JP2598477B2 - Fluorine-containing AB type block copolymer - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-containing AB type block having a polymer chain having an affinity for a polymer material and a polymer chain containing fluorine. It relates to a copolymer.

More specifically, the fluorine-containing AB type block copolymer according to the present invention is a polymer in which a polymer chain having an affinity for a polymer material is fixed to the polymer material, while the fluorine-containing polymer chain is modified by a polymer. It works by orienting to the surface or interface of the material, and has the corrosion resistance, water resistance, solvent resistance, chemical resistance, non-adhesion, peelability, low friction, low abrasion, and stain resistance of fluorine atoms. A copolymer that can impart excellent properties such as water repellency, oil repellency, weather resistance, heat resistance, biocompatibility and charging properties to a polymer material, more specifically, a paint additive, a resin additive And a copolymer that can be used as a release agent, a release agent, a water repellent, a hot water repellent, a surfactant, a charge control agent, and a toner additive.

2. Description of the Related Art In order to modify the surface or interface of a polymer material and make the effect of the modification permanent, it is effective to blend a certain type of fluorine-containing block copolymer into the polymer material. Already known.

Although many attempts have been made to synthesize such fluorine-containing block copolymers, there are not many examples of synthesis using ordinary radical polymerization methods. JP-A-60-221410
Japanese Patent Application Laid-Open Publication No. H11-163873 proposes that a block copolymer containing a (per) fluoroalkylene group or a (per) fluoroalkyl group can be synthesized using a polymeric peroxide or a polyazo compound.

However, when synthesizing a fluorine-containing block copolymer using this polymeric peroxide or polyazo compound, it is difficult to obtain a high-purity block copolymer because not only the molecular weight cannot be controlled but also a homopolymer is formed as a by-product. There is a problem that is.

[Summary of the Invention]

SUMMARY An object of the present invention is to provide a solution to the above points, and various properties of a fluorine atom on the surface or interface of a polymer material to be modified, for example, water repellency, oil repellency, An object of the present invention is to provide a copolymer which gives stain resistance, electric resistance, and the like, and whose improvement effect is permanent.

That is, the fluorine-containing AB-type block copolymer according to the present invention comprises a high molecular weight compound comprising one or more compounds (M ¹ ) selected from the group of compounds represented by the following general formulas (a) to (b). Having a molecular chain and a fluorine-containing polymer chain composed of one or more compounds (M ² ) selected from the group of compounds represented by the following general formulas (c) to (f); I)
It is represented by

(Wherein, M is M ² _m M ¹ _n or M ¹ _n M ² _m
R ¹ is a hydrocarbon group having 1 to 10 carbon atoms, R ² is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ³ is a benzyl group, (R ⁴ represents an alkyl group having 1 to 18 carbon atoms) or an alkyl group having 1 to 18 carbon atoms. m and n are both 20
It is a natural number of ~ 5000. ) Compound (M ¹ ) (Meth) acrylic acid ester residue represented by the formula (wherein, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is
A hydrocarbon group having 1 to 18 carbon atoms, or a hydrocarbon group having 1 to 18 carbon atoms substituted with an alkoxy group or a hydroxyl group. ) (Wherein R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents a phenyl group or an alkylphenyl group) Compound (M ² ) Wherein R ¹⁰ is a hydrogen atom, a methyl group, a fluorine atom or a fluorine-substituted alkyl group having 1 to 16 carbon atoms, and R ¹¹ is a fluorine-substituted alkyl group having 1 to 16 carbon atoms. , Shown.) Fluorine-containing vinyl residue (wherein represented in, R ^10, respectively R ¹⁰ and R ¹¹ in the general formula (C)
And R ¹¹ have the same meaning as defined above, and R ¹² has 1 to 1 carbon atoms.
10 represents an alkylene group, and R ¹³ represents an alkyl group having 1 to 10 carbon atoms. ) Fluorine-containing vinyl residue (wherein represented in, R ^10, respectively R ¹⁰ and R ¹¹ in the general formula (C)
And the meanings defined as for R ^11, R ¹² and R ¹³ the meaning defined as in R ¹² and R ¹³ in the general formula (d) respectively indicate. ) (Wherein R ¹⁰ has the same meaning as defined for R ¹⁰ in formula (C), and R ¹⁴ represents an alkylene group having 1 to 10 carbon atoms or 1 to 10 carbon atoms.) R ¹⁵ is a carbon atom having 1 carbon atom
An alkyl group having 1 to 10 carbon atoms or a fluorine-substituted alkyl group having 1 to 10 carbon atoms. However, at least one of R ¹⁰ , R ¹⁴ , and R ¹⁵ contains fluorine. According to the present invention, the above-mentioned conventional problems are overcome,
Blocks of polymer chains that have an affinity for the polymer material whose surface properties are to be modified sufficiently `` fix '' the fluorine-containing polymer chains to the polymer chains of the target polymer material,
Various properties inherent to the fluorine-containing polymer chain are imparted to the polymer material to modify its surface properties.

