JPH06329736A - Resin and its production - Google Patents

Abstract

PURPOSE:To provide the title production process which can be conducted without a problem of environmental health and in which the conversion is improved, and the obtained resin is improved in water repellency, oil repellency, electrical insulation properties, etc., and the resin can be obtained in the form of a stable dispersion. CONSTITUTION:The resin is produced by reacting a polymerizable vinyl monomer with a reactive silicone compound in a solvent containing a silicone oil as the principal component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a non-aqueous resin using silicone oil as a polymerization solvent. More specifically, it is a treatment agent for fibers, paper, plastic surfaces, metal surfaces, printing inks, ink jet inks, dry type inks. The present invention relates to a method for producing a vinyl-based resin useful for toners, electrophotographic toners including wet toners, paints, rubber roller materials, cosmetics, rubber roller coating materials, cosmetics and the like.

[0002]

2. Description of the Related Art Many methods for producing vinyl resins are known, and a typical example thereof is Japanese Patent Publication No. 40-19.
No. 186, Japanese Patent Publication No. 45-14545, Japanese Patent Publication No. 56-9
There is one described in a publication such as No. 189. Polymerization solvents used in the methods described in these documents include aromatic hydrocarbons such as toluene, xylene, and benzene; esters; alcohols; fats such as n-hexane, n-heptane, isooctane, isododecane, and mixtures thereof. Group hydrocarbons and the like.

Although these polymerization solvents are generally inexpensive, have excellent resin solubility, and have good volatility, they are odorous and toxic, and therefore have a problem in environmental hygiene and have a low flash point. There are safety problems, and the temperature at the time of polymerization is limited due to the low boiling point. Further, like the aliphatic hydrocarbon solvent, when heat polymerization is carried out, the solvent is oxidized and the odor becomes strong. Furthermore, conventional polymerization solvents cannot be expected to have many effects of increasing the polymerization rate of monomers or improving the properties such as water repellency, oil repellency, and electrical insulation of the obtained resin. In order to improve these points, it has been proposed to use silicone oil as a polymerization solvent (JP-A-3-223302). However, in this method, the obtained polymer is not stably dissolved or dispersed.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems in the prior art, and by using silicone oil as a polymerization solvent, there is no problem of environmental hygiene and characteristic deterioration, high safety, and polymerization. The present invention provides a method for producing a resin in which the resin and the water repellency, oil repellency, electrical insulation, etc. of the resin are improved and the obtained resin is stably dissolved or dispersed in silicone oil.

[0005]

The method for producing a resin of the present invention comprises the steps of dissolving or dispersing a polymerizable vinyl monomer and a reactive silicone compound in a polymerization solvent containing silicone oil as a main component, It is characterized in that the polymerization is carried out in the presence of a reaction catalyst. In the polymerization step of the present invention, the polymerizable vinyl monomer and the reactive silicone compound are graft-polymerized to another suitable resin, or copolymerized in the presence of a crosslinking agent composed of a polyfunctional monomer such as a divinyl monomer. You can In any case, in the method of the present invention, the polymerizable vinyl monomer and the reactive silicone compound are used in a state of being dissolved or dispersed in the polymerization solvent.

The silicone oil used as a polymerization solvent in the present invention has not only good heat resistance and acid resistance, but also small viscosity and temperature change, low surface tension, excellent electric insulation, water repellency, oil repellency and defoaming. It is known to have the properties of mold release and releasability. Therefore, it has different properties from various solvents (synthetic products), natural mineral oils, animal and vegetable oils, and the like. Due to these characteristics, silicone oil is
There are many applications such as capacitors, electronic parts, moisture-proof fillers for transistors, heat transfer media, water repellents, oil repellents, mold release agents and defoamers.

However, there is no known application of silicone oil as a polymerization solvent. This is probably because the silicone oil itself is a kind of resin and the price of the silicone oil is higher than that of a general organic solvent.

