JPH02269717A - Fluorine-containing graft copolymer - Google Patents

Abstract

PURPOSE:To obtain a fluorinated graft copolymer with oil and water repellency, flexibility, durability, etc., by grafting a fluoromonomer onto an esterified copolymer obtained from a specified monomer, an unsaturated carboxylic acid and a glycidyl monomer. CONSTITUTION:A copolymer is obtained by copolymerizing a monomer (a) of formula I (wherein R is -H or -CH3; A is a group of formula II or III; and n is 6-20) with an unsaturated carboxylic acid (b) or a glycidyl monomer (c) in a weight ratio of component (a) to component (b) or component (c) of (99.9-80): (0.1-20) at 70-150 deg.C. 100 pts.wt. this copolymer is esterified with 0.1-20 pts.wt. component (b) or (c) not contained in the copolymer at 30-120 deg.C in the presence of an esterification catalyst to obtain an esterified copolymer. 5-100 pts.wt. fluoromonomer (d) is grafted onto 100 pts.wt. this copolymer at 70-150 deg.C to obtain the title copolymer of a particle diameter of 0.1-5mum.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to water and oil repellent treatment agents for textiles, paper, plastic surfaces, metal surfaces, etc., or dry or wet toners for electrophotography,
This invention relates to a method for producing a fluorine-containing graft copolymer useful for paints, etc.

[Prior art]

Traditionally, textiles, paper, plastic surfaces, metal surfaces and 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 binders such as printing inks. 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) etc. For the purpose of improving durability and flexibility, a method has been proposed in which 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. 157380/1983). ing. However, although this method has a satisfactory level of durability, it has not yet been sufficiently effective in terms of flexibility. We are also trying to introduce a softening component into water and oil repellent treatment agents.

method by copolymerization of fluorine-containing (meth)acrylate and siloxane-containing (meth)acrylate (JP-A-1989-1999-
130408), a method using a reaction product of a fluorine-containing urethane compound and a reactive organopolysiloxane (
(Japanese Patent Application Laid-Open No. 60-81278).

Method using an organopolysiloxane having a perfluoroalkyl group in the side chain (Japanese Patent Publication No. 61-6187)
However, 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.

[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 graft compound that can simultaneously impart oil and water repellency, flexibility, durability, adhesion, dispersion stability, and other properties. An object of the present invention is to provide a polymer.

[Structure and operation of the invention]

The fluorine-containing graft copolymer of the present invention has the following formula: (a) General formula ■ CH2=C (b) [However, R is -H or -CH, group, A is 10000nH2
n+, or ○CnH2rl+□ (n is an integer from 6 to 20)
represents. ] A step of copolymerizing the monomer represented by the formula with an unsaturated carboxylic acid or a glycidyl group-containing monomer; a step of esterifying with a monomer having a group, or with an unsaturated carboxylic acid when the constituent monomers include a glycidyl group,
as well as.

(c) It is obtained in a step of graft polymerizing a fluorine-containing monomer to this esterified copolymer.

The method for producing the copolymer of the present invention is carried out in a solvent or in the absence of a solvent (a
) and (b) in the presence of a polymerization catalyst;
) step is carried out in the presence of an esterification catalyst.

The present inventors previously described in Japanese Patent Publication No. 57-56940,
We proposed a graft copolymer-containing latex useful as a binder for paints and electrophotographic toners. In this latex, waxes are added as a dispersion stabilizer during or after the manufacturing process, and in step (C), (meth)acrylic acid or a lower alkyl ester thereof (having 1 to 4 carbon atoms), instead of the fluorine-containing monomer, It is produced by substantially the same method as the present invention except that a vinyl monomer such as styrene is used.

However, although the latex thus obtained has excellent adhesive properties and dispersion stability, it is somewhat lacking in durability and flexibility, and it does not have water repellency or oil repellency.

The present invention uses a fluorine-containing monomer in the graft copolymerization step (c) to impart water repellency and oil repellency to the proposed graft copolymer while maintaining excellent adhesiveness and dispersion stability. , with improved durability and flexibility.

