JPH0451572B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION The present invention relates to coating compositions, in particular coating compositions 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 silicon-based monomer as a coating composition. Conventionally, as an example of application of this type of coating composition, it has been known to impart a water-repelling oil function to fiber yarn. 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 by the above-mentioned properties could not be obtained. The reason for this is not clear, but when the base material is different,
In some respects, it is difficult to believe that they would exhibit the same effects, 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 problem) To outline the present invention, A general formula (In the formula, R represents H or _CH3 , and X represents H or F.
shows. Moreover, m is an integer of 1-3, and n is an integer of 1-5. ) Monomer 1~
40% by weight B(a) Acrylic acid or methacrylic acid alkyl ester 40 to 95 parts by weight (b) Hydroxyalkyl-containing ester of α,β-ethylenically unsaturated carboxylic acid 5 to 20 parts by weight (c) Other copolymerizable materials vinyl monomer
The present invention relates to a coating composition whose film-forming component is a polymer containing 99 to 60% by weight of monomers consisting of 0 to 40 parts by weight. According to the research conducted by the present inventors, the coating film formed by covering the fluorine-based copolymer or silicone-based copolymer of the conventionally known antifouling materials is not polymerized by crosslinking. It was found that the stain prevention function does not last for this reason. The present invention was completed based on this knowledge,
When producing a polymer whose constituent monomers are a fluorine group-containing monomer and an α,β-ethylenically unsaturated monomer composition, a crosslinkable monomer containing an OH group in the molecule is used. By polymerizing it as an essential monomer component, they succeeded in maintaining its 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. (In the formula, R represents H or _CH3 , X represents H or F, m is an integer of 1 to 3, and n is 1 to
It is an integer of 5. ) In this case, the reason why the number of methylene groups in the molecule is limited to 1 to 3 is because if the number of methylene groups is 4 or more, the glass transition temperature will be low, resulting in stickiness and reducing the stain prevention effect, which is undesirable. be. Also, limiting the number of CF ₂ groups to 1 to 5 is because CF ₂
This is because when the number of groups is 6 or more, the water repellency and oil repellency due to the fluorine groups increase, making it difficult for printing ink etc. to adhere to the coating film, which is not preferable. 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, butyl acrylate, butyl methacrylate, lauryl acrylate. , lauryl methacrylate, stearyl acrylate, stearyl methacrylate, hexyl acrylate, 2-ethylhexyl methacrylate, heptyl acrylate, heptyl methacrylate, etc., which have about 20 carbon atoms in the alkyl group.
Similar esters with up to can be used. (B) As the hydroxyalkyl-containing ester of α,β-ethylenically unsaturated carboxylic acid, 2
-Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4
-Hydroxybutyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, etc. can be used. Other copolymerizable vinyl monomers of component (iii) include styrene, α-alkylstyrene, α-chlorostyrene, vinyltoluene, acrylonitrile, vinyl acetate, and the like. The usage ratio of the monomer composition of component B is as follows:
The range is 40 to 95 parts by weight, 5 to 20 parts by weight of component (b), and 0 to 40 parts by weight of component (c). In the present invention, the blending amount of component (B) in particular affects the long-term sustainability of the stain prevention effect, and if component (B) is less than 5 parts by weight, sustainability cannot be obtained;
If it exceeds 20 parts by weight, it is undesirable because it causes the coating film to become sticky. In the present invention, the composition of component A and component B is
It is necessary to set the proportions to be 1 to 40% by weight of component and 60 to 99% by weight of component B. This means that if the A component is less than 1% by weight, it will affect the long-term sustainability of the stain prevention effect, whereas if the A component is less than 1% by weight, the
This is because, if it exceeds this value, the tackiness increases and the stain-preventing effect becomes worse than the stain-preventing effect due to the water-repellent and oil-repellent properties of the fluorine group. The polymerization reaction in the present invention is carried out by mixing and stirring component A and component B, then adding the mixture in several portions into a flask, and stirring at reflux temperature for 8 to 12 hours. Examples of organic solvents used in the present invention include alcohols such as methanol, ethanol, and propanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone;
Ester systems such as ethyl acetate and butyl acetate, and hydrocarbon systems such as benzene, toluene and 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. 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 primer layer for the purpose of preventing bleeding of the plasticizer. Examples are shown below to more specifically explain the present invention. In the examples, all parts are parts by weight. Example 1 Into a three-four neck flask equipped with a stirrer, a thermometer, and a reflux condenser, 5 parts of a fluorine-based acrylic monomer (trade name FM-108, manufactured by Kyoeisha Yushi Co., Ltd.),
85 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 were charged under reflux.
Stirring was performed for 8 hours to prepare a copolymer. Then,
A coating composition was obtained in which the resin solid content was adjusted to 20% by weight by adding 312 parts of toluene. 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.

【table】
｜ ‖
Fluorine monomer *2 CH ₂
=C−C−O−CH ₂ −(CF ₂ ) ₄ −H
Experimental Example Using the coating compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 2, the coating compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 2 were applied to a PVC canvas (trade name: Crafter K355, manufactured by Kuraray Co., Ltd.) using a gravure printer (95 mesh), and heated at 80°C. After drying for 1 minute, a coated piece was prepared. The performance of each coated piece was tested and the results are shown in Table 2.

[Table] 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 components shown in Table 3, left in a dryer at 80°C for 15 minutes, and then shaken for an additional 3 minutes. Repeat this process 4 times. After removing the piece and washing it with water, the percentage of dirt on its surface was visually determined. In addition, in the bending resistance test, the coated piece was attached to a bending tester and flexed 10,000 times, then the coated piece was placed in the dirt component mentioned above, shaken for 3 minutes, taken out, and the surface The crack occurrence rate was determined visually. Furthermore, the weather resistance test was conducted using a sunshine weather meter, and then the crack occurrence rate on the surface of the coated piece was visually determined. In the table, ◎...Not at all, excellent ○...Slight occurrence △...Conspicuous occurrence ×...Full surface occurrence

【table】

[Table] Examples 7 to 11 and Comparative Examples 3 to 4 Reactions were carried out in the same manner as in Example 1, except that the monomer composition was changed to that shown in Table 4, and copolymers were obtained. Coating compositions having a resin solid content of 20% by weight were obtained by adding toluene. Using the coating compositions obtained in Examples 7 to 11 and Comparative Examples 3 to 4, the performance of each coated piece was tested according to the above experimental example, and the results are shown in Table 5.

[Table] However, fluorine monomer *1 and fluorine monomer *2 are
Same as those listed in Table 1.

[Table] (Effects of the Invention) As is clear from the above explanation, the coating composition of the present invention has excellent stain prevention properties, maintains this effect for a long period of time, and does not crack even when bent. It has the effect of being difficult to use.

Claims (1)

[Claims] 1 A General formula (In the formula, R represents H or _CH3 , and X represents H or F.
shows. Moreover, m is an integer of 1-3, and n is an integer of 1-5. ) 1 to 40% by weight of the monomer represented by B(a) Acrylic acid or methacrylic acid alkyl ester 40 to 95 parts by weight (b) Hydroxyalkyl-containing ester of α,β-ethylenically unsaturated carboxylic acid 5 to 20 Part by weight (c) Other copolymerizable vinyl monomers
A coating composition comprising, as a film-forming component, a polymer containing 99-60% by weight of monomers consisting of 0-40 parts by weight as a constituent monomer.