JPS63137934A - Coating composition - Google Patents

Abstract

PURPOSE:To obtain a composition exhibiting excellent strain-proofing function over a long period and having high adhesivity to substrate, by adding a crosslinkable monomer containing OH group in the polymerization of a silicon- containing monomer and an alpha,beta-ethylenic unsaturated monomer. CONSTITUTION:A monomer mixture of (A) 1-40wt% monomer of formula (R1 is H or CH3; R2 is H or 1-6C alkyl; m is 1-6; n is 1-6) and (B) 99-60wt% monomers consisting of (i) 40-95wt% alkyl acrylate or methacrylate, (ii) 5-20wt% hydroxyalkyl-containing ester of an alpha,beta-ethylenic unsaturated carboxylic acid and (ii) 0-40wt% other copolymerizable monomer is polymerized and the obtained polymer is used as a coating film component. The coating composition is suitable for the application to tent or sheet produced by using a plasticized polyvinyl chloride as a base material.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to coating compositions, particularly for plasticized polyvinyl chloride.

(Prior Art) In recent years, there has been a strong demand for imparting stain prevention functions to the surfaces of various substrates, and many coating compositions have been proposed.

For example, it has been proposed to coat with a polymer mainly composed of methyl methacrylate, or to use a copolymer with a fluorine-based monomer or a silicone-based monomer as a coating composition.

Conventionally, it has been known that this type of coating composition has been applied to impart a water-fighting oil function to fibers and carpets.

In this case, although the original function of the silicone resin was exhibited, when it was used on a surface based on plasticized polyvinyl chloride, the stain prevention effect required at the same time as the above-mentioned properties could not be obtained.

Although the reason for this is not clear, it is difficult to believe that different substrates will exhibit the same effect, and there has been a desire to develop a coating composition that can solve these drawbacks.

(Problems to be Solved by the Invention) An object of the present invention is to provide a coating composition that has excellent adhesion to a substrate and exhibits an excellent stain prevention function for a long period of time.

(Means for solving the problem) The present invention can be summarized as follows: 1. A, general formula (provided that R, -H or CH2, R -■ or carbon number 1 to 6
1 to 40% by weight of a monomer represented by an alkyl group, m = 1 to 6, n = 1 to 6) B, (a) acrylic acid or methacrylic acid alkyl ester 40 to 95% by weight (b) α , hydroxyalkyl-containing ester of β-ethylenically unsaturated carboxylic acid 5 to 20% by weight (c) Other copolymerizable vinyl monomers 0 to 40% by weight Monomers consisting of 99 to 60% by weight The present invention relates to a coating composition containing a polymer as a coating film-forming component.

According to the research conducted by the present inventors, the coating film formed by coating the fluorine-based copolymer or silicone-based copolymer of the conventionally known antifouling agent is not polymerized by crosslinking. It was discovered that the stain prevention function was not maintained for this reason.

The present invention was completed based on this knowledge, and when producing a polymer whose constituent monomers are a silicon-containing monomer and an α,β-ethylenically unsaturated monomer composition, O
By polymerizing a crosslinkable monomer containing an H group as an essential monomer component, they succeeded in maintaining the stain prevention function for a long time.

41 To explain the present invention in more detail, among the coating film forming components of the coating composition, as component A, a silicon-containing monomer, a compound represented by the following general formula is used.

R, siR1 (however, R,=H or C84, R,t=H or carbon number 1~
6 alkyl group, l1l-1 to 6, n=1 to 6)
In this case, the number (m) of methylene groups in the molecule is limited to 1 to 6 because copolymerizability is poor if the number is 6 or more.

Also, R.

0-3i-R> The number of groups is limited to 1 to 6 because 6R2
This is because if the amount exceeds that amount, the copolymerizability will be poor.

The monomer composition of component B includes (a) acrylic acid or methacrylic acid alkyl ester, (b) hydroxyalkyl-containing ester of α,β-ethylenically unsaturated carboxylic acid, and (c) other copolymerizable vinyl monomers. It consists of a quantity.

Examples of acrylic acid or methacrylic acid alkyl esters include methyl acrylate, methyl metal acrylate,
Ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate,
These include butyl acrylate, butyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl meate, hexyl acrylate, 2-ethylhexyl methacrylate, heptyl acrylate, heptyl methacrylate, and similar substances having up to 20 carbon atoms in the alkyl group. esters can be used.

(B) The hydroxyalkyl-containing esters of α, β-ethylenically unsaturated carboxylic acids include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxy Propyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, etc. can be used.

