JPH02269111A - Manufacturing method of fluorine-containing copolymer - Google Patents

Abstract

PURPOSE:To obtain the title copolymer useful as a water-repellent or oil- repellent treating agent, having excellent durability, flexibility, adhesiveness and dispersion stability by polymerizing a mixture of an unsaturated carboxylic acid ester-based monomer, divinylbenzene, etc., adding a fluorine-containing monomer to the polymer and polymerizing the monomer. CONSTITUTION:A monomer mixture of (A) an unsaturated carboxylic acid ester-based monomer (e.g. lauryl methacrylate) and (B) divinylbenzene or an alkyl ester derivative thereof (e.g. o-butyldivinylbenzene; is polymerized with a radical polymerization initiator at 80 deg.C for 4 hours, the formed polymerization system is mixed with (C) a monomer containing a fluorine-containing monomer (e.g. fluoroalkyl methacrylate) and a radical polymerization initiator and polymerization reaction is carried out under heating at 80 deg.C to give the aimed fluorine- containing copolymer.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a fluorine-containing compound useful as a water- and oil-repellent treatment agent for textiles, paper, plastic surfaces, metal surfaces, printing inks, electrophotographic toners, paints, etc. Relating to polymers.

[Prior art]

Traditionally, textiles, paper, plastic surfaces, metal surfaces, paints,
Fluorine-containing acrylate copolymers, fluorine-containing polyether copolymers, fluorine-containing urethane oligomers, and the like are used as water- and oil-repellent treatment agents for printing inks and the like. However, although these are satisfactory in terms of water and oil repellency, other performance
e.g. durability, flexibility (especially when used on textiles and paper)
, adhesion (related to durability), dispersion stability (particularly when used in paints and printing inks), etc.

For the purpose of improving durability and flexibility, organopolysiloxane is used as a softening component in combination with the above-mentioned fluorine-containing treatment agent, or separately in a two-stage treatment (Japanese Patent Laid-Open No. 59-15
73110) has been 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 compound, A method using a reaction product with a reactive organopolysiloxane (Japanese Patent Application Laid-open No. 81278/1983)
, a method using an organopolysiloxane having a perfluoroalkyl group in the side chain (Japanese Patent Publication No. 61-6187) is known, but highly flexible treatment agents have low initial performance or durability, and Higher processing agents tend to result in poor texture.

In addition, a composition for coating an organosol of fluorine-containing copolymer particles composed of two layers, a core part and a shell part (Japanese Patent Publication No. 63-63
No. 584), a water and oil repellent in which a fluorine-containing supernatant is grafted onto an acrylic-diene backbone polymer (Japanese Patent Publication No. 1983-
67511), a crosslinked composition comprising a fluorine-containing thermoplastic copolymer and a fluoroelastomer (Japanese Patent Publication No. 63-50
3148), a molded article made of a composition containing a fluorine-containing resin mixed with a polyfunctional monomer and irradiated with radiation (JP-A-63-305151), a fluorine-containing terpolymer and its m.

P and a second polymer having a higher thermal decomposition point (Japanese Unexamined Patent Publication No. 63-312337) have been proposed.

However, although these conventional water and oil repellent treatment agents can provide water and oil repellency, it is difficult to simultaneously satisfy durability, flexibility, adhesiveness, dispersion stability, etc.

[Problem 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 develop a fluorine-containing copolymer that can simultaneously impart properties such as oil and water repellency, flexibility, durability, adhesion, and dispersion stability. It is to provide a combination.

The method for producing a fluorine-containing copolymer of the present invention involves polymerizing a monomer mixture containing (A) an unsaturated carboxylic acid ester monomer and (B) divinylbenzene or an alkyl ester derivative thereof, and adding (C) It is characterized by adding a monomer containing a fluorine-containing monomer and further polymerizing it.

The polymerization medium can be water, an organic solvent, or a solvent-free state, and the polymerization methods are bulk and solution.

Either a suspension or emulsion polymerization solution can be used.

Unsaturated carboxylic acid ester monomer (hereinafter referred to as upper A)
) is a component used to further improve durability, adhesion, and dispersion stability, and is an ester of acrylic or methacrylic acid or fatty acid of aliphatic alcohol or alicyclic alcohol with a relatively long carbon chain. There are also vinyl compounds. Specific examples include lauryl acrylate, lauryl methacrylate, stearyl methacrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, dodecyl methacrylate, dodecyl acrylate, hexyl methacrylate, hexyl acrylate, octyl acrylate, octyl acrylate, cetyl methacrylate, cetyl acrylate,
Vinyl laurate, vinyl stearate, nonyl methacrylate, nonyl acrylate, decyl methacrylate, decyl acrylate, cyclohexyl methacrylate.