The inventors of the present invention have conducted research and studies on the use of silicone oil as a polymerization solvent, and have found the following characteristics and effects, and have completed the present invention based on these characteristics and effects. That is, it was confirmed that the polymerization rate was particularly improved, and the water repellency, oil repellency and electrical insulation of the produced resin were improved. It is considered that this is because the purity of silicone oil is higher than that of general organic solvents, and radicals are less likely to be trapped in the polymerization solvent. Further, the water-repellent, oil-repellent and electrical insulating properties of the obtained resin are improved because the silicone oil as a polymerization solvent is involved in a part of the reaction during the polymerization of the monomer (for example, in the case of dialkyl silicone oil, an alkyl group is used). Polymerization by hydrogen abstraction reaction) is also considered.

Since the silicone oil as a polymerization solvent generally has low solubility, the resin polymerized in the silicone oil solvent has poor solubility, so that the resin and the polymerization solvent are separated from each other. In the present invention, by allowing a reactive silicone to coexist with a vinyl monomer, the obtained resin can be stably dissolved or dispersed in a polymerization solvent.

Examples of the silicone oil used as the polymerization solvent in the present invention include dialkyl silicone oil represented by the following general formula (I); cyclic polydialkylsiloxane or cyclic polyalkylphenylsiloxane; alkylphenylsiloxane and the like. In addition, higher fatty acid modified silicone oil, methyl chlorinated phenyl silicone oil, alkyl modified silicone oil, methyl hydrogen silicone oil, amino modified silicone oil, epoxy modified silicone oil and the like can be used.

[0011]

[Chemical 1]

[However, R ¹ , R ² , R ³ , R, R ⁴ , R ⁵ ,
R ⁶ , R ⁷ and R ⁸ represent —C _n H _{2n + 1} (n = 1 to 20),
These may be the same or different. x is 0 or an integer of 1 or more. When the dialkyl silicone oil represented by the general formula (I) is used, there is an advantage that the temperature during polymerization can be freely selected. Of these, use of dimethylpolysiloxane is advantageous. The silicone oil represented by the general formula (I) preferably has a viscosity at 25 ° C. of 0.01 to 1,000,000 cs (centistokes). Further or more, it is desirable to use a compound of the general formula (I) in which x is 1 to 20,000.

Further, when a cyclic polydialkyl siloxane or a cyclic polyalkyl phenyl siloxane is used, the resin obtained has a drying property of the polymerization solvent, so that especially the coating property of the resin is improved and gloss is obtained. It is advantageous. If an alkylphenyl siloxane (especially using methylphenyl silicone oil) is used,
Introducing a phenyl group (5 to 50 mol%) improves the solubility, which is advantageous for increasing the dispersion stability of the resin solution. Specific examples of these various silicone oils are as follows.

Examples of (I) dialkyl silicone oils:

[0015]

[Table 1]

(II) Examples of cyclic polydialkylsiloxane and cyclic polyalkylphenylsiloxane (contents of phenyl groups are 5, 10, 20, 50 mol%): cyclic polydimethylsiloxane, cyclic polymethylphenylsiloxane, cyclic poly Diethyl siloxane, cyclic polyethylphenyl siloxane, cyclic polydibutyl siloxane, cyclic polybutylphenyl siloxane, cyclic polydihexyl siloxane, cyclic polyhexyl phenyl siloxane, cyclic polydilauryl siloxane, cyclic polymethyl chlorophenyl siloxane, cyclic poly distearyl siloxane, cyclic polymethyl Bromphenyl siloxane.

Examples of (III) alkylphenyl silicone oils:

[0018]

[Table 2]

Commercially available examples of these silicone oils are KF-96L [0.65, manufactured by Shin-Etsu Chemical Co., Ltd.].
1.0, 1.5, 2.0 centistokes (cs)],
KF-96 [10, 20, 30, 50, 500, 100
0,3000 (cs)], KF-56, KF-58, K
F-54, etc., and Toshiba Silicone Co., Ltd.
Made TSF451 series, TSF456 series, T
SF410, 411, 440, 4420, 484, 48
3,431,433 series, THF450 series,
TSF404, 405, 406, 451-5A, 451
-10A, 437 series, TSF440, 400, 4
01, 4300, 4445, 4700, 4450, 47
02, 4730 series, TSF 434, 4600 series, HS-200 manufactured by Toray Silicone Co., Ltd., and the like.

