JPH03223302A - Production of resin - Google Patents

Abstract

PURPOSE:To produce a resin improved in water repellency, oil repellency, electrical insulation, etc., in high conversion while improving the hygiene and safety of working environment by polymerizing a polymerizable vinyl monomer in a polymerization solvent based on a silicon oil. CONSTITUTION:A polymerizable vinyl monomer is dissolved or dispersed in a polymerization solvent based on a silicone oil and polymerized in the presence of a polymerization catalyst. Examples of the silicone oil include a dialkyl- silicone oil of formula I [wherein R<1> to R<8> are each -CnH2n+1 (wherein (n)=1-20) and they may be the same or different; and (x) is 0 or an integer of 1 or greater], a cyclic polydialkylsiloxane, a cyclic polyalkylphenylsiloxane and an alkylphenylsiloxane. The polymerizable vinyl monomer may be grafted onto a suitable resin or may be copolymerized in the presence of a crosslinking agent comprising a polyfunctional monomer such as a divinyl monomer.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a non-aqueous resin using silicone oil as a polymerization solvent, and more specifically, a method for producing a non-aqueous resin using silicone oil as a polymerization solvent. The present invention relates to a method for producing a vinyl resin useful for printing inks, electrophotographic toners, paints, rubber roller materials, rubber roller coating materials, etc.

[Conventional technology]

Many methods for producing vinyl resins are known, and representative examples include those described in Japanese Patent Publications No. 40-19186, Japanese Patent Publication No. 45-14545, and Japanese Patent Publication No. 56-9189. Polymerization solvents used in the methods described in these documents include aromatic hydrocarbons such as toluene, xylene, and benzene; esters; alcohols;
Aliphatic hydrocarbons such as hexane, n-hebutane, isooctane, isododecane, and mixtures thereof.

These polymerization solvents generally have advantages such as being inexpensive, having excellent resin solubility, and having good volatility.

It is odoriferous and toxic, which poses environmental health problems.

The low flash point poses safety issues, and the low boiling point limits the temperature during polymerization. In addition, some solvents, such as aliphatic hydrocarbon solvents, become oxidized and have a strong odor when heated and polymerized.

Furthermore, conventional polymerization solvents cannot be expected to have many effects of increasing the polymerization rate of monomers or improving the properties of the resulting resin, such as water repellency, oil repellency, and electrical insulation.

Yet again. Conventional polymerization solvents have high solubility of resin, so in order to separate the obtained resin from the solvent, heating drying, vacuum drying, and the use of a poor solvent (precipitating the resin in a poor solvent) are required.
The reality is that there are many things that require a lot of time and effort.

[Problem to be solved by the invention]

The present invention solves the above-mentioned problems in the prior art, and by using silicone oil as a polymerization solvent, there are no problems with environmental hygiene or property deterioration.

Production of resins that are highly safe, improve the polymerization rate, water repellency, oil repellency, electrical insulation, etc. of the resin, facilitate the separation of the resin from the solvent, and greatly expand the temperature range during polymerization. The present invention provides a method.

[Means to solve the problem]

The method for producing the resin of the present invention is characterized by dissolving or dispersing a monopolymerizable vinyl heptamer in a polymerization solvent containing silicone oil as a main component, and then polymerizing it in the presence of a monopolymerization catalyst.

In the polymerization process of the present invention, it is possible to graft-polymerize the polymerizable vinyl hexamer onto other suitable resins, or to copolymerize it in the presence of a crosslinking agent consisting of a polyfunctional monomer such as a divinyl monomer. can. In either case, in the method of the present invention, the polymerizable vinyl hexamer is used in a state dissolved or dispersed in the polymerization solvent.

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

However, there are no known examples of applying silicone oil as a polymerization solvent, because silicone oil itself is a type of resin, the price of silicone oil is higher than general organic solvents, and This is probably due to the fact that the properties of polymers using silicone oil as a polymerization solvent had not been measured.