Examples include cyclohexyl acrylate. This component solvates into the aliphatic hydrocarbon after polymerization.

Examples of divinylbenzene or its alkyl ester derivatives (hereinafter sometimes referred to as 7-mer B) include 0-
Divinylberzene 1m-Divinylbenzene, P-divinylbenzene, p-methyldivinylbenzene, 0-ethyldivinylbenzene, p-butyldivinylbenzene, m-
Hexyldivinylbenzene, 0-nonyldivinylbenzene, p-decyldivinylbenzene, 0-undecyldivinylbenzene, p-stearyldivinylbenzene, 0-
Methyldivinylbenzene, p-ethyldivinylbenzene, 0-butyldivinylbenzene, p-hexyldivinylbenzene, p-nonyldivinylbenzene, m-decyldivinylbenzene, p-undecyldivinylbenzene,
Examples include 0--stearyldivinylbenzene.

Monomer □-B is a component that forms a graft point or a crosslinked structure.

The fluorine-containing supermer (hereinafter sometimes referred to as "seven-C") used in the present invention is fluoroalkyl acrylate (the fluoroalkyl moiety is -CH, CF, -CH2
C,F-CH,C.

F,, -CH,C,H,, -〇H,C,Ft,, -CF
x Ct F 1m, -CHz Cs F 1t,
CHa Cs F is, -CH, C aFzz, etc.),
Fluoroalkyl methacrylate (fluoroalkyl moiety is -CH.

CF,,-CH,(CF,CF,),Hl-CH,CH
i C3F? , (CHz)s Cs F 1□, -
CH, (CF2OF,) □H1-CHI (CF, CF,
), Hl-(CHi)a (CF zL CF a, -
CH,C,. F, □, etc.).

After polymerization, the fluorine-containing coating material becomes a component that contributes to water and oil repellency.

The following monomers may be used at the beginning or during the polymerization as needed.

One of them is a hepatoma (hereinafter referred to as
It is a monomer that, like Monomer C, contributes to improvements in adhesiveness, flexibility, dispersion stability, etc. Specific examples thereof include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid. Examples of glycidyl group-containing sevenmers include glycidyl acrylate, glycidyl methacrylate, glycidylpropyl methacrylate, glycidylpropyl acrylate, Examples include glycidyl butyl acrylate, glycidyl butyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, and as basic additives, vinylpyridine and diethylaminoethyl methacrylate.

In addition, a nanatsumar (hereinafter sometimes referred to as nanatsumar-E) for improving film-forming properties and adhesion to objects can be used in combination. Specific examples include methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate, propyl methacrylate, propyl acrylate, n-butyl methacrylate, 1s
o-butyl methacrylate, vinyl acetate, vinyltoluene, styrene, chlorstyrene.

and so on.

In addition, the polymerization catalyst used in the polymerization method of the present invention includes:
Examples include azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), phenylazotriphenylmethane, lauryl peroxide, di-t-butyl peroxide, t-butyl peroxide, and cumene hydroperoxide.

Examples of nonaqueous solvents include petroleum aliphatic hydrocarbons such as kerosene, ligroin, n-hexane, n-hebutane, n-octane, i-octane, and i-dodecane (commercially available products include Isopar H and G manufactured by Exxon). , L, to; naphtha N
Q6; Tsurpez 100, etc.); Examples include halogenated aliphatic hydrocarbons, such as carbon tetrachloride and perfluoroethylene. A small amount of an aromatic solvent such as toluene or xylene can also be added to these aliphatic hydrocarbon solvents.

The polymerization before addition of the fluorine-containing supernatant may be carried out in one stage, but may be divided into two or more stages as necessary.

Monomer C creates water and oil repellency, and monomer B creates graft points or crosslinked structures.

Monomer A is solvated in non-polar solvents such as aliphatic hydrocarbons and contributes to dispersive adhesion. Monomer D increases polarity control effect and dispersion stability.

The monomer weight ratio during polymerization varies depending on the use, but is preferably monomer A/B/C/D=1 to 5010.0.
Approximately 1 to 20/30 to 8010.01 to 20 parts by weight are appropriate.