Other solvents can be mixed with the above silicone oil polymerization solvent to the extent that the characteristics of the silicone oil are not impaired. Examples of such a solvent include aromatic hydrocarbon solvents such as toluene, xylene and benzene;
Ethers; Esters; Alcohol solvents; Aliphatic hydrocarbons such as n-hexane, n-octane, iso-octane, iso-dodecane, and mixtures thereof (commercially available from Isoxon H.G.L. V etc.)
Etc. The mixing ratio of such other solvent is about 0.1 to 500 parts by weight with respect to 100 parts by weight of silicone oil.

On the other hand, the following may be mentioned as specific examples of the polymerizable vinyl monomer. First, examples of polymerizable vinyl monomers for homopolymerization or copolymerization with other monomers such as a crosslinking agent are as follows.

Examples of polymerizable vinyl monomers: (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, cinnamic acid, crotonic acid, vinylbenzoic acid, 2-methacryloxyethylsuccinic acid. , 2-methacryloxyethyl maleic acid, 2-methacryloxyethyl hexahydrophthalic acid, 2-methacryloxyethyl trimellitic acid, vinylsulfonic acid, allylsulfonic acid, styrenesulfonic acid, 2-sulfoethylmethacrylate, 2-acrylamido- 2-methylpropanesulfonic acid, 3-chloroamidophosoxypropyl methacrylate, 2-methacryloxyethyl acid phosphate,
Hydroxystyrene, glycidyl methacrylate, 2-
Hydroxyethyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-
Propyl methacrylate, 2-chloroethyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, (meth) acrylonitrile, vinyl chloride, isobutyl-2-cyanoacrylate, 2-cyanoethyl acrylate, ethyl-2-cyanoacrylate, methacryl Acetone, tetrahydrofurfuryl methacrylate, trifluoroethyl methacrylate, p-nitrostyrene, vinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol tri (meth) acrylate, butanediol di (meth) Acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmeth Tri (meth) acrylate, tetra methylol methane tetra (meth) acrylate, dipropylene glycol di (meth) acrylate,
Trimethylolhexane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,3
-Dibutylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, N-methylaminoethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate , N, N-diethylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl acrylate, N-phenylaminoethyl methacrylate, N, N-diphenylaminoethyl methacrylate, aminostyrene, dimethylaminostyrene, N
-Methylaminoethylstyrene, dimethylaminoethoxystyrene, diphenylaminoethylstyrene, N-phenylaminoethylstyrene, vinylpyrrolidone, 2-
N-piperidylethyl (meth) acrylate, 2-vinylpyridine, 4-vinylpyridine, 2-vinyl-6-methylpyridine, acrylamide, methacrylamide,
N, N-dimethylmethacrylamide, N, N-dibutylmethacrylamide, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl ( (Meth) acrylate, vinyl laurate, lauryl methacrylamide, stearyl methacrylamide, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (Meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, styrene, vinyl tol Emissions, vinyl acetate, and the like.

In the present invention, the reactive silicone compound coexisting with the vinyl monomer in the polymerization system has a functional group such as Si-H group, vinyl group, amino group, hydroxyl group, epoxy group and methacryloxy group in the molecule. Is a silicone compound. Such silicone compounds have already been put on the market and commercial products thereof can be used. For example

[0024]

[Chemical 2]

[0025]

[Chemical 3]

Alternatively, a reactive silicone compound such as X-22-161 sold by Shin-Etsu Chemical Co., Ltd.
A, KF867, KF-865, X22-163B, X
-22-169AS, X-22-162C, KF-60
02, X22-164C, X22-5002, X22-
980, X22-165B, X22-174D, KF-
862, X22-3667, X22-3959A, X2
2-2421, X22-5004C.

