JPS6354411A - Waxy fluorinated copolymer - Google Patents

Abstract

PURPOSE:To obtain the title copolymer excellent in miscibility with resins and waxes and solubility in solvents and useful as a surface modifier for oily substances, by reacting a fluoroalkyl group-containing polymerizable monomer with a specified alkyl group-containing polymerizable monomer. CONSTITUTION:10-80wt% fluoroalkyl group-containing polymerizable monomer such as a (meth)acrylate, vinyl ester, vinyl ether, fumarate (maleate) or alpha-olefin having a polyfluoroalkyl group or a perfluoroalkyl group (e.g., a compound of the formula) is copolymerized with 20-90wt% 16C or higher alkyl group- containing polymerizable monomer such as a (meth)acrylate, an alkylvinyl ester, an alkyl vinyl ether, an alkyl fumarate (maleate) or an alpha-olefin (e.g., stearyl methacrylate) to obtain the title copolymer of an m.p. of 25-100 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to waxy fluorine-containing copolymers. The waxy fluorine-containing copolymer of the present invention is easily miscible with resins and waxes, has good solubility in solvents, has no sticky feeling on the surface, and is suitably used for surface modification, etc. The purpose is to modify the surface to be water repellent, T8 oily, non-adhesive, highly lubricious, etc. by blending it into oil-based cosmetics, waxes for furniture, cars, etc., or blending or applying it to resins. Available for

[Conventional technology]

Water repellent and i8 oil agents for textiles are known as surface modifiers using fluorine-based copolymers;
As described in Japanese Patent No. 118882, it is a copolymer of fluoroalkyl group-containing vinyl monomers, long-chain alkyl (meth)acrylates, and other copolymerizable vinyl monomers, and is used in emulsions and halogen-based solvent solutions. Ru. Regarding the properties of the fluorine-based copolymer used in such conventional TA water and oil repellents, there is no clear description, and there is no prior art that limits the wax-like substance.

[Problem that the invention seeks to solve]

When such water and oil repellents are used for surface modification of resins and waxes, the following problems arise.

Emulsion-type products are difficult to mix and apply to oil-based substances, and solution-type products use special halogen-based solvents such as trichlorotrifluoroethane and tetrachlorodifluoroethane. In addition, the bulk properties of the copolymer are viscous, high melting point, and glassy, which impairs the physical properties and feeling of use of resins and waxes. It was not satisfactory.

Under these circumstances, a fluorine-based copolymer suitable for surface modification of resins and waxes has been desired.

[Means for solving problems]

The present inventors focused on the properties of fluorine-based copolymers as a way to solve these problems, and as a result of conducting intensive research,
It has been found that the above-mentioned problems can be solved by controlling the melting point of the fluorine-based copolymer at 25 to 100° C. to form it into a waxy state.

That is, the present invention comprises 10 to 80% by weight of a polymerizable monomer (A) having a fluoroalkyl group, and a polymerizable monomer (A) copolymerizable with (A) having an alkyl group having 16 or more carbon atoms.
B) A copolymer containing 90 to 20% by weight as a constituent unit,
A waxy fluorine-containing copolymer having a melting point range of 25°C to 100°C is provided.

The compound (B) copolymerizable with (A) has as an essential component a compound having an alkyl group having 16 or more carbon atoms, but other copolymerizable compounds can also be used in combination.

The waxy fluorine-based copolymer of the present invention is preferably a fluoroalkyl (meth)acrylate 10 to 8
It is a copolymer containing 0% by weight and 20 to 90% by weight of a linear alkyl (meth)acrylate having 16 or more carbon atoms.

As the polymerizable monomer (A) having a fluoroalkyl group used in the present invention, (meth)acrylate having a polyfluoroalkyl group and a perfluoroalkyl group,
Known compounds such as vinyl esters, vinyl ethers, malates, fumarates, and α-olefins can be mentioned. More preferred fluoroalkyl groups include polyfluoroalkyl groups and perfluoroalkyl groups having 4 or more carbon atoms.

Examples of these compounds include, for example, C) 11CHCOzCtHaCJ+3. CHt-CH
COzCtHtC*F+t.

C) Iz-(JCOzCtHaC+ oF□, CHt
-C(CHs)COtCtH*CaF+s.

CHz・C(CIC(hC1H4,CIFI), C
HI-C(CHff)CoIC,H,Cl0F□.

CHz*CHOCOCtH4C*F+y, CHtlI
CHOCtH4C1F+t.

CsF+vCtH40COCH-CHCOOCJtC*
Examples include Ftt, C*F+tCH-CHt, and the like.

Examples of the polymerizable monomer (B) having an alkyl group having 16 or more carbon atoms that can be copolymerized with (A) of the present invention include (meth)acrylic acid ester, alkyl vinyl ester, alkyl vinyl ether, alkyl maleate, and fumarate. ,α
-olefins, such as cetyl acrylate, stearyl acrylate, stearyl methacrylate, behenyl acrylate, behenyl methacrylate,
Examples include vinyl stearate, stearyl vinyl ether, distearyl maleate, distearyl fumarate, 1-octadecene, and the like. In addition, as other copolymerizable compounds, compounds whose properties, particularly melting points, do not exceed the range of 25 to 100°C of the waxy fluorine-containing copolymer of the present invention may be copolymerized in amounts that do not exceed the range. is also possible.