The present inventors have conducted research and examination on the use of silicone oil as a polymerization solvent, and have discovered the following features and effects, and have completed the present invention based on these findings. That is, in particular, an improvement in the polymerization rate and an improvement in the water repellency, oil repellency, and electrical insulation properties of the produced resin were observed. this is,
This is thought to be because silicone oil has a higher purity than general organic solvents, so radicals are less likely to be trapped in the polymerization solvent. In addition, the reason why the obtained resin has improved water repellency, oil repellency, and electrical insulation properties is that the silicone oil as a polymerization solvent participates in some reactions during the polymerization of monomers (for example, in the case of dialkyl silicone oil, alkyl groups It is also possible that polymerization by hydrogen abstraction reaction from

Furthermore, since silicone oil as a polymerization solvent generally has low solubility, a resin polymerized in a silicone oil solvent has poor solubility, and therefore it is easy to separate the resin from the polymerization solvent. For example, polylauryl methacrylate polymerized in toluene.

In contrast, polylauryl methacrylate, which is polymerized in a silicone oil solvent, does not become sticky even after the silicone oil is removed, and can be obtained as a plastic resin. Of course, it is possible to mix and use other polymerization solvents as long as such characteristics of the silicone oil are not impaired.

In the present invention, examples of the silicone oil used in the polymerization solvent include dialkyl silicone oil represented by the following general formula (1): cyclic polydialkylsiloxane or cyclic polyalkylphenylsiloxane; alkylphenylsiloxane. Others include higher fatty acid-modified silicone oil, methylchlorinated phenyl silicone oil, alkyl-modified silicone oil, methylhydrogen silicone oil, amino-modified silicone oil,
Epoxy-modified silicone oil etc. can be used.

[However, R", R", R3, R, R', Rs, R'
, R7,R'' represent -CnH2n+1 (n=1 to 20), which may be the same or different.
or an integer greater than or equal to 1. ] When a dialkyl silicone oil represented by the general formula 1) is used, there is a particular advantage that the temperature during polymerization can be freely selected. Among them, it is advantageous to use dimethylpolysiloxane. Moreover, the silicone oil represented by this general formula (I) is 2
Viscosity at 5℃ is 0.01-1,000,000cs
(centistokes) is preferred6. It is preferable to use the compound represented by the general formula (1) in which X is 1 to 20,000.

Furthermore, when a cyclic polydialkylsiloxane or a cyclic polyalkylphenylsiloxane is used, the resulting resin has a drying property of the polymerization solvent, so it is particularly advantageous for improving the coating properties of the resin and producing gloss. be. When alkylphenylsiloxane (especially methylphenyl silicone oil is preferably used) is used, the introduction of phenyl groups (5 to 50 mol%) improves solubility, resulting in improved dispersion stability of the resin solution. It is advantageous to raise the

Specific examples of these various silicone oils are as follows.

(I) Examples of dialkyl silicone oils: cyclic polydimethylsiloxane, phenylsiloxane cyclic polydiethylsiloxane, cyclic polymethyl cyclic polyethylphenylsiloxane cyclic polydibutylsiloxane, cyclic polybutylphenylsiloxane cyclic polydihexylsiloxane, cyclic polyhexylphenylsiloxane cyclic Examples of polydilaurylsiloxane, cyclic polymethylchlorophenylsiloxane, cyclic polydistearylsiloxane, cyclic polymethylbromphenylsiloxane (III) alkylphenyl silicone oil: Commercially available examples of these silicone oils include KF' manufactured by Shin-Etsu Chemical Co., Ltd. -96L (0,65,1,0,1,
5,2,0 centistokes (as)), KF-96 (
10,20,30,50,500゜1000.3000
(cs)), KF-56, KF-58, KF-54, and TSF4 manufactured by Toshiba Silicone Corporation.
51 series, TSF456 series, TSF410,
411,440,4420゜484,483,431,
433 series, T)lF450 series, TSF40
4.405, 406, 451-5A, 451-1OA,
437 series, TSF4440, 400, 401
, 4300 , 4445 , 4700 , 4450
, 4702, 4730 series, TSF434, 46
00 series, and R5 manufactured by Toshi Silicone Co., Ltd.
-200 etc. are mentioned.

Other solvents can be mixed with the above silicone oil polymerization solvent to the extent that the properties of the silicone oil are not impaired. Such solvents include aromatic hydrocarbon solvents such as toluene, xylene, and benzene; ethers;
Esters; Alcohol solvent; Aliphatic hydrocarbons such as n-hexane, n-octane, 1ro-octane, 1ro-dodecane, and mixtures thereof (commercially available products include Isopar H, G, L, and V manufactured by Exxon Chemical Co.) etc. The mixing ratio of such other solvents is approximately 0.1 to 500 parts by weight per 100 parts by weight of silicone oil.