In the method for producing the resin of the present invention, silicone oil is used as the reaction solvent. In a silicone oil, for example, a polymerizable (meth) acrylic monomer is not polymerized and then uniformly dissolved or dispersed in the silicone oil. Therefore, in the present invention, the reactive silicone compound and the polymerizable vinyl monomer are polymerized in the presence of a polymerization initiator.

In the present invention, the polymerizable vinyl monomer and the reactive silicone compound are reacted by weight such that the polymerizable vinyl monomer / reactive silicone compound = 1 / 0.01 to 9, preferably 1 / 0.1 to 7. It is desirable to let
When the reactive silicone compound is 0.01 or less, the dispersion and solubility in the silicone solvent are poor, and when it is 9 parts by weight or more, the adhesive force of the resin is poor. The polymerizable vinyl monomer and the reactive silicone oil can be combined with each other according to the required characteristics. For example, by using a monomer having an acidic group, a polar monomer, a polyfunctional monomer, a basic monomer, an acrylic acid (meth) ester, etc., with a reactive silicone compound by copolymerization, graft polymerization, block polymerization, esterification reaction, etc. It is possible to produce a functionalized polymer having dispersibility in oil, adsorptivity to pigments, polarity control, adhesiveness, water repellency, oil repellency, storability and the like.

The silicone oil used as the reaction solvent is the above-mentioned polydialkylsiloxane or cyclic polydialkylsiloxane having a viscosity at 25 ° C. of 0.01 to 1,000.
10,000 centistokes, preferably 1 to 10.0
00 centistokes is preferred.

If it is less than 0.01 centistokes, it is apt to evaporate, the temperature during the polymerization must be lowered, the reaction time becomes long, and the product evaporates quickly. On the other hand, 1,000,
It has been found that, when the viscosity is 000 centistokes or more, the crosslinking tends to proceed due to the polymerization using the crosslinking monomer.

The reactive silicone compound has a molecular weight of 5
It was experimentally confirmed that those having an amount of 00 to 50,000 have high polymerizability with the polymerizable vinyl monomer. When the molecular weight is less than 500 or exceeds 50,000, the polymer with the polymerizable vinyl monomer tends to settle in the silicone oil, resulting in poor water repellency and oil repellency. In addition, by adding an acidic substance or a basic substance to the resin obtained as an additive, the viscosity of the resin can be adjusted and the dispersion stability can be improved.

Examples of such an acidic substance include saturated aliphatic or aromatic carboxylic acids: formic acid, acetic acid, glycolic acid, octanoic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, cyanoacetic acid, trimethylacetic acid, monofluoroacetic acid, Monobromoacetic acid, methoxyacetic acid, mercaptoacetic acid, cyclohexanemonocarboxylic acid, lactic acid, nonanoic acid,
Pyruvic acid, hexanoic acid, heptanoic acid, propionic acid,
Butyric acid, levulinic acid, adipic acid, azelaic acid, oxaloacetic acid, citric acid, glutaric acid, succinic acid, oxalic acid, tartaric acid, naphthoic acid, 2-sulfoethyl methacrylate, 2-acrylamido-2-methylpropanesulfonic acid, 3-chloro Amidophosphoxypropyl methacrylate, 2-methacryloxyethyl acid phosphate,
Hydroxystyrene etc. are mentioned.

Examples of the basic substance include 2-aminoethanol, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine, ethylenediamine, cyclohexylamine,
Tris (hydroxymethyl) methylamine, butylamine, 1,6-hexanediamine, hexylamine, dihexylamine, methylamine, dimethylamine, trimethylamine, aniline, chloroaniline, dinitroaniline, dimethylaniline, nitroaniline, methylaniline, benzylamine , Methylbenzylamine, glycine, imidazole, bipyridyl, pyridine, aminopyridine, dimethylpyridine, trimethylpyridine, monomethylpyridine, pyridoxine, pyrrolidine, piperazine, piperidine, benzimidazole, purine, cysteine and the like. In the resin polymerization method, dispersibility, adhesiveness, water repellency and oil repellency can be further enhanced by graft polymerization, block polymerization, crosslinking reaction and the like.

