JPS6361032A - Coating composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition for plasticized polyvinyl chloride, containing a polymer consisting of a fluorine group-containing monomer having a specific structure as a film-forming component, having excellent antistaining property whose effect is maintained for a long-period and almost free from crack. CONSTITUTION:(A) 1-40wt% fluorine group-containing monomer expressed by the formula (R is H or CH3; m is 1-3; n is 1-5; X is H or F) is polymerized with (B) 99-60wt% monomers consisting of (i) 40-95% acrylic acid alkyl ester or methacrylic acid alkyl ester, (ii) 5-20%, alpha,beta-ethylenic unsaturated carboxylic hydroxyalkyl-containing ester and (iii) 0-40% other copolymerizable vinyl monomer, as constituting monomers to provide the aimed composition. As components (i), (ii) and (iii), e.g., methyl acrylate, etc., 2-hydroxyethyl acrylate, etc., styrene, etc., is respectively preferably used.

Description

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

(Conventional technology) In recent years, it has become necessary to add stain prevention functions to the surfaces of various base materials.

This is highly desirable 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 silicon-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 fluororesin 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 it has been desired 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 Problems) The present invention can be summarized as follows: 1. A, general formula % monomer represented by X=H or F) 1 to 40% by weight B, (a) acrylic acid or Methacrylic acid alkyl ester 40 to 95% by weight (b) Hydroxyalkyl-containing ester of α,β-ethylenically unsaturated carboxylic acid 5 to 20% by weight (c) Other copolymerizable vinyl monohungs 0 to 40% by weight The present invention relates to a coating composition containing, as a film-forming component, a polymer containing 99 to 60% by weight of monomers as constituent monomers.

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 fluorine group-containing monomer and an α,β-ethylenically unsaturated monomer composition, niO
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.

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

(However, R is H or CH3, m=1 to 3, n=1 to 5,
(■ or F) In this case, the number of methylene groups in the molecule is limited to 1 to 3 because if the number of methylene groups is 4 or more, the glass transition temperature will be low, resulting in stickiness and a decrease in stain prevention effect. This is because it is not desirable.

In addition, the number of CF2 groups is limited to 1 to 5 because when the number of CF2 groups is 6 or more, the fluorine groups increase water resistance and oil resistance, making it difficult for printing ink etc. to adhere to the coating film. This is because it is not desirable.

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 is made up of quantities.

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.

Other copolymerizable vinyl monomers of component (c) 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-fold section, (b) component 5 to 20-fold section, 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 the A component and the 8 components is A component 1
-40 parts by weight, and the most suitable weight is 60 to 99 parts by weight of component B.

This is because if the amount of component A is less than 1 part by weight, it will affect the long-term sustainability of the stain prevention effect, while if it exceeds 40 parts by weight, the tackiness will increase more than the stain prevention effect due to the water-repelling and oil-repelling properties of the fluorine group. This is because the stain prevention effect deteriorates.

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 articles, artificial leather, wallpaper, etc., which are based on plasticized polyvinyl chloride.

Therefore, it is preferable to form a primer layer for the purpose of preventing plasticizer bleed.

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

Example 1 Fluorinated acrylic monomer (trade name FM
-108 (manufactured by Kyoeisha Yushi Co., Ltd.), 90 parts of methyl methacrylate, 5 parts of 2-ethylhexyl acrylate, 5 parts of 2-hydroxyethyl acrylate, 3 parts of ditertiary-butyl peroxide, and 100 parts of toluene. A copolymer was prepared by stirring for hours.

Then, 312 parts of toluene was added to obtain a coating composition in which the resin solid content was adjusted to 20 parts and 1 Mm%.

Examples 2 to 6 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. Toluene was added to obtain each coating composition with a resin solids content of 20% by weight.

EXPERIMENTAL EXAMPLES Using the coating compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 2, PVC canvas (trade name: Crafter 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 immersed in a glass container containing the stain-preventing ingredients listed in Table 3, left in a dryer at 80°C for 15 minutes, and then roughly shaken for 3 minutes four times. After repeatedly taking out the coated piece and washing it with water, 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, stirred for 3 minutes, and then taken out, and the crack generation rate on the surface was visually determined.

In the table, ◎... Not at all, excellent O... Slight occurrence Δ... Occurred to a noticeable degree 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=H or CH_3, m=1-3, n=1-5,
(monomer represented by 5-20% by weight of an alkyl-containing ester (c) 0-40% by weight of other copolymerizable vinyl monomers A polymer comprising 99-60% by weight of a monomer consisting of 0-40% by weight of other copolymerizable vinyl monomers is used as a coating film-forming component. Coating composition.