JPH02242808A - Production of fluorine-containing polymer - Google Patents

Abstract

PURPOSE:To obtain the subject polymer excellent in water-and-oil repellency, durability, flexibility, dispersion stability, etc., thus useful in the form of a water-and-oil repellent treating agent for paper, ink, etc. by polymerization of monomers including a fluoroalkyl (meth)acrylate and polyfunctional (meth) acrylic ester. CONSTITUTION:The objective polymer useful in the form of a water-and-oil repellent treating agent for textiles, paper, plastic surfaces, metallic surfaces, printing inks, toners for electrophotography, coatings, etc., can be obtained by polymerization of monomers at least including (A) a fluoroalkyl (meth) acrylate and (B) a polyfunctional (meth)acrylic ester (e.g. ethylene glycol diacrylate) in the presence of an initiator.

Description

[Detailed description of the invention] [Industrial applicability! lf] The present invention relates to a method for producing a fluoropolymer useful as a water- and oil-repellent treatment agent for fibers, paper, plastic surfaces, metal surfaces, printing inks, electrophotographic toners, paints, and the like.

[Conventional technology] Conventionally, textiles, paper, plastic surfaces, metal surfaces, paints,
Fluorine-containing acrylate copolymers, fluorine-containing polyether copolymers, and water- and oil-repellent treatment agents for printing inks, etc.
Fluorine-containing urethane oligomers are used. However, although these are satisfactory in terms of water and oil repellency, they have other properties such as durability, flexibility (especially when used on textiles and paper), adhesion (also related to durability), and dispersion stability (especially when used on textiles and paper). (When used in paints and printing inks) For the purpose of improving durability and flexibility, there is a method in which organopolysiloxane is used as a softening component in combination with the fluorine-containing treatment agent, or separately in a two-stage treatment (Japanese Patent Laid-Open Publication No. 157380/1982). Proposed. However, although this method has a satisfactory level of durability, it has not yet been sufficiently effective in terms of flexibility. In addition, as an attempt to introduce a softening component into a water and oil repellent treatment agent, a method of copolymerizing a fluorine-containing (meth)acrylate and a siloxane-containing (meth)acrylate (Japanese Unexamined Patent Publication No. 130408/1983), a method using a fluorine-containing urethane A method using a reaction product of a compound and a reactive organopolysiloxane (JP-A-60-8
1278), a method using an organopolysiloxane having a perfluoroalkyl group in the side chain (Japanese Patent Publication No. 1278),
6187), etc., but processing agents with high flexibility tend to have low initial performance or durability, and processing agents with high durability tend to have poor texture.

As described above, although conventional water and oil repellent treatment agents can provide water and oil repellency, it is difficult to simultaneously satisfy durability, flexibility, adhesion, dispersion stability, etc.

[Problems to be Solved by the Invention] The purpose of the present invention is to eliminate the above-mentioned drawbacks of conventional oil and water repellent treatment agents, and to improve oil and water repellency, flexibility, durability, adhesion, dispersion stability, etc. An object of the present invention is to provide a method for producing a fluoropolymer that can simultaneously impart properties.

[Means for Solving the Problems] In order to solve the above problems, the present inventors have conducted repeated research and found that at least a fluoroalkyl (meth)acrylate and a polyfunctional (meth)acrylic ester are combined together. It was discovered that a fluorine-containing polymer obtained by polymerization is effective, leading to the present invention.

That is, the present invention provides (1) a fluorine-containing method characterized by polymerizing a monomer containing at least a fluoroalkyl (meth)acrylate and a polyfunctional (meth)acrylic ester in the presence of a polymerization initiator. Polymer manufacturing method and (2
) A fluorine-containing polymer characterized by polymerizing at least a polyfunctional (meth)acrylic acid ester and graft-polymerizing at least a fluoroalkyl (meth)acrylate to the obtained polymer in the presence of a polymerization initiator. This is the manufacturing method.