[0034]

EXAMPLES Next, examples will be shown. Examples 1 to 3, Comparative Example 1 300 g of the polymerization solvent shown in Table 1 below was placed in a container equipped with a stirrer, a thermometer, and a reflux condenser, and heated to 95 ° C. In this, 2-ethylhexyl methacrylate 150 g, glycidyl methacrylate 50 g, reactive silicone compound [X22-5002 (MW421) manufactured by Shin-Etsu Chemical] 25
g and azobisisobutyronitrile (3 g) were added dropwise over 1 hour, and then a polymerization reaction was carried out at 95 ° C. for 4 hours. The resin thus obtained was reprecipitated with methal and then purified by repeating the operation of dissolving in toluene three times.

Next, the water repellency, oil repellency and electric resistance of each purified resin were measured and the results shown in Table 1 were obtained. The polymerization rate is also shown in Table 1. Comparative Example 1 is a case where polymerization was performed except for X22-5002 in Example 1.

[0036]

[Table 3]

(Note) The measuring method is as follows.

Polymerization rate: (resin solid content / theoretically charged solid content) × 100 (%) Water repellency: The contact angle of the resin surface with ion-exchanged water was measured using a contact angle measuring instrument manufactured by Kyowa Chemical Co., Ltd. . Oil repellency: The contact angle of the resin surface to iso-dodecane was measured using a contact angle measuring instrument manufactured by Kyowa Chemical Co., Ltd.

Dispersibility: storage at 50 ° C. for 3 months, ○: no sedimentation, Δ: separation, ×: large sedimentation, Example 4 FM produced by Nitrogen Co., Ltd. in place of the reactive silicone compound of Example 1 Polymerization was carried out in the same manner as in Example 1 except that -0725 (MW 10,000) was used. as a result,
The polymerization rate is 92.4, the water repellency is 34.0, the oil repellency is 29.1, and the dispersibility is ◯.

Example 5 Silicone oil (HS-2 was added to the same reactor as in Example 1).
00) 400 g, and after heating to 95 ° C., stearyl methacrylate 150 g, a reactive silicone compound [FM-0725 (MW 10,000) manufactured by Nitrogen Co., Ltd.]
80 g], a mixed solution of 30 g of glycidyl acrylate and 2 g of benzoyl peroxide were added dropwise over 1 hour, and then the mixture was stirred for 3 hours at 95 ° C. to complete the reaction and prepare a copolymer. Subsequently, 1 g of lauryldimethylamine, 15 g of methacrylic acid and 0.1 g of hydroquinone were added to the reaction solution, and 9
The esterification reaction was carried out at 5 ° C. for 10 hours. The degree of esterification was 30%. Next, add isooctane 60 to this reaction solution.
While adding 0 g and maintaining the temperature at 95 ° C., a mixed solution containing 60 g of styrene and 4 g of benzoyl peroxide was added dropwise over 3 hours, and the reaction was further performed for 5 hours. 200 g of silicone oil (HS-200) was added to this reaction product and cooled. As a result of the polymerization, the polymerization rate was 95.2% and the particle size was 0.63μ.
m, dispersibility is good and stable, and adhesive strength is 1120 (g
/ 20), adhesive strength of polyethylene surface, water repellency 35.1,
The oil repellency was 30.0.

Example 6 After stirring, 3.0 with thermometer, condenser and dropping funnel.
Silicone oil (KF961.
1 cs) 500 g was charged, heated to 80 ° C., and stirred therein as a silicone compound F manufactured by Nitrogen Co., Ltd.
100 g of M0711 (MW1000), a monomer of the following formula (1).