(c) Other copolymerizable vinyl monomers in the component include:
Examples include styrene, α-alkylstyrene, α-chlorostyrene, vinyltoluene, acrylonitrile, and vinyl acetate.

The usage ratio of the monomer composition of component B is 40 to 40% for component (A).
95 parts by weight, (b) 5 to 20 parts by weight of component, and (c)
A range of 0 to 40 parts by weight of the components is preferred.

In the present invention, the blending amount of component (B) in particular affects the long-term sustainability of the stain prevention effect; if component (B) is less than 5, sustainability cannot be obtained, while if it exceeds 20, This is undesirable as it causes the paint film to become sticky.

In the present invention, the composition of component A and component B is as follows: component A 1
A suitable ratio is 40 parts by weight for component B and 60 to 99 parts by weight for component B.

If the A component is less than 1 part by weight, it will affect the long-term sustainability of the stain-preventing effect, while if it exceeds 40 parts by weight, the anti-stain effect due to the water and oil repellency of the silicone group will be outweighed by the adhesiveness and stains. This is because the prevention effect becomes worse.

In the polymerization reaction in the present invention, components A and B are mixed and stirred, then added in several portions into a flask, and heated to reflux temperature for 80 minutes.
This is done with stirring for ~12 hours.

Examples of organic solvents used in the present invention include alcohols such as methanol, ethanol, and propatool; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate and butyl acetate; and benzene, toluene, Hydrocarbons such as xylene are suitable.

The coating composition of the present invention is suitable for surface coating of tents, sheets, molded products, artificial leather 1, wallpaper, etc., which are made of plasticized polyvinyl chloride.

However, when plasticized polyvinyl chloride is used as a base material, the adhesion of the coating film may deteriorate due to bleeding of the plasticizer, so it is preferable to form a single layer of primer in order to prevent bleeding of the plasticizer.

Examples will be shown below to more specifically explain the present invention. In the examples, all parts are parts by weight.

Example 1 Silicone-based acrylic monomer (trade name
-22-5002 manufactured by Shin-Etsu Chemical Co., Ltd.> 45 parts, 105 parts of methyl methacrylate, 3 parts of di-tert-butyl peroxide, and 100 parts of toluene were charged and stirred for 8 hours under reflux to prepare a copolymer. Next, toluene 312
A coating composition was obtained in which the resin solid content was adjusted to 20% by weight.

Examples 2 to 3 and Comparative Examples 1 to 2 Copolymers were prepared by carrying out reactions in the same manner as in Example 1, except that the monomer composition was changed to that shown in Table 1, and Toluene was added to obtain each coating composition with a resin solids content of 20% by weight.

-〇- Experimental Examples Using the coating compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 2, PVC canvas (trade name: Crafter ni 355
Gravure printer (manufactured by Kuraray) (95 meshes)
A coated piece was prepared by drying at 80'C for 1 minute.

The performance of each coated piece was tested and the results are shown in Table 2.

Margin below However, the stain prevention test was conducted as follows.

A coated piece (3 cm x 3 cm) was soaked in a glass container containing the stain-preventing ingredients shown in Table 3, left in a dryer at 80'C for 15 minutes, and then roughly shaken for 3 minutes. After repeating the test, the coated piece was taken out and washed with water, and the percentage of dirt on its surface was visually determined.

In addition, for the bending resistance test, the coated piece was attached to a bending tester and 1
After flexing 10,000 times, the coated piece was placed in the stain component, shaken for 3 minutes, taken out, and the rate of crack occurrence on the surface was visually determined.

In the table, ◎...Not at all, excellent ○...Slight occurrence Δ...Conspicuous occurrence X: Entire occurrence (effect of the invention) As is clear from the above explanation, the present invention The coating composition has excellent stain prevention properties, maintains this effect for a long period of time, and is resistant to cracking even when bent.

Claims (1)

[Claims] 1. A. General formula▲ Numerical formula, chemical formula, table, etc.▼ (However, R_1=H or CH_3, R_2=H or an alkyl group having 1 to 6 carbon atoms, m=1 to 6, n = indicates 1 to 6)
1 to 40% by weight of the monomer represented by B, (a) 40 to 95% by weight of alkyl acrylic acid or methacrylate (b) 5 to 20% by weight of hydroxyalkyl-containing ester of α,β-ethylenically unsaturated carboxylic acid % (iii) Other copolymerizable vinyl monomers 0 to 40% by weight A coating composition comprising a polymer as a constituent monomer comprising 99 to 60% by weight of other copolymerizable vinyl monomers as a coating film forming component.