On the other hand, specific examples of polymerizable vinyl hexamers include the following. First, examples of polymerizable vinyl monomers for homopolymerization or copolymerization with other monomers such as crosslinking agents are as follows.

Examples of polymerizable vinyl styrene: P-methylstyrene, α-methylstyrene, 2,5-dichlorostyrene, α-vinylpyridine, acrylonitrile, vinyl acetate, vinyl methyl ether.

Vinyl ethyl ether, vinyl isobutyl ether, vinyl chloride, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl formal, vinyl acetoacetal, vinyl propional, vinyl butyral, vinyl hexylal, vinyl alcohol, methyl acrylate, methyl methacrylate, ethyl acrylate, Ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 1so-butyl acrylate, n-
Octyl methacrylate, lauryl methacrylate, stearyl methacrylate ζ methacrylic acid, acrylic acid,
Na methacrylate, Na acrylate, divinylbenzene, styrene, ethylene glycol dimethacrylate, triethylene glycol triacrylate, etc.

In addition, examples of the above-mentioned polymerizable vinyl septamers for copolymerization include the following combinations.

(1) General formula (II) 1 CH2=C...(n) λ [However, R1 is -H or =CH, A is -COOCnH
z net or -0COCnH,net (n is 6 to 20
and the general formula (III) 1 CH2=C...CDI), which is an integer of

[However, R2 and R3 are -H or -CH□, and Otori is 1-2
It is an integer of 0. ] A combination of Shitsummer B represented by and monomer C having a carboxyl group or glycidyl group (Japanese Patent Application Laid-Open No. 62-1
(described in Publication No. 8410).

(2) A combination of the monomer A and a polyfunctional acrylic ester and/or a polyfunctional methacrylic ester (described in JP-A-56-79111).

(3) Combination of the monomer A and divinylbenzene or its alkyl (1 to 20 carbon atoms) derivative (JP-A-56
-145911)).

(4) The monomer A and the general formula (rV)2 [However, R2 and R3 are -H or =CH, and turtle is 1 to 2
It is an integer of 0. ] A combination of Nanatsumer-D represented by and Nanatsumer-C having a carboxyl group or a glycidyl group (JP-A-62-1
Described in Japanese Patent No. 8410 (5) The monomer A is represented by the general formula (V) (wherein R8 is -H or -CH, X is a halogen, and n represents an integer from 1 to 20.) Combination with Nanatsuma-E (JP-A-59-981
(described in Publication No. 14).

(6) The monomer A and the general formula (VI) [provided that R'
Lt-H Mata 4:! -CH,,R'',R1,R',RJi
halogen, -R5-COoHl-OH or a C1-C4 alkyl group, n is an integer of 1 to 20; ] (described in JP-A-60-248711).

(7) The monomer A and the general formula (■) (where R is -
H or -CH, n is an integer from 1 to 20. ) combination with monomer G shown in (JP-A-60-226512
(described in the issue).

(8) The above monomer A and the general formula (■) = shi12 (where, X is 10, -CH, or halogen, and n is 1-1
It is an integer of 0. ) combination with monomer H represented by (JP-A-60-24
(described in Publication No. 8718).

(9) The monomer A and the general formula (IK) 1 (wherein R1 and R2 are -H or -CH, and the parent is 1 to 2
It is an integer of 0. ) (Japanese Patent Application Laid-open No. 60-24
(described in Publication No. 8712).

(10) General formula (■') [However, R is hydrogen or a methyl group, A' is -COOCnH
, n+0. -0COCnH2n+, (n is an integer of 6 to 20), 2-ethylhexyl carbonate or cyclohexyl carbonate group. ] Monomer A' represented by general formula (X) (however, R2,
R1 is hydrogen or a methyl group, and ■ is an integer from 1 to 20.

) combination with monomer J shown in (JP-A-57-172
(described in Publication No. 905).

All known polymerization initiators can be used, such as benzoyl peroxide, lauryl peroxide, di-t
-Butyl peroxide, cumene hydroperoxide, hydrogen peroxide, anthin persulfate, potassium persulfate, azobisisobutyronitrile, and the like. In addition, dimethylaniline, pyridine, Co- or M as a polymerization accelerator
N-naphthinate etc. can be used in combination.