In the method for producing a fluorine-containing graft copolymer of the present invention, (a)
A fluorine-containing monomer may be used in the copolymerization step or the esterification step (b), but in order to obtain desired properties such as water repellency and oil repellency, the fluorine-containing monomer may be used in the graft polymerization step (c). It is preferable to use

Next, manufacturing conditions, materials used, etc. in the method of the present invention will be explained.

First, the copolymerization reaction in step (a) is usually 70 to 150
It is carried out at a temperature of °C. Further, the weight ratio of the monomer of general formula I to the unsaturated carboxylic acid or the monomer having a glycidyl group is 99.9 to 80:80: 0.1 to 2.
Approximately 0 is appropriate.

Examples of monomers of general formula I are lauryl, 2-ethylhexyl, stearyl of acrylic acid or methacrylic acid,
Higher alkyl esters such as vinyl stearyl (CG to C
2゜) and this.

Examples of unsaturated carboxylic acids that can be copolymerized with monomers include acrylic acid, methacrylic acid, fumaric acid, crotonic acid, itaconic acid, and maleic acid, and examples of monomers having a glycidyl group include glycidyl acrylate, glycidyl methafreyrate, and glycidyl propyl. Examples include acrylate, glycidylpropyl methacrylate, glycidyl butyl acrylate, glycidyl butyl methacrylate, and the like. Further, as polymerization catalysts, azobisisobutyronitrile (AIBN), benzoyl peroxide (BP
O), phenylazotriphenylmethane, lauryl peroxide, di-t-butyl peroxide, t-butyl peroxide.

Examples include cumene hydroperoxide.

Next, the esterification reaction in step (b) is usually carried out at 30 to 1
It is carried out at a temperature of 20°C. The appropriate amount of the glycidyl group-containing monomer or unsaturated carboxylic acid used here is about 0.1 to 20 parts by weight based on 100 parts by weight of the copolymer obtained in step (a).

Examples of the esterification catalyst include pyridine and lauryldimethylamine.

Through this esterification reaction, the copolymer is esterified,
Grafting active sites are formed at the esterification site. The esterified copolymer thus obtained becomes the frame portion of the graft copolymer obtained in the final step.

Finally, the graft polymerization reaction in step (c) is usually carried out at 70%
It is carried out at a temperature of ~150°C. The amount of fluorine-containing monomer used is 5 to 5 parts by weight per 100 parts by weight of the esterified copolymer.
100 parts by weight is suitable.

As the fluorine-containing monomer, fluoroalkyl acrylate (the fluoroalkyl part is 10H2CF3.-CH2C
2F,, -CH2C,F,, -CH,C4H,, -CH
2C, F□0. -CH2C,Fl,.

CH2Cs F 1-r -CH2Cs F t s
, CH2C-0F2□, etc.), fluoroalkyl methacrylate (the fluoroalkyl part is -CH2CF, -
CH2(CF2CF2)2H, -CH2CH2C,F,
.

(CH2)sC,F, , -CH, (CF2CF2),
H.

CHz (CF 2 CF2) 4H, (CH2) 2 (C
FzL.

CF, -CH2C2°F41, etc.).

As mentioned above, the method of the present invention is carried out in a solvent or without a solvent, and an organic solvent or water is used as the solvent.

Examples of organic solvents include toluene; tetrahydrofuran; benzene; Exxon Isopar H, L, Naphtha Nα6
; Tsurpez 100, etc.); halogenated aliphatic hydrocarbons, such as carbon tetrachloride, perfluoroethylene; and mixtures thereof.

The fluorine-containing graft copolymer obtained as described above has a particle size of about 0.5 μm, has good dispersion stability, and has intermolecular adhesive strength, so it can be used especially in paints, printing inks, magnetic fluids, etc. Suitable as semi-solid ink, electrophotographic dry or wet toner material, etc.

In the method of the present invention, a polymerizable monomer such as a lower alkyl ester (C1 to C4) of acrylic acid or methacrylic acid can be used in combination in the step (C).

Further, in the present invention, a wax having a softening point of 60 to 130° C. is used in one or more of the steps, preferably step (c), mainly to further improve dispersion stability.