If Nanatsumar-C is less than 1 part by weight, the water- and oil-repellent effect will be small, and if it is more than 50 parts by weight, the adhesiveness will be reduced, and if Monomer B is less than 0.01 part by weight, it will be difficult to form the polymer into particles. If it is more than 1 part by weight, the crosslinked portion will be too large and it will be difficult to disperse the two. Adhesive strength also decreases.

If monomer A is less than 30 parts by weight, it will have poor adhesive properties and will be difficult to disperse in an aliphatic hydrocarbon solvent. If the amount exceeds 80 parts by weight, the oil repellency to non-aqueous solvents will decrease.

If 0.01 part by weight or more of Nanatsumar-D is used as necessary, polarity control and dispersion effects will occur, and if it is 20 parts by weight or more, hydrophilicity will increase and water repellency will deteriorate.

The fluorine-containing copolymer obtained as described above has a particle size of 0.
Dispersion stability is good at about 1 to 5 μm.

Due to its intermolecular adhesive strength, it is particularly suitable as a material for paints, printing inks, and toners.

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

Example 1 100 g of lauryl methacrylate, 10 g of divinylbenzene, and 1 g of BPO were added to a flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping funnel, and a polymerization reaction was carried out at 80° C. for 4 hours. 2 g 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 fluorine-containing polymer was 22% with water.
°, kerosene was 26 @ Example 2 Kerosene loog was taken in the same flask as Example 1, and 9
Heated to 0°C. While stirring, 90 g of 2-ethylhexyl methacrylate, 30 g of p-methyldivinylbenzene
g and 2 g of BPO were added, and a polymerization reaction was carried out for 6 hours.

Next, 0.5 g was added to this and polymerized at 80° C. for 5 hours. The polymerization rate was 93.5%, and the contact angle of the obtained fluorine-containing polymer was 28% with water.
°, and kerosene was 30°. Next, a cloth was impregnated with the fluorine-containing copolymer of the present invention and its surface was treated.

I washed this in the washing machine 10 times, and the contact angle with water was 2.
Considerable durability was observed in 01. Flexibility was also good.

Example 3 400 g of water and 2 g of sodium dodecylbenzenesulfonate were placed in a flask similar to Example 1, heated to 90°C,
Add 20% of cyclohexyl acrylate into this while stirring.
0g, styrene 50g, o-butyldivinylbenzene 1
0g, methacrylic acid 5g, glycidyl methacrylate 1
A monomer solution consisting of 0 g and 3 g of BP was added, and the polymerization reaction was carried out at the above temperature for 4 hours. Thereto was added 1 g of vinylpyridine O, and the polymerization reaction was carried out at 80° C. for 10 hours.

Next, 50 g of AIBN and 3 g of AIBN were added, and 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 38° with water and 42° with kerosene.
Met.

Note that the dispersion containing this fluorine-containing copolymer did not settle even if it was left at room temperature for more than 6 months.

Example 4 Polyethylene wax (Allied Chemical Co., Ltd. 1ijAc polyethylene 1103) was added to the flask used in Example 1.
50g was taken and heated to 90°C to dissolve it.

A monomer solution consisting of 100 g of methyl methacrylate, 10 g of 0-stearyldibee-pbenzene, 1 g of acrylic acid, 8 g of glycidyl acrylate, and AIBNlog was added dropwise to this solution over a period of 2 hours using a dropping funnel, and the polymerization reaction was carried out at the above temperature for 6 hours with stirring. Ta. Next, 100g of methyl methacrylate.

5 g of peroxide was added, and a polymerization reaction was further carried out at 130°C for 6 hours with stirring. The polymerization rate was 98.5%, and the contact angle of the obtained fluorine-containing copolymer was 33° with water and 42° with kerosene.

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

〔Effect of the invention〕

The fluorine-containing copolymer of the present invention not only has sufficient water- and oil-repellent effects, but also satisfies other properties such as durability, flexibility, adhesion, and dispersion stability. ,
Suitable as a water and oil repellent for textiles, paper, plastic surfaces, metal surfaces, etc.

Claims (1)

[Claims] 1. (A) unsaturated carboxylic acid ester monomer and (B
) A monomer mixture containing divinylbenzene or its alkyl ester derivative is polymerized, and the resulting polymerization system is (
C) A method for producing a fluorine-containing copolymer, which comprises adding a monomer containing a fluorine-containing monomer and further polymerizing the mixture.