The fluorine-containing monomer used in the present invention is fluoroalkyl acrylate (fluoroalkyl moiety It-CH
2CFS, -CH,C2F5, -CHz Cx
Ft CH2C4FeCI2 Cs F -CHl C7F 18q-CH,C8F, -C
Hz C9F 19, CH2CIOF 21, etc.)
Fluoroalkyl methacrylate (fluoroalkyl moiety is -CH2CFs, -C112 (CF2 CF2
) 2 H.

-CH2CH2CIFr, -(CI2)qC
a FI7, CH2(CF2CFt)s H.

CH2 (CF2 CF2 ) < H- (CH2)2 (CF2 ) r CF3, CH2C2
0F42, etc.).

These fluorine-containing monomers are components that particularly contribute to water and oil repellency after proper mixing.

Further, the polyfunctional (meth)acrylic acid ester used in the present invention is a component that serves as a grafting active site or a crosslinking point. Examples of such polyfunctional esters include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol methacrylate, triethylene glycol triacrylate, triethylene glycol trimethacrylate, butanediol diacrylate, butanediol dimethacrylate, 1,6-Hexanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethanetetraacrylate, tetramethylol Methane tetramethacrylate, dipropylene glycol diacrylate, dipropylene glycol dimethacrylate, trimethylolhexane triacrylate, trimethylolhexane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, 1゜3-butylene glycol diacrylate, 1゜3
-Butylene glycol dimethacrylate, trimethylolethane triacrylate, trimethylolethane methacrylate, and the like.

In the present invention, the above-mentioned fluoroalkyl (meth)
The essential monomers are acrylate and polyfunctional (meth)acrylic acid ester, but other vinyl may be added as necessary to further improve durability, adhesion, dispersion stability, and film-forming properties. Monomers can also be used.

Specific examples include methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate, propyl methacrylate, propyl acrylate,
n-butyl methacrylate, 1so-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl methacrylate, 2
-Ethylhexyl methacrylate, 2-ethylhexyl acrylate, dodecyl methacrylate, dodecyl acrylate, hexyl methacrylate, hexyl acrylate, octyl acrylate, octyl methacrylate, cetyl methacrylate, cetyl acrylate, vinyl laurate, vinyl stearate, nonyl methacrylate, nonyl acrylate (meth)acrylic acid esters such as , decyl methacrylate, decyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid; glycidyl acrylate, glycidyl Monomers having a glycidyl group such as methacrylate, glycidylpropyl methacrylate, glycidylpropyl acrylate, glycidyl butyl acrylate, glycidyl butyl methacrylate; carboxylic acid vinyl esters such as vinyl acetate; toluene,
Examples include styrene monomers such as styrene and p-chlorostyrene; unsaturated carboxylic acid nitriles such as acrylonitrile and methacrylate; nitrogen-containing monomers such as dimethylaminoethyl methacrylate, vinylpyridine, and dimethylaminomethyl methacrylate.

In another embodiment of the present invention, a fluoroalkyl (meth)acrylate is grafted onto a polymer obtained by polymerizing at least a polyfunctional (meth)acrylic acid ester. A copolymer resin having a three-dimensional structure in which both components, fluoroalkyl (meth)acrylate and polyfunctional (meth)acrylic acid ester, are crosslinked to each other in a network form is obtained. Here, the polyfunctional (meth)acrylic acid ester itself has the property of being solvated with a petroleum aliphatic hydrocarbon or its halide solvent before polymerization, but not solvating with this solvent after polymerization. On the other hand, fluoroalkyl (meth)acrylate itself has the property of not being solvated with the solvent before or after polymerization. Therefore, the resulting resin is considered to be a polyfunctional (meth)acrylate ester and a fluoroalkyl (meth)acrylate bonded to the periphery thereof, which are dispersed in the solvent.