It is preferable to add waxes such as low molecular weight polyolefins and ethylene-ethyl acrylate-maleic anhydride copolymers. However, in this case, a non-aqueous solvent such as a petroleum-based aliphatic hydrocarbon or its halide is used as the reaction solvent, and the mixture is completely dissolved in this solvent during one reaction. The amount of wax used in step (a) is 10% of the mixture of monomer ① and unsaturated carboxylic acid or glycidyl (meth)acrylate.
5 to 50 parts by weight per 0 parts by weight, and 5 to 50 parts by weight per 100 parts by weight of the copolymer in step (b).

In step (C), it is appropriate to use 1 to 40 parts by weight per 100 parts by weight of the esterified copolymer.

In any case, since waxes themselves do not participate in the reaction in any process, they do not have a substantial effect on the quality of the final non-aqueous resin. In order to increase the rate, it is preferable to include step (c).

By cooling the reaction solution in the final step in this way, the dissolved waxes are precipitated in the form of fine particles.

The present inventors discovered that during this precipitation, as a result of the graft copolymer suspended in the reaction solution being adsorbed to wax fine particles at the same time, the wax was used as a core and the outside was coated with the graft copolymer. It has been found that a latex in which resin particles are suspended is obtained. The size of particles in latex can be changed by changing the type and concentration of wax, or conditions such as stirring and cooling, but generally the concentration of wax is low, for example, a dilute solution of 1 to 10% is used. When rapidly cooled, it becomes fine particles of 0.1 to 0.3μ,
Also, when a concentrated solution, for example 20 to 50%, is gradually cooled, 0
．． This results in large particles of about 5 to 20 microns. Therefore, rapid cooling is preferred in order to obtain fine particles.

It is thought that the surfaces of the thus obtained resin particles are coated with a graft polymer and a polar polymer that are soluble or insoluble in a non-aqueous solvent, and the center is mostly composed of a wax core.

The features of one example of the method of the present invention are as follows.

(1) The latex particles have polar groups that provide dispersion stability, and the specific gravity of the wax core is similar to that of the nonaqueous solvent used as the dispersion medium, so the dispersion stability is good and it is difficult to aggregate.

For example, latex with a solid content of 1% is stable for more than three months.

(2) Latex particles provide fixing properties and are well adsorbed to various pigments such as titanium oxide, zinc oxide, calcium carbonate, and silica, and have clear polarity in non-aqueous solvents, and (1)
For this reason, the dispersion stability of the pigment is also good.

(3) Latex particles have polar groups that provide fixing properties, so when used as paint or electrophotographic toner,
Good fixation on hydrophilic or hydrophobic surfaces such as paper, plastic plates, metal plates, etc.

(4) The manufacturing method is simple and the desired product can be obtained in a short time and with high yield.

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

Example 1 300 g of Isovar G (manufactured by Esso Standard Oil Co., Ltd.) was placed in a container equipped with a stirrer, a thermometer, and a reflux condenser, and heated to 95°C. In this, 200 g of 2-ethylhexyl methacrylate, 10 g of glycidyl methacrylate
A mixture of 3 g and 3 g of azobisisobutyronitrile was added dropwise at a constant rate over 3 hours, and the mixture was further stirred for 1 hour to complete the reaction. 5 g of acrylic acid, 0.1 g of hydroquinone, and 1 g of lauryl dimethylamine were added to this and reacted at 90° C. for 15 hours to esterify the copolymer obtained in the reaction. The degree of esterification was in the range of 25-30% from measurements of acid value reduction.

Next, 0,500 g of Isovar was added to the esterification reaction solution, and the fluoroacrylate CH represented by the following formula was heated at 90°C.

CH,=C COOCR2C,H.

50 g of azobisisobutyronitrile and 3 g of azobisisobutyronitrile were added dropwise at a constant rate over 3 hours, and the liquid temperature was maintained at the above temperature for about 5 hours to complete the reaction.

Furthermore, 300 g of this reaction product was added with 630 Isobar.
After adding 0 g, the mixture was heated to 90°C and a polymerization reaction was carried out for 3 hours to produce a fluorine-containing graft copolymer.