That is, the corrosion resistance of fluorine atoms, water resistance, solvent resistance, chemical resistance, non-adhesion, peelability, low friction, low abrasion, stain resistance, water repellency, oil repellency, weather resistance, heat resistance, Excellent properties such as biocompatibility and charging characteristics can be imparted to the polymer material, and this effect can be maintained for a long time.

Therefore, paint additives, resin additives, release agents, release agents,
It can be used as a water repellent, oil repellent, surfactant, charge control agent and toner additive.

In the block copolymer according to the present invention, it is desirable to select an appropriate polymerization initiator as a problem peculiar to the polymerization of the fluorine-containing polymer, but a preferable polymerization initiator is a simple compound as described below. In addition to being a well-known compound, a block copolymer is also easy and is within the range of conventional techniques. Provides an extremely practical technology.

[Specific description of the invention]

Fluorine-containing AB-type block copolymer The fluorine-containing AB-type block copolymer according to the present invention comprises a polymer chain having an affinity for a polymer material to be modified (hereinafter, also referred to as an affinity polymer chain) and fluorine. There is a structure having a structure in which a polymer chain is chemically engaged with a contained polymer chain, and is represented by the above-mentioned general formula (I). In addition,
In the present specification, the “residue” in the general formulas (a) to (f) indicates a repeating unit itself when a monomer having a vinyl group is bonded by addition polymerization.

Each of m and n in the general formula (I) is a natural number of 20 to 5,000. Specific numbers of m and n can be appropriately determined depending on the types of the polymer chains (M ¹ ) and (M ² ), the weight average molecular weight of the target polymer material or the block copolymer described below, and the like. But preferably m is 30
-500, n is 30-500, and m + n is 60-1,000.

When such a AB type block copolymer is blended with a polymer material to be modified using a method such as melt-kneading to synthesize a composition, the fluorine-containing polymer chain portion of the copolymer becomes a composition. The polymer is oriented on the surface or interface of the polymer material so as to take the form (morphology) that minimizes the free energy of the entire system, while the affinity polymer chain portion is buried in the polymer material to convert the copolymer into a polymer. It is presumed to play a role in fixing the copolymer to the material. Therefore, such a
The AB type block copolymer modifies the surface or interface of the polymer material and easily bleeds out.
The mold block copolymer itself is not easily separated from the resin.

Therefore, the fluorine-containing AB-type block copolymer of the present invention can impart various properties possessed by fluorine atoms to the surface or interface of the polymer material and can impart permanence to the properties.

(1) Polymer chain having affinity for polymer material The polymer chain having affinity for polymer material is one or two selected from the group of compounds represented by the following general formulas (a) to (b). It comprises at least one compound (M ¹ ) and forms the block (A) of the AB-type block copolymer according to the present invention. When the polymer chain is composed of two or more compounds, strictly speaking, the block (A) may not be said to be a block portion in which the same monomer is bound to the other, but the affinity for the polymer material is increased. Compound (M ¹ )
In that it is treated as a single block.

(Meth) acrylic acid ester residue represented by the formula (wherein, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is
And represents a hydrocarbon group of 1 to 18, preferably 1 to 8, or a hydrocarbon group of 1 to 18, preferably 1 to 8 carbon atoms substituted with an alkoxy group or a hydroxyl group. The monomers forming the (meth) acrylate residue (a) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. Hexyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic acid Hydroxyethyl, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, pentaethylene glycol monomethyl ether (meth) acrylate, diethylene glycol (meth) acrylate Monoethyl ether, diethylene glycol (meth) acrylate (Meth) acrylic acid esters such as rumonobutyl ether; here,
It goes without saying that the expression “(meth) acrylic acid” includes both “acrylic acid” and “methacrylic acid”.