[0042]

[Chemical 4]

A monomer solution consisting of 50 g, 10 g of methacrylic acid and 5 g of azobisisobutyronitrile was added dropwise over 2 hours. Then, it was polymerized at this temperature for 4 hours. Further, 20 g of methyl methacrylate, 3 g of glycidyl methacrylate and 2 g of azobisisobutyronitrile were dropped into the above polymer at 80 ° C. over 1 hour to synthesize a graft polymer. Polymerization rate is 94.1%, particle size is 0.95μ, dispersibility is good and stable, adhesive strength (adhesive strength on polyethylene surface) is 960 (g / 20), water repellency 36.0, oil repellency 31 It was 0.0.

Example 7 800 g of KF96L (viscosity 1.5 cs) was placed in a 2 liter flask equipped with a stirrer, a thermometer and a reflux condenser and heated to 90 ° C. A solution of 170 g of FM-2241 manufactured by Nitrogen Co., Ltd., 80 g of diethylene glycol dimethacrylate and 8 g of benzoyl peroxide was added dropwise thereto as a silicone compound over 2 hours to cause a polymerization reaction, and then the reaction was completed. Polymerization rate is 93.5
%, The particle size was 3.2 μ, the dispersibility was good and stable, and the adhesive strength was 360 (g / 20) (the adhesive strength on the polyethylene surface), the water repellency was 32.0, and the oil repellency was 26.5.

Example 8 10 g of methacrylic acid in 100 g of lauryl methacrylate
Was mixed with 3 g of azobisisobutyronitrile in a flask and polymerized at 80 ° C. for 4 hours. 50 g of a silicone compound [FM-0521 manufactured by Nitrogen Co., Ltd.] and 0.1 g of dodecylamine were mixed therein and reacted at 80 ° C. for 25 hours. The reaction product is silicone oil KF9937 300 g
Dispersed. The adhesive force of the obtained resin is 1250 (g /
The adhesive strength of the polyethylene surface was 20).

Example 9 FM-0711 100 g manufactured by Nitto K.K. 100 g Glycidyl methacrylate 30 g Methacrylic acid 25 g Lauryl methacrylate 30 g Benzoyl peroxide 3 g Silicone oil KF995 100 g was polymerized in a flask at 85 ° C. for 4 hours. After completion of the polymerization, 0.05 g of pyridine was added and an esterification reaction was carried out at 80 ° C. for 30 hours to introduce a crosslinked structure. Polymerization rate 92.9%,
Adhesive force 816 (g / 20 adhesive force on polyethylene surface),
The water repellency was 29.3 and the oil repellency was 32.0.

Example 10 To 100 g of the resin of Example 1 was added 0.5 g of octanoic acid as an additive, and the mixture was mixed at 80 ° C. for 2 hours. Dispersibility is good and stable, water repellency 28.0, oil repellency 24.8
Met. Also, the dispersibility when used as a colorant was improved.

Example 11 0.5 g of the additive pyrrolidine was added to 100 g of the resin of Example 5.
Add and mix at 80 ° C. for 2 hours. The dispersibility was good and stable, and the water repellency was 34.0 and the oil repellency was 29.2.
In addition, dispersibility when used as a colorant was improved.

[0049]

According to the present invention, the obtained resin is odorless, has high safety, is excellent in water repellency and oil repellency, and has high dispersibility and stability in silicone oil.

Front Page Continuation (72) Hidemi Uematsu, Inventor Hidemi Uematsu 1-3-6 Nakamagome, Ota-ku, Tokyo Within Ricoh Co., Ltd. (72) Shin Ogawara 2-81-211 Ookayama, Meguro-ku, Tokyo

Claims (3)

[Claims] 1. A resin characterized by reacting a polymerizable vinyl monomer with a reactive silicone compound using a solvent containing silicone oil as a main component, and a method for producing the same. 2. The method for producing a resin according to claim 1, wherein graft polymerization is performed in the polymerization step. 3. The method according to claim 1, wherein a crosslinking agent is present during the polymerization step.