In addition, the ratio of polyfunctional (meth)acrylic acid ester to fluoroalkyl (meth)acrylate is 0.01 to
A ratio of about 1:1 (weight) is appropriate. When the other vinyl monomers are also used, preferably fluoroalkyl (meth)acrylate: polyfunctional (meth)acrylic acid ester: other vinyl monomer - (0,5-50
) : (0,1~20) two (5
0 to 90) (weight ratio).

In the present invention, silica fine particles and softening point 6 are used in the polymerization medium.
Wax or polyolefin having a temperature of about 0 to 180°C can be added. When fine silica particles are used, the resin is considered to be obtained with the fine silica particles incorporated into its network structure. In this case, the silica itself does not undergo physical changes such as dissolution during the reaction. In any case, in the case of silica, the specific gravity should be similar to that of the aliphatic hydrocarbon or its halide, which is the dispersion medium;
And by preventing gelation of the resin, dispersion stability can be further improved. On the other hand, when wax or polyolefin is used, these are dissolved in the reaction system during the polymerization reaction or after the completion of the polymerization reaction by addition and heating.
It is thought that after the reaction, the resin is precipitated into fine particles by cooling, and as a result, the resin is obtained in a state where it is absorbed by these fine particles. Here, wax or polyolefin has a specific gravity similar to that of the dispersion medium, prevents the resin from gelling, and has a molecular structure similar to that of the dispersion medium, so it not only helps improve dispersion stability, but also has a low softening point. It also helps improve adhesion. The appropriate amount of silica, wax or polyolefin to be added is about 5 to 50 parts by weight per 100 parts of resin.

Next, the polymerization solvent used in the present invention will be explained.

Petroleum aliphatic hydrocarbons or their halides used in the present invention include globin, n-hexane, n-
Pentane, n-hebutane, n-octane, i-octane, i-dodecane, i-nonane (commercially available products include Exxon's Isopar H@G-L-, naphtha Nα6, and Shell Oil's Shellsol). etc.), carbon tetrachloride, perfluoroethylene, etc.

These aliphatic hydrocarbons have a higher flash point than aromatic solvents such as benzene and toluene, and are also less toxic. Since the solubility of the resin of the present invention is poorer than that of aromatic solvents, it also has the advantage that the resin does not gel or solidify during the polymerization reaction or during storage. These petroleum aliphatic hydrocarbons or their halides are solvents with high insulation properties (electrical resistance of 103 μm or more) and low dielectric constants (dielectric constant of 8 or less). Furthermore, aromatic solvents such as benzene and toluene may be added to these aliphatic solvents as long as they are in small amounts.

The solvent used in the present invention is preferably an aliphatic hydrocarbon as described above, but water or an aromatic solvent may also be used, and it is also possible to polymerize with low molecular weight polyolefin, paraffin wax, or no solvent.

As the polymerization initiator, benzoyl peroxide, t-butyl barbenzoate, cyamyl peroxide, di-t-butyl peroxide, lauryl peroxide, azobisisobutyronitrile, etc. can be used.

The fluoropolymer obtained in the above manner has a particle size of 0,
Since it has good dispersion stability with a diameter of 1 to 5 μm and has intermolecular adhesive strength, it is particularly suitable as a material for paints, printing inks, and toners.

(Example) The present invention will be explained below by way of examples.

Example 1 100z of lauryl methacrylate, 5g of methylolpropane trimethacrylate and BPOI in a flask equipped with a stirrer, thermometer, condenser and dropping funnel. Og was added dropwise from the dropping funnel over 1 hour and polymerized at 80°C. The polymerization rate was 96%, and the contact angle of the obtained fluoropolymer was 22.1° with water and 19.5° with kerosene.

The contact angle was measured using KyowaConta manufactured by Kyowa Kagaku Co., Ltd.
Measured using ct Anglometer CA-D type. Dissolve the resin in THF (tetrahydrofuran) (
5%) was coated on an aluminum plate and dried at 100° C. for 2 hours to prepare a sample.