(In the formula, R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents a phenyl group or an alkylphenyl group.) A monomer that forms an aromatic vinyl residue (b) as,
Styrene, paramethylstyrene, orthomethylstyrene, α-methylstyrene, β-methylstyrene and the like can be mentioned.

(2) Fluorine-containing polymer chain The fluorinated polymer chain is composed of one or more compounds (M ² ) selected from the group of compounds represented by the following general formulas (c) to (f). is there. When this polymer chain is composed of two or more kinds of compounds (M ² ), it may not be strictly said that the same monomer is a block portion in which the other monomer is bound to the other, but a specific compound group containing a fluorine atom (C) to (f), which are treated as a single block in that they have the same effect.

In the formula, R ¹⁰ represents a hydrogen atom, a methyl group, a fluorine atom or a fluorine-substituted alkyl group having 1 to 16, preferably 1 to 8 carbon atoms, and R ¹¹ represents 1 to 1 carbon atoms. A fluorine-containing alkyl group of 16, preferably 1 to 10 is shown.) Examples of the monomer forming a fluorine-containing vinyl residue of the general formula (C) include CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCH _{= CH 2, CF 3 (CF} 2) 4 CH 2 CH 2 OCOC (CH 3) = CH 2, CF 3 CH 2 OCOCH = CH 2, H (CF ₂ ) ₈ CH ₂ OCOCH = CH ₂ , H (CF ₂ ) ₄ CH ₂ OCOCH = CH ₂ , H (CF ₂ ) ₆ CH ₂ OCOC (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₃ CFHCF ₂ CH ₂ OCOCH = CH ₂ , And the like.

Fluorine-containing vinyl residue (wherein represented in, R ^10, respectively R ¹⁰ and R ¹¹ in the general formula (C)
And R ¹¹ have the same meaning as defined above, and R ¹² has 1 to 1 carbon atoms.
R 10 represents an alkyl group having 1 to 5, preferably 1 to 5, and R ¹³ represents an alkyl group having 1 to 10, preferably 1 to 5 carbon atoms. Here, "R ¹⁰ and R ¹¹ are each represented by the general formula (C)
It indicates the meaning defined as in R ¹⁰ and R ^11. "
When the compound of (d) and the compound of (c) is co-used, than that in show that the R ¹⁰ of (D) and R ¹⁰ of (c) is required to be always the same is In other words, it shows that the definition of R ^{10 in} the general formula (d) is the same as the content defined in R ¹⁰ of the general formula (c).

As the monomer forming the fluorine-containing vinyl residue of the general formula (d), CF ₃ (CH ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , CF ₃ ( CH ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOCH = CH ₂ ), C ₈ F ₁₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₁₀ OCOCH = CH ₂ , C ₂ F ₅ SO ₂ N (C ₂ H ₅ ) CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , C ₈ F ₁₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₄ OCOCH = CH ₂ , C ₂ F ₃ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , C ₂ F ₅ SO ₂ N (C ₂ H ₅ ) C (C ₂ H ₅ ) HCH ₂ OCOCH = CH ₂ , And the like.

Fluorine-containing vinyl residue (wherein represented in, R ^10, respectively R ¹⁰ and R ¹¹ in the general formula (C)
And the meaning defined as in R ^11, the meaning defined as in R ¹² and R ^13, respectively R ¹² and R ¹³ in the general formula (d) shows. Here, "having the same defined meaning" means that the contents to be defined are the same. As the monomer forming the fluorine-containing vinyl residue of the general formula (e), C ₇ F ₁₅ CON (C ₂ H ₅ ) CH ₂ OCOC (CH ₃ ) = CH ₂ , C ₂ F ₅ CON (C _{2 H 5) CH 2 OCOCH = CH} 2, CF 3 (CF 2) 2 CON (CH 3) CH (CH 3) CH 2 OCOCH = CH 2, CH 3 (CF 2) 7 CON (CH 2 CH 2 CH 3) CH ₂ OCOC (CH ₃ ) = CH ₂ , And the like.