The polymerization rate was 93%, and the contact angle of the copolymer with water was 3
2' and 28'' to kerosene, showing water and oil repellency.

Example 2 A fluorine-containing graft copolymer was prepared in the same manner as in Example 1 except that maleic acid was used instead of acrylic acid to esterify the 2-ethylhexyl methacrylate-turglycidyl methacrylate copolymer. did. The polymerization rate was 92.
8%, and the contact angle of the copolymer with water was 90' and the contact angle with kerosene was 29°, indicating water and oil repellency.

Example 3 400 g of toluene was placed in the same reactor as in Example 1.

After heating to 95°C, a mixed solution of 200 g of inbutyl methacrylate, 10 g of glycidyl acrylate, and 2 g of benzoyl peroxide was added dropwise over 1 hour, and then stirred at 95°C for 3 hours to complete the reaction and prepare a copolymer. did. Subsequently, 1 g of lauryl dimethylamine, 3 g of methacrylic acid, and 0.1 g of hydroquinone were added to the reaction solution, and an esterification reaction was carried out at 95° C. for 10 hours. The degree of esterification is 3
It was 0%. Next, 600 g of toluene was added to this reaction solution, and while maintaining the temperature at 95° C., a fluoroacrylate represented by the following formula, CH2=C Coo(CH,),C,H, was prepared over a period of 3 hours.

100 g + 40 g styrene and 4 benzoyl peroxide
A mixed solution consisting of g was added dropwise, and the graft reaction was further carried out for 5 hours. Add 200 g of toluene to this reaction product,
Paraffin wax at 5℃ (softening point 70-72℃) 50
After adding and dissolving g, cool with tap water while stirring,
A latex in which resin particles were suspended was obtained. The polymerization rate was 94.
2%, and the contact angle of the resin particles was 45° for water and 31° for n-hexane, showing water and oil repellency. Moreover, the durability and adhesion were also good.

Example 4 400 g of Isovar L was placed in a reactor similar to Example 1 and heated to 90°C, followed by 200 g of lauryl methacrylate, 3 g of crotonic acid and benzoyl peroxide I.
g of the mixture was added dropwise over a period of 2 hours, and then the temperature was maintained for 3 hours to complete the reaction. To this reaction solution, 1 g of lauryl dimethylamine and glycidyl methacrylate L were added.
og was added and the mixture was allowed to undergo an esterification reaction at 90°C for 20 hours. The degree of esterification at this time was 50%. 600 g of Isovar L was added to this reaction solution, heated to 90° C., and 40 g of ethyl acrylate and 45 g of fluoromethacrylate of the following formula were added to CH.

A mixed solution of CH2=C C00 (CH2), C2, F41 and 4 g of benzoyl peroxide was added dropwise over 3 hours, and the reaction was further carried out for 5 hours.

Add 200 g of Isovar L to 200 g of this reaction product.
20 g of polyethylene (DYNH manufactured by Union Carbide) was added and dissolved at 90°C, and the reaction was continued for 1 hour. Next, 3 g of nitrostyrene and 0.5 g of benzoyl peroxide were added to this solution and polymerized at 90° C. for 4 hours, followed by cooling with tap water while stirring to obtain a latex in which resin particles were suspended.

The polymerization rate of this product was 98.3%, and the contact angle was 69° with respect to water and 42° with respect to n-hexane.

Example 5 400 g of water and 2 g of nonionic surfactant were added to the same reaction solution as in Example 1, heated to 85°C, and then 200 g of 2-ethylhexyl methacrylate and 5 g of methacrylic acid were added.
A mixed solution of 3 g of azobisisobutyronitrile and 3 g of azobisisobutyronitrile was added dropwise over 2 hours, and then maintained at 85° C. for 2 hours to complete the reaction. Next, add 1 g of lauryl dimethylamine to the reaction solution.
Then, 5 g of glycidyl acrylate was added and reacted at 85° C. for 18 hours. The degree of esterification at this time was 50%.

After adding 400 g of water to this reaction product and heating it to 90°C, fluoromethacrylate 50r of the following formula was obtained.