The waxy fluorine-containing copolymer of the present invention contains 10 to 80% by weight of a polymerizable monomer (A) having a fluoroalkyl group.
and alkyl (meth)acrylate having 16 or more carbon atoms 20
It is a copolymer containing ~90% by weight.

If the amount of the polymerizable monomer (A) having a fluoroalkyl group is less than 10% by weight, the amount of fluorine will decrease and the effect of fluorine will not be exhibited. Solubility deteriorates, which is not preferable.

As the method for producing the waxy fluorine-containing copolymer of the present invention, general polymerization methods such as bulk, solution, suspension, and precipitation polymerization can be applied, and the production method is not particularly limited. The waxy fluorine-containing copolymer of the present invention produced by the above method is isolated by common polymer isolation methods such as reprecipitation, drying, and solvent topping.

〔Example〕

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited only to these Examples.

Example I 20.0 g of CHz=C(CH3)COOCzHtCsFtt (hereinafter referred to as FMA), 30.0 g of stearyl methacrylate.

50 g of n-hexane and 2,2'-azobis(2,4-
dimethylvaleronitrile) 0.32gG 300cc4
After dissolving and purging with nitrogen under stirring, polymerization was carried out in a nitrogen atmosphere at 60 to 65°C for 5 hours and then for 0.5 hours under reflux. The polymerization proceeded homogeneously from beginning to end. . The resulting copolymer solution was precipitated using ethanol as a precipitant, and then dried under reduced pressure under heat to isolate the copolymer. The yield of the copolymer was 97%, the polymerization average molecular weight was 87,000 (in terms of polystyrene), and the melting point was 36.
A waxy fluorocopolymer having a temperature of 5° C. was obtained.

Examples 2 to 3 and Comparative Examples 1 to 2 Fluorine-containing copolymers were obtained in the same manner as in Example 1, except that stearyl methacrylate in Example 1 was replaced with the alkyl (meth)acrylate shown in Table 1. . However, only in Example 3, CHg-CtlCOOC was used instead of FMAO.
J*CsF r t was used.

From Table 1, if an alkyl (meth)acrylate with a CI# or lower is used as the alkyl group of the alkyl (meth)acrylate, only a viscous product will be obtained and will not be wax-like.On the other hand, if an alkyl group with a CI# of 00 or more is used, , a waxy fluorine-containing copolymer is obtained.

Examples 4 to 6, Comparative Example 3 FMA and bebenyl methacrylate (hereinafter referred to as BHMA) were copolymerized in the proportions shown in Table 2 according to Example 1. The results are shown in Table-2.

From Table 2, when the copolymerization ratio of alkyl (meth)acrylate is about 10%, fluorine (such as trifluorotoluene)
It only dissolves in special solvents that dissolve meth)acrylate polymers.

20% alkyl (meth)acrylate as in the present invention.
When copolymerized, it becomes soluble in solvents such as toluene and n-hexane.

Usage Example An automobile wax model was prepared by dissolving 30 parts by weight of solid paraffin and 10 parts by weight of the fluorine-containing copolymer of Example 1 (or Example 2, Comparative Example 1.2) in 60 parts by weight of n-hexane. Prepared. A film was formed by casting these n-hexane solutions on a glass plate, and the oil repellency of the film was examined by measuring the contact angle with liquid paraffin. The results are shown in Table-3.

Table 3 shows that when the waxy fluorine-containing copolymer of the present invention is blended, the surface of solid paraffin can be modified to be ia oily.
And there is no stickiness on the surface.

Table 3 [Effects of the Invention] From the results of the above Examples and Comparative Examples, it is clear that the waxy fluorine-containing copolymer obtained by the present invention has a remarkable effect of imparting In oiliness to the surface of wax, etc. It has the characteristic that it does not have any adverse effects on the surface, and has great utility as a surface modifier for oily substances.

Applicant's agent: Kaoru Furuya Procedural Negotiations (spontaneous) October 13, 1985 1. Indication of the case Japanese Patent Application No. 1987-196877 2. Title of the invention: Waxy fluorine-containing copolymer 3. Amendment. Relationship with the patent applicant (091) Kao Co., Ltd. 4, agent Nakai Building, 1-3 Nihonbashi Yokoyama-cho, Chuo-ku, Tokyo Column 6 of the detailed description of the invention in the specification, Contents of the amendment

Claims (1)

[Claims] 1. Polymerizable monomer (A) having a fluoroalkyl group 1
A waxy fluorine-containing copolymer having a melting point range of 25°C to 100°C, consisting of 0 to 80% by weight and 90 to 20% by weight of a polymerizable monomer (B) having an alkyl group having 16 or more carbon atoms. Combined. 2. The copolymer according to claim 1, wherein the polymerizable monomer having a fluoroalkyl group is a fluoroalkyl (meth)acrylate.