A fluorine-containing vinyl residue represented by the formula: wherein R ¹⁰ has the same meaning as defined for R ¹⁰ in formula (C), and R ¹⁴ represents an alkylene having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. A group or a fluorine-substituted alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and R ¹⁵ is an alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms or 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. 5 represents a fluorine-substituted alkyl group, provided that at least one of R ¹⁰ , R ¹⁴ and R ¹⁵ contains fluorine.) The fluorine-containing vinyl residue of the general formula (f) The monomers to be formed include CF ₃ CH ₂ OCH ₂ CH ₂ OCOCH = CH ₂ , HCF ₂ CF ₂ OCH ₂ CH ₂ OCOCH = CH ₂ , C ₂ F ₅ CH ₂ CH ₂ OCH ₂ OCOCH = CH ₂ , C ₈ F ₁₇ OCH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₄ OCH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , And the like.

Specific examples of the fluorinated vinyl compound forming the fluorinated polymer are as described above, and one or more of these are used as main components of the fluorinated vinyl compound.
A fluorine-containing vinyl compound or vinyl compound other than the above-mentioned main component can be added within a range in which the modifying effect of the block copolymer on the surface of the polymer material can be exerted.

(3) Production of block copolymer The block copolymer is formed by block copolymerization as described above.

That is, a monomer (M ¹ ) that should form an affinity polymer chain
One of the monomers (M ² ) which should form a fluorine-containing polymer chain is polymerized by the action of a radical polymerization initiator to correspond to an affinity polymer chain or a fluorine-containing polymer chain and to have a free radical or a precursor at its terminal It is common to form a polymer chain having a free radical source consisting of (first step) and then polymerize the other monomer with this free radical source to form a block copolymer (second step).

In this case, the radical polymerization initiator preferably has both functions of chain transfer and termination. One specific example of such a radical polymerization initiator is one that provides a dithiocarbamate group at the end of the resulting polymer chain. The dithiacarbamate group formed at the polymer chain end of one block is decomposed by giving light energy to generate free radicals, and starts generating another block therefrom.

As described above, an initiator preferably used for synthesizing a block copolymer in the present invention is a so-called initiator which has both functions of chain transfer and termination in a radical polymerization process (Otsu, Polymers 33, 3). , 222
(1984)) Specifically, sulfur compounds are represented by the following general formula (g). A block copolymer can be synthesized using one or more of these.

General formula (Wherein, R ¹ represents a hydrocarbon group having 1 to 10, preferably 2 to 5 carbon atoms; R ² represents a hydrogen atom or a hydrocarbon group having 1 to 10, preferably 2 to 5 carbon atoms; ³ is a benzyl group, (In the formula, R ⁴ represents an alkyl group having 1 to 18, preferably 2 to 10 carbon atoms.) Or 1 to 18, preferably 2 to 2 carbon atoms.
And 10 alkyl groups. Unless the electronic state of these initiators is significantly changed or the steric hindrance is remarkably increased to reduce the radical initiating ability, the hydrogen atom of R ³ is replaced with a halogen, a hydroxyl group, an alkoxy group or a carboxylic acid. It may be substituted with a group or the like.

These compounds are generally used as reagents for rubber, or can be synthesized from the corresponding halide and dithiocarbamate in good yield.
For example, N, N-diethylbenzyldithiocarbamate can be synthesized from benzyl bromide and sodium N, N-diethyldithiocarbamate.

These compounds can use ultraviolet rays having a wavelength of 300 to 500 nm in order to decompose themselves and function as an initiator, that is, to start the first step and the second step of block copolymerization. .

(4) Copolymer As described above, such a block copolymer can be synthesized by the following two steps.

(First Step) The first vinyl monomer is polymerized using the above-mentioned sulfur-based radical polymerization initiator to synthesize a polymer initiator having a dithiocarbamate group at a polymer terminal.

(Second step) The second vinyl monomer is polymerized using the polymer initiator synthesized in the first step to obtain a block copolymer. Here, the dithiocarbamate at the polymer terminal is decomposed and becomes a radical initiation site (details will be described later).

In these two steps, a fluorinated monomer can be used as the first monomer and an affinity vinyl monomer can be used as the second monomer. Conversely, an affinity vinyl monomer can be used as the first monomer, and a fluorine-containing monomer can be used as the second monomer.

When performing photopolymerization through the first and second steps,
The temperature is preferably 150 ° C. or lower from the viewpoint of protecting the polymerized dithiocarbamate group.