In the method of the present invention, polymerization solvent/polymerizable vinyl monomer/
The weight ratio of the polymerization initiator is 10-90/10-9010.0
Approximately 01-5 is appropriate.

In the polymerization process of the present invention, silica fine particles and softening point 60
Wax or polyolefin at about ~130°C can be added.

When fine silica particles are used, the resin is considered to be obtained with the fine silica particles incorporated in its crosslinked structure (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, dispersion stability can be further improved by having a specific gravity similar to that of an aliphatic hydrocarbon as a dispersion medium and by preventing gelation of the resin.

When wax or polyolefin is used.

These are dissolved in the reaction system by heating during the polymerization reaction, but
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 adsorbed on these fine particles. Here, wax or polyethylene 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. The appropriate amount of silica, wax or polyolefin, which also helps to improve adhesion, is about 5 to 50 parts by weight per 100 parts by weight of the resulting resin.

In addition, wax or polyolefin (softening point 60-13
Specific examples of commercially available products (at 0°C) are as follows.

Sensand (USA) Philips (USA) DuPont (USA) Allied Chemical (USA) Sanyo Chemical Union Carbide (USA) DYNI YNF DYNI (YNJ 3 ALATHON 10 ALATHON 12 ALATHON 14 ALATHON 16 ALATHON 20 ALATHON 22 ALAT)ION 25 AC-Polyethylene 1702 AC-Polyethylene 6 & 6A AC-Polyethylene 615 Sunwax 131-P Sunwax 151-P Sunwax 161-P 111 Sunwax 165-P 107 Sunwax 171-P 105 Sunwax E- 20095 Genuine Chemical Paraffin Wax 60-9
8 Kobayashi Kako exposed beeswax 65 cetanol 80 Nagai Kako exposed beeswax 65 made iron chemical Frozen 110 Mitsui Dupont Evaflex 210 80-95 Newucrell N100-110 Also, polymerizable vinyl monomers and resins used in graft polymerization Examples of combinations are as follows.

(1) An epoxy resin having an epoxy equivalent of 50 to 5,000 and the above-mentioned formula (
Polymerize monomer A represented by n).

The epoxy resin used here is sparingly soluble or insoluble in non-aqueous solvents with a solubility parameter of 8.5 or less,
Any synthetic resin having an epoxy group with an epoxy equivalent of 50 to 5000 can be used (Japanese Patent Publication No. 56-50
(described in Publication No. 893).

Specific examples of epoxy resins include the following manufactured by Shell Oil Company.

(2) Monomer A represented by the above-mentioned formula (II) and the general formula (X
I) R1 (However, R1 is -H or -CH, All is -COOH...(Xi) (However.

R1 is -H or -CH, a group.

B represents glycidyl methacrylate or glycidyl acrylate when -COOH or lylic acid is present, and when glycidyl methacrylate or glycidyl acrylate is present in the formula (■') or (X[), B represents acrylic acid. Or methacrylic acid. ] The esterified copolymer is esterified with a heptamer represented by
(described in Japanese Patent Publication No. 53-7952 and Japanese Patent Publication No. 56-9189).

(3) a) Copolymerizing the above-mentioned Shitsummer-A with an unsaturated carboxylic acid or glycidyl (meth)acrylate, b)
When this copolymer contains an unsaturated carboxylic acid in the composition of the copolymer, glycidyl (meth)acrylate is used, and when the copolymer contains glycidyl (meth)acrylate, it is unsaturated. C) The esterified copolymer is esterified with a carboxylic acid, and the esterified copolymer is esterified with acrylic acid, methacrylic acid, or a lower alkyl ester thereof (having 1 to 4 carbon atoms), styrene, methylstyrene, vinyltoluene, vinyl acetate, etc. Grafting with a vinyl monomer, d) This graft copolymer has the general formula (XI) [where 1 CH,=C B' R1 is -H or -CH,...(xl) B' is C00H1-COOC2H40H1-COOCH ,-C
H-C) I,, ゝ'0R' (However, R' is -CQ, - Sen, Sasa H1- (C Show 2,
-OH or -N82 group), polymerized with at least one member of the polar compound group consisting of a vinyl monomer represented by maleic acid, fumaric acid, atropic acid, allylamine, vinylamine, aroyl alcohol, vinylsulfonic acid, and vinylphosphoric acid. (Unexamined Japanese Patent Publication No. 1973)
-19085).