A mixed solution of CH3 CH2= C c o o (CH2) 2 C-2F 2 s and 3 g of azobisisobutyronitrile was added dropwise over 3 hours, and the reaction was further carried out for 5 hours. Next, 200 g of water was added to 200 g of this reaction product and cooled to obtain a fluorine-containing copolymer.

The polymerization rate of this product was 90.3%, and the contact angle was 55' with water and 33° with n-hexane. Also, the adhesiveness, durability, and flexibility were good.

Example 6 300 g of isooctane was placed in the same reactor as in Example 1, heated to 90°C, and 200 g of 2-ethylhexyl methacrylate and 1 g of glycidyl methacrylate were added thereto.
A mixture of 0 g and benzoyl peroxide was added dropwise over 2 hours, and the temperature was maintained for 4 hours to complete the reaction. Furthermore, in this copolymer liquid, 1°g of lauryldimethylamine, 3g of maleic acid, hydroquinone o, os
g was added thereto, and the mixture was reacted at 90°C for 15 hours. The acid value of the reaction product was 20. This product is then added with 5 isooctane.
After adding 20g, add 40g of vinyl toluene at 90℃.
A mixture of 30 g of fluoroacrylate of the following formula CH,=C C00CH,C4F,H and 3 g of benzoyl peroxide was added dropwise over 3 hours, and the reaction was continued for 5 hours. This reactant product 20
After adding 200 g of isooctane to 0 g and heating to 90°C, 20 g of ethylene-ethyl acrylate-maleic anhydride (weight ratio 98:1:1) copolymer was added, dissolved, and reacted for 1 hour to form resin particles. A suspended latex was obtained.

The polymerization rate of this product was 96.1%, and the contact angle was 32° with respect to water and 21° with respect to kerosene. It also had excellent adhesion and durability.

Example 7 0 g of Isovar H3O was placed in the same device as in Example 1 and heated to 90°C, followed by 200 g of stearyl acrylate.
, glycidyl methacrylate 20g, fluoromethacrylate 5g CH of the following formula.

A mixed solution of CH,=C C00CH, CH2C□2F24H and 3 g of azobisisobutyronitrile was added dropwise over 5 hours. Next, add 10 g of acrylic acid, 1 g of lauryl dimethylamine, and 0.5 g of hydroquinone, and
The esterification reaction was carried out at 0°C for 10 hours. Next, 0 g of Isovar H3O was added, and at 95°C, a mixture of 40 g of the same fluoromethacrylate, 5 g of styrene, and 3 g of azobisisobutyronitrile was added over 3 hours, and an additional 5 g of
A time reaction was performed. Next, 200 g of Isovar H and 40 g of polyethylene wax (Sunwax 171 P manufactured by Kochu Kasei Co., Ltd.) were added to 150 g of this reaction product and dissolved at 95° C., followed by reaction for 1 hour.

Next, 10 g of droxyethyl methacrylate and 0.3 g of azobisisobutyronitrile were added to the reaction solution, and the mixture was heated at 95°C.
After polymerization for 3 hours, the mixture was rapidly cooled while stirring to obtain a latex in which resin particles were suspended.

The polymerization rate of this product was 89.6%, and the contact angle was 48° for water and 35° for kerosene. It also had excellent adhesion and dispersion stability.

[Function and effect of the invention]

The fluorine-containing graft copolymer of the present invention not only has sufficient polishing and oil repellent effects, but also has durability, flexibility, adhesiveness, dispersion stability rings,
Since it satisfies other properties, it is suitable as a water- and oil-repellent treatment agent for paints, printing inks, electrophotographic toners, fibers, paper, plastic surfaces, metal surfaces, and the like.

Claims (1)

[Claims] 1. (a) General formula I ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, R is -H or -CH_3 group, A is -COOC_n
H_2_n_+_1 or OC_nH_2_n_+_1(
n represents an integer from 6 to 20). ] A step of copolymerizing the monomer represented by the formula with an unsaturated carboxylic acid or a monomer having a glycidyl group, (b) When the copolymer contains an unsaturated carboxylic acid in the constituent monomers of the copolymer, (c) Graft polymerization of a fluorine-containing monomer to this esterified copolymer. Fluorine-containing graft copolymer obtained in the process.