When photopolymerization is employed in these two steps, the polymerization may be either homogeneous or heterogeneous, provided that sufficient light energy is transmitted to the initiation site for dissociation. However, in general, bulk polymerization or solution polymerization is used in the first step, and solution polymerization or solution polymerization in which a polymer initiator is dissolved with a second monomer is used in the second step.

The molecular weight of each component of the block copolymer can be controlled by the molar ratio between the initiator and the monomer. For example, when 1 mol% of benzyl N, N-diethyldithiocarbamate is added to methyl methacrylate having a monomer molecular weight of 100, the number average molecular weight is about 10,000, which corresponds to m = 100. Similarly, the case of 0.1 mol% addition corresponds to about 100,000 and m = 1,000.

Similarly, in the second step, the molecular weight can be controlled by the molar ratio between the polymer initiator and the second monomer.

Suitable block copolymers have a weight average molecular weight of 5,000 to 1
It is about 00,000 (m + n = about 50 to 1,000), and contains 5 to 75% by weight of a fluorine-containing polymer chain. If the weight average molecular weight of the block copolymer is less than 5,000, the bleed-out from the polymer material tends to be insufficient and the life of the effect is not sufficient.On the other hand, if the weight average molecular weight exceeds 100,000, the diffusion rate of the surface of the block copolymer is low, so the blend is not necessarily used. It does not migrate to the surface, and the water / oil repellency is not sufficient.

If the content of the fluorine-containing polymer chain in this block copolymer is less than 5% by weight, the water- and oil-repellent chain cannot sufficiently cover the entire surface of the blend, so that the water- and oil-repellent effect is sufficient. On the other hand, when the content of the water- and oil-repellent chains exceeds 75% by weight, the content of the affinity chains becomes relatively small.
Insufficient affinity for polymer materials causes poor dispersion.

Use of the block copolymer of the present invention Target polymer material The target polymer material whose surface properties are to be modified by kneading the block copolymer according to the present invention,
It can be of any polymer, except that it is thermoplastic because it can be kneaded.

One group of such polymeric materials is formed by homopolymerization or copolymerization of ethylenically unsaturated monomers, and another group of such polymeric materials is a polycondensation or polyaddition reaction. It is formed by.

Another group of the polymer materials that are the subject of the present invention consists of natural polymers.

The present invention is intended to improve the inherent surface characteristics of such a polymer material, and the resulting blend is obtained by kneading a surface modifier polymer with the target polymer material. Utilizes the phenomenon of having properties different from the material-specific surface properties (for example, improved oil and water repellency), but such blends are made of amorphous polymeric materials Needless to say, it can be a fiber, a film or sheet, a pipe, a plate, a block, or other molded products.

That is, the fluorine-containing AB-type copolymer according to the present invention can be used for resins such as synthetic polymers and natural polymers, fibers, foams, rubber and other materials, and more specifically for plastics. Paints, fibers, films, fabrics, sealants, and other materials that use molecules can all be covered.
More specifically, the present invention is a polyacrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, ABS resin, styrene-butadiene resin, AS resin,
Polyethylene resin, polypropylene resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polyamide resin, polyester resin, epoxy resin, polyphenylene oxide resin, polycarbonate resin, noryl resin, polyurethane resin, nitrocellulose resin, cellulose acetate resin, ethyl cellulose resin, cellulose Acetate butyrate resin, cellulose acetate propionate resin, ethylene-vinyl acetate resin, urea resin,
Melamine resin, polyvinyl ether resin, petroleum resin, chroman resin, indene resin, phenol resin, acetal resin, acrylonitrile-butadiene rubber, chloroprene rubber, acrylic rubber, butyl rubber, polybutadiene rubber, polyisoprene rubber, ethylene-propylene-gen rubber, poly Acrylic fiber, nylon fiber, polyester fiber, polyvinyl alcohol fiber, polyvinyl chloride fiber, polyvinylidene chloride fiber, polyethylene fiber, polypropylene fiber, polyurethane fiber, polyvinyl acetal fiber, expanded polystyrene, expanded polypropylene,
Synthetic polymer materials such as foamed polyurethane and natural polymer materials such as rosin, natural rubber, cotton, hemp, wool, and silk can be used.