(4) a> Copolymerize the monomer ^ with a monomer K having a glycidyl group or a vinyl monomer having an aromatic carboxyl group.

b) The obtained copolymer is esterified with monomer if monomer K is used in step a), or with monomer if monomer L is used in step a), and C) the obtained copolymer is obtained. The esterified copolymer with the general formula (XIV) 1 CH, -C-Z -(Xm [However, R1 is -H or -CH3, Z is -cooco Peng H211+1 (II is an integer from 1 to 4), - 0COCm'
H,,'. 1 (,' is an integer from 1 to 6), -COOH1-COOC, H40H or -COOCH2
-CH-CH, is grafted with a compound represented by ]0', a monomer N selected from the group consisting of styrene, vinyl acetate, vinyltoluene, and chlorostyrene (as described in JP-A-55-90521). description).

(5) a) Nanatsuma-A and general formula (XV) (R is -H or -CH3 group, ALL is -COOH or -CO
OCH, -CH-CH, representing a group) ゝ0' is copolymerized, and b) this copolymer is formed into the general formula (XVI) CH2=C-(XVI) Bl/ ( However, R is -H or -CH' group, B'' is -COOH or when lylic acid is present, B'' represents glycidyl methacrylate or glycidyl acrylate, and monomer A or the above general formula (XV) is glycidyl methacrylate or glycidyl acrylate. If glycidyl acrylate is present, B
′ represents acrylic acid or methacrylic acid, C) The esterified copolymer is esterified with acrylic acid, methacrylic acid, or a lower alkyl ester thereof (C)
), grafting with polymerizable vinyl monomers such as styrene, vinyltoluene, and vinyl acetate (JP-A-50-98)
(described in Publication No. 592).

Furthermore, as the polymerization catalyst used in the present invention, AIBN
, BPO, phenylazotriphenylmethane, lauryl peroxide, di-t-butyl peroxide, t
-Butyl peroxide, cumene hydroperoxide, etc.

When the resin or resin dispersion obtained as described above is used for paints, electrophotographic liquid developers (or toners), printing inks, etc., colorants, other resins, etc. may be added to the resin or dispersion. For example, in the case of a developer, colorants include carbon black, oil blue, alkali blue, phthalocyanine blue, phthalocyanine green, spirit black, aniline black, oil violet, pendizine yellow, and methyl orange.

Examples include dyes or pigments such as brilliant carmine, fast red, and crystal violet. Other resins that can be added to the developer include natural resins such as acrylic resins, ester gums, and hardened rosins, maleic resins modified with these natural resins, phenolic resins, polyesters, and pentaerythritol resins.

〔Example〕

The present invention will be explained below by way of examples. Note that parts here are based on weight.

Example 1-3 and Comparative Example 1 Table 1 below was placed in a container equipped with a stirrer, thermometer, and reflux condenser.
300 g of the polymerization solvent described in 1 was taken and heated to 95°C.

In this, 150 g of 2-ethylhexyl methacrylate,
A mixture of 50 g of glycidyl methacrylate and 3 g of azobisisobutyronitrile was added dropwise over 1 hour, and the polymerization reaction was further carried out at 95° C. for 4 hours. The obtained resin was purified by reprecipitating it with metal and then dissolving it in toluene three times.

Next, the water repellency, oil repellency, and electrical resistance of each purified resin were measured, and the results shown in Table 1 were obtained.

In addition, the polymerization rate is also listed in Table-1.

Table-1 (Note) The measurement method is as follows.

Polymerization rate = (solid content of resin / theoretical solid content) x 100
(%) Water repellency: The contact angle of the resin surface to ion-exchanged water was measured using a contact angle measuring device manufactured by Kyowa Chemical Co., Ltd.

Oil repellency: The contact angle of the resin surface to 1so-dodecane was measured using a contact angle measuring device manufactured by Kyowa Kagaku Co., Ltd.

Electrical resistance: Measured using a vibration capacitance type microcurrent meter manufactured by Yokogawa Electric.

Examples 4 to 6 and Comparative Example 2 300 g of the polymerization solvent shown in Table 2 below was placed in the same reactor as Examples 1 to 3, and heated to 85°C. A mixture of 300 g of styrene and 3 g of benzoyl peroxide was added dropwise to this mixture over 1 hour, and then a polymerization reaction was further carried out at the above temperature for 3 hours. The obtained resin was purified in the same manner as in Example 1-3.