Lauryl methacrylate 100g C112 days CI! In the case of a comparative copolymer obtained by reacting 5 g of C00Ctl 2 CIOP 21 at 80°C for 1 hour in the presence of BPOl and Og, the contact angle was 1 with water.
0 @ and 16″ for kerosene, the product of the present invention had greater water and oil repellency.

Example 2 100g of kerosene was taken into the same flask as in Example 1, and 9
Heated to 0°C. While stirring, 90 g of 2-ethylhexyl methacrylate, 30 g of ethylene glycol dimethacrylate, and 2 g of BP were added, and a polymerization reaction was carried out for 6 hours. Next, 10 g and 5 g of BPOo were added, and graft polymerization was carried out at 80° C. for 5 hours. The polymerization rate was 92.0%, and the contact angle of the obtained fluorine-containing graft copolymer was 36e1 with water.
It was 42@ for kerosene.

Next, the fluorine-containing graft copolymer of the present invention was diluted to about 1% with toluene and impregnated into a cloth for surface treatment. This is 10
I washed it twice in the washing machine, and the contact angle with water was 30'', indicating considerable durability.It also had good flexibility.

Example 3 400g of toluene was placed in a flask similar to Example 1, and 9
After heating to 0° C. and stirring, a monomer solution consisting of 200 g of cyclohexyl acrylate, 10 g of diethylene glycol dimethacrylate, 5 g of methacrylic acid, 10 g of glycidyl methacrylate, and 3 g of BP0 was added, and the polymerization reaction was carried out at the above temperature for 4 hours. To this was added 0.1 g of vinylpyridine, and a polymerization reaction was carried out at 80° C. for 10 hours. Next, in this, CH2H2CO1li ) C00CH2(CP 2 CF2 ) i H50g,
3 g of AIBN was added and graft polymerization was carried out at the above temperature for 1 hour. As a result, the polymerization rate was 98%, and the contact angle of the obtained fluorine-containing graft copolymer was 31@ with water and 26@ with kerosene.
It was °. Note that the dispersion containing this fluorine-containing graft copolymer did not settle even if it was left at room temperature for more than 6 months.

Example 4 Polyethylene wax (AC polyethylene 1l103 manufactured by Allied Chemical Co., Ltd.) 50% was added to the flask used in Example 1.
was heated and dissolved at 90°C. To this, add 100 g of methyl methacrylate, 20 g of limethylolhexane triacrylate, 1 g of acrylic acid, 8 g of glycidyl acrylate, and 5 g of t-butylba-oside.
A polymerization reaction was carried out at 30°C for 6 hours with stirring.

The polymerization rate was 98.5%, and the contact angle of the obtained fluorine-containing graft copolymer was 38'' with water and 42'' with kerosene.

Next, when this fluorine-containing graft copolymer was hot-melt bonded to a polyethylene terephthalate film, both adhesiveness and flexibility were good.

Example 5 The same procedure was used as in Example 2 except that 100 g of water and 0.2 g of ammonium dodecylbenzenesulfonate were used instead of 100 g of kerosene. The polymerization rate is 90.3%, and the contact angle is 3 with water.
8@, it was 44″ with kerosene.

[Effects of the Invention] The fluoropolymer obtained by the present invention not only has sufficient water and oil repellency effects, but also satisfies other properties such as durability, flexibility, adhesion, and dispersion stability, so it can be used in paints. It is suitable as a water and oil repellent for printing inks, electrophotographic toners, fibers, paper, plastic surfaces, metal surfaces, etc.

Claims (2)

[Claims] (1) A method for producing a fluoropolymer, which comprises polymerizing a monomer containing at least a fluoroalkyl (meth)acrylate and a polyfunctional (meth)acrylic acid ester in the presence of a polymerization initiator. . (2) A fluorine-containing polymer characterized by polymerizing at least a polyfunctional (meth)acrylic acid ester and graft-polymerizing at least a fluoroalkyl (meth)acrylate to the resulting polymer in the presence of a polymerization initiator. Method of manufacturing coalescence.