Surface property modification The surface property modification of polymer materials
It can be carried out by blending the AB type copolymer with the above-mentioned polymer material. For example, a method of dissolving or dispersing the block copolymer according to the present invention in a solvent and applying it to the surface of a polymer material, mixing the polymer material during molding, or mixing the polymer material and the block copolymer with a solvent Dissolving into a film by dissolving the block copolymer into a sheet, bonding the block copolymer to the surface of the polymer material under heating or bonding with an adhesive, or heating the block copolymer to a polymer A method of welding on the surface of the material can be used. Among these, an embodiment in which the block copolymer and the target polymer material are united through a state of being dissolved or melted is preferable.

In this case, the blending amount of the block copolymer is
The range is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight. If the amount is less than 0.01 part by weight, the effect of the present invention will be reduced, and if it exceeds 30 parts by weight, the inherent properties of the polymer material may be impaired. Further, the block copolymer in the present invention can be used alone by being blended with a polymer material to be modified, or can be blended with a known fluorine-containing surfactant. The amount of these fluorinated surfactants used is 0 to 50 relative to the block copolymer in the present invention.
% By weight. If it exceeds 50% by weight, the effect of the present invention is impaired.

The polymer material after the surface modification is preferably in the form of a molded product.

[Examples] The present invention will be specifically described by the following examples, but the present invention is not limited to these experimental examples.

In addition, the number of parts and% in each Example are all based on weight.

Reference Example 1 (A) Synthesis of Polymer Initiator Apparatus: H400PL made by Toshiba Denshi with 400W output in a 50 ° C constant temperature bath
A container of Pyrex glass with a diameter of 3 cm and a volume of 200 ml at a distance of 10 cm from the ultraviolet lamp.

Monomer: Methyl methacrylate 50 parts Ethyl acrylate 50 parts Benzyl N, N-diethyldithiocarbamate 2.39 parts Polymerization operation: The above monomer was charged into the above-mentioned container, and the inside of the container was replaced with nitrogen. The photopolymerization reaction was performed by irradiating ultraviolet rays for a period of time. The obtained acrylic polymer initiator was pale yellow and transparent and fixed, and the remaining monomer was 1.6% in total for both monomers. The number average molecular weight in terms of polystyrene by GPC (hereinafter simply referred to as _MN ) is 9,800,
The polystyrene-reduced weight average molecular weight (hereinafter simply referred to as M _W)
Was 22,000.

(B) Synthesis of block copolymer After thoroughly mixing and dissolving, the mixture is charged into the same apparatus as in the above (A), the inside of the container is replaced with nitrogen, and then irradiated with ultraviolet rays for about 10 hours to carry out a photopolymerization reaction, thereby obtaining a translucent substance. After obtaining a white polymer dispersion, the composition was reprecipitated with methanol, dried, and subjected to repeated extraction procedures using acetone or the like to obtain 66 parts of a block copolymer. M _N is 21000, M _W of the resulting block copolymer was 45000, the synthesis of the monomer remaining was less than 1%. m = 98, n = 22.

Reference Example 2 A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 50 parts of methyl methacrylate, 50 parts of ethyl acrylate, 2 parts of benzoyl peroxide, and 200 parts of methyl ethyl ketone. After heating for 6 hours to complete the reaction, M _N = 52000, M _W = 130,000
To obtain a colorless and transparent acrylic coating solution. The resin content in the solution was 33%.

Examples 1 to 3 The block copolymer synthesized in Reference Example 1 was added to the acrylic coating solution synthesized in Reference Example 2, and the resulting coating film was measured for water and oil repellency. The water and oil repellency was measured after forming a film on a wash primer-treated iron plate so that the film thickness after drying was 20 μm and air-drying for 24 hours. In addition, as a durability test, the test piece was immersed in distilled water at 25 ° C. for one week, and the water / oil repellency was also measured.

 The composition and results are shown in Table 1.

Comparative Example 1 A film was formed and measured under the same conditions as in Examples 1 to 3, except that the block polymer synthesized in Reference Example 1 was not added.

 The results are shown in Table 1.

From Table 1, it can be seen that the addition of the block copolymer of the present invention imparts water and oil repellency to the surface of the coating film as compared with the case where the block copolymer is not added, and the surface thereof is modified. It is clear that they also have

Reference Example 3 (A) Synthesis of Polymer Initiator 100 parts of styrene and 2.39 parts of benzyl N, N-diethyldithiocarbamate were charged into the same apparatus as in Reference Example 1 (A), the inside of the vessel was replaced with nitrogen, and the vessel was sealed. Photopolymerization was performed by irradiation with ultraviolet rays for 15 hours. The obtained styrene polymer initiator was a pale yellow transparent solid, and the remaining styrene monomer was 1.5%. The produced polymer _MN is 110
00, M _W was 25,000.

