 0.5 part of t-butyl peroxybenzoate was added, and the reaction was further continued at 140°C for 2 hours to obtain a resin solution having a heating residue of 56.3% and a number average molecular weight of 7,500 as shown in Table 1.

Using the same reaction apparatus as Synthetic Leather Example 1, except for using the solvent, monomer, and polymerization initiator shown in the compounding ratios in Table 1,
The reaction was carried out according to the same reaction procedure as in Synthetic Leather Example 1. The properties of the obtained varnish are shown in Table 1. The resin solutions obtained in each of the above synthesis examples were mixed according to the conventional coating method at the blending ratios listed in Table 2. , respectively, obtained the paint. The obtained paint was applied to a commercially available polypropylene plate coated with the product name "Primatsu & 1500 Primer" (Nippon Oil & Fats Co., Ltd.) to a dry film thickness of 15 μm, and the dry film thickness was 30 μm. 80
Baked at ℃ for 30 minutes. Next, a performance test was conducted for each item shown in the same table. The results are summarized in Table 2.

5-8 Ratio 5-7 Paints were obtained from the resin solutions obtained in each of the above synthesis examples in accordance with a conventional paint-forming method at the blending ratios shown in Table 3. The obtained paint was applied to a Bonderite #3114 treated steel plate so that the dry film thickness was 30 μm.
After standing for 7 days at 20° C. and 75% relative humidity, performance tests were conducted on each item shown in Table 3. The results are summarized in Table 3.

*1) Coronate EH: manufactured by Nippon Polyurethane Industries Co., Ltd., trade name, hexamethylene diisosiapho 1-trimer,
Effective NC○2], 3%. 100% heating residue.

*2) Manufactured by Ishihara Sangyo Co., Ltd., trade name, rutile type titanium dioxide.

*”) Based on JIS K 5400.6.760 degree specular gloss.

*4) After sanding the test piece with #1500 abrasive paper, compound (FMC831-P) was applied.

Waxing is performed using the product name (manufactured by Ishihara Pharmaceutical Co., Ltd.),
The degree of gloss recovery was evaluated.

0 The original luster is restored X Gloss does not recover NeS) After sanding the specimen as described above.

Rub carbon black on it. Next, the condition after removing the dirt with white gasoline was evaluated.

○ No stains left x Black stains left *') Judged by the color difference (△E) after 1000 hours on a sunshine weather meter according to JIS D 0205.7.6 accelerated weathering test method.

O△E is within 2.0 × △E is 2.0 or more *7) After standing in a humidity tester at a temperature of 45° C. and a relative humidity of 100% for 120 hours, the following judgment is made.

○ No abnormality × Even the slightest blister occurs 0 〇) Place the back side against a 1-inch diameter mandrel and bend the test piece. The state of the coating film at that time was evaluated as follows.

○ No abnormalities × Cracks occur in the coating *g) According to JIS D 0202.8.10 pencil scratch test method.

Thu 1'') The test was conducted in the same manner as in *7), except that the test time was 48 hours, and the test was evaluated in the same manner.

15 As is clear from Table 2, the coating compositions of the present invention (Examples 1 to 4) have excellent gloss, scratch resistance, stain resistance,
Although it exhibits weather resistance, water resistance, and flexibility, Comparative Examples 1 to 4 do not simultaneously satisfy the above various performances. Furthermore, as is clear from Table 3, the coating compositions of the present invention (Examples 5 to 5)
8) shows excellent pencil hardness, weather resistance, and water resistance,
Comparative Examples 5 to 7 do not simultaneously satisfy the above various performances.

Claims (1)

Claims: 1) A coating composition comprising a vinyl copolymer containing 5 to 50% by weight of polymerized units of dicyclohexyl fumarate and having an average molecular weight of 1,000 to 50,000. 2) 7 based on 100 parts by weight of the vinyl copolymer
The coating composition according to claim 1, characterized in that it contains 0 parts by weight or less of a crosslinking agent.