(B) Synthesis of Block Copolymer A block copolymer was synthesized under the same conditions as in Reference Example 1 (B) except that the acrylic polymer initiator of Reference Example 1 (B) was changed to a styrene polymer initiator. M _N of the formed block copolymer is 21
000, M _W is 46000, the synthesis of the monomer remaining was less than 1%. m = 105, n = 20.

Examples 4 to 6 The polystyrene resin powder, the block copolymer obtained in Reference Example 3 and the ratio shown in Table 2 were kneaded with an extruder to form a sheet, and further pressed to form a sheet having a thickness of 2 mm. And This sheet had no coloring, no bleeding on the surface, and good workability.

A part of this sheet was further sandwiched between Teflon films and pressed at 150 ° C. for 2 hours to form a 1 mm sheet.

The water repellency and oil repellency of these two sheets were measured in the same manner as in Examples 1 to 3. In addition, as a durability test, the test piece was immersed in distilled water at 25 ° C. for one week, and the water / oil repellency was also measured.

Comparative Example 2 A sheet was prepared in the same manner as in Example 4 except that only the polystyrene resin powder was used without using the block copolymer.

The water / oil repellency of this sheet was measured in the same manner as in Example 4. The results are shown in Table 2.

From Table 2, when the block copolymer of the present invention is added to polystyrene resin, the sheet surface is imparted with water / oil repellency and the surface thereof is modified as compared with the case where the block copolymer is not added, and It is clear that it also has persistence.

Claims (1)

(57) [Claims] 1. A polymer chain comprising ^one or more compounds (M ¹ ) selected from the group of compounds represented by the following general formulas (a) to (b): A fluorine-containing AB type block represented by the following general formula (I) having a fluorine-containing polymer chain comprising one or more compounds (M ² ) selected from the group of compounds represented by (f): Polymer. (Wherein, M is M ² _m M ¹ _n or M ¹ _n M ² _m
R ¹ is a hydrocarbon group having 1 to 10 carbon atoms, R ² is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ³ is a benzyl group, (R ⁴ represents an alkyl group having 1 to 18 carbon atoms) or an alkyl group having 1 to 18 carbon atoms. m and n are both 20
It is a natural number of ~ 5000. ) Compound (M ¹ ) (Meth) acrylic acid ester residue represented by the formula (wherein,
R ⁵ is a hydrogen atom or a methyl group, R ⁶ represents a hydrocarbon group having 1 to 18 carbon atoms which is substituted with a hydrocarbon group having 1 to 18 carbon atoms or an alkoxy group or a hydroxyl group,. ) (Wherein R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents a phenyl group or an alkylphenyl group) Compound (M ² ) Wherein R ¹⁰ is a hydrogen atom, a methyl group, a fluorine atom or a fluorine-substituted alkyl group having 1 to 16 carbon atoms, and R ¹¹ is a fluorine-substituted alkyl group having 1 to 16 carbon atoms. , Shown.) Fluorine-containing vinyl residue (wherein represented in, R ^10, respectively R ¹⁰ and R ¹¹ in the general formula (C)
And R ¹¹ have the same meaning as defined above, and R ¹² has 1 to 1 carbon atoms.
10 represents an alkylene group, and R ¹³ represents an alkyl group having 1 to 10 carbon atoms. ) Fluorine-containing vinyl residue (wherein represented in, R ^10, respectively R ¹⁰ and R ¹¹ in the general formula (C)
And the meanings defined as for R ^11, R ¹² and R ¹³ the meaning defined as in R ¹² and R ¹³ in the general formula (d) respectively indicate. ) (Wherein R ¹⁰ has the same meaning as defined for R ¹⁰ in formula (C), and R ¹⁴ represents an alkylene group having 1 to 10 carbon atoms or 1 to 10 carbon atoms.) R ¹⁵ is a carbon atom having 1 carbon atom
An alkyl group having 1 to 10 carbon atoms or a fluorine-substituted alkyl group having 1 to 10 carbon atoms. However, at least one of R ¹⁰ , R ¹⁴ , and R ¹⁵ contains fluorine. )