The performance of each purified resin is shown in Table 2. In addition, odor is also described in Table 2.

(Left below) Examples 7 to 9 and Comparative Example 3 Polymerization solvent 3 listed in Table 3 was placed in the same reactor as Examples 1 to 3.
00g was taken and heated to 130°C. In this, 300 g of lauryl methacrylate and 5 g of lauryl peroxide.
After dropping the mixture of g over 1 hour, the polymerization reaction was further carried out for 2 hours. The obtained resin was purified in the same manner as in Examples 1-3.

The performance of these purified resins is shown in Table 3. Table 3 also describes the separability of the resins.

(The following is a blank space) Furthermore, for Example 8 and Comparative Example 3, the drying properties of the obtained resins and the stability of the resin dispersions were investigated. The results are shown in the table-
4.

Table-4 The method for measuring these performances is as follows.

Drying property of resin: This is the drying time when a resin dispersion liquid was applied to a thickness of 10 pm on an AQ board and dried at 50°C.

Stability of dispersion: The presence or absence of sedimentation was examined when the resin dispersion was stored at 50°C for one month.

Examples 10-12 and Comparative Example 4 In the same reactor as Examples 1 to 3, 250 g of the polymerization solvent described in Cloth-5 below and 50 g of Isopar H were placed and heated to 90°C. In this, 100g of methylstyrene, 1g of methacrylic acid
Add 5g and 10g of azobisisobutyronitrile,
After 0 drops, which were added over a period of time, the polymerization reaction was further carried out at 90° C. for 4 hours. The obtained resin was purified in the same manner as in Examples 1-3.

The performance of these purified resins is shown in Table 5, and Example 11
Regarding the resin dispersion of Comparative Example 4, the coating properties were also described.

(Left below) Example 13 Silicone oil KF96L (lcs) in a four-way flask equipped with a stirrer, condenser, thermometer, and dropping funnel.
300g was taken and heated to 90°C.

Next, a mixed solution consisting of 90 g of 2-ethylhexyl methacrylate, tog of maleic acid, and 3 g of azobisisobutyronitrile was added dropwise to the flask for 1 hour to polymerize, and the mixture became cloudy after 30 minutes. Furthermore, when 1.0 g of diethylamine was added and polymerized at 90° C. for 6 hours, a resin dispersion with a polymerization rate of 98.9% was obtained.

The resulting resin dispersion was heated at 50"C, 20'C, and O'C for 3
Although it was stored for 0 days, there was no aggregation or phase separation in any case. Additionally, this resin showed good water and oil repellency.

Example 14 Silicone oil KFS4 100g Epicron 200 (I wipe!! shoe ester type 2 I Kishi I!, Dainippon Kagakusha 1
) 50g lauryl methacrylate 6
After polymerizing a mixed solution consisting of 30 g of paraffin wax (manufactured by Junsei Kagaku Co., Ltd., softening point 82°C) at 90°C for 4 hours in a flask, azobisisobutyronitrile was further added. Ig was added and polymerized for 2 hours to obtain a resin dispersion with a polymerization rate of 980 g%.

The resulting resin dispersion was stable even when stored at 50°C for one month.

Example 15 A mixed solution consisting of H5-200 (silicone oil, manufactured by Toshi Silicone Co., Ltd.) 100 g, isooctane 150 g, lauryl methacrylate 20 g, cetyl methacrylate 25 g, Eport YD-115log (manufactured by Tobu Kasei Co., Ltd., epoxy resin), fumaric acid 10 g, benzoyl peroxide 2 g After polymerizing in a flask at 95° C. for 4 hours, 300 g of isooctane was added to prepare a resin dispersion. The resulting resin dispersion was stable even when stored at 50°C for one month. Note that the polymerization rate was 97.8%.

Example 1G Stearyl methacrylate 100g Methyl methacrylate 30g Epoxy resin (Chissonox CX-206 manufactured by Chisso Chemical Co., Ltd.) 15
gAcrylic acid 20g Polyethylene ACS & 6A (manufactured by Allied Chemical Co., Ltd.) 50g F58 (silicone oil) 150g Azobisisobutyronitrile After polymerizing a mixed solution consisting of 5g at 90°C for 2 hours in a flask, azobisisobutyronitrile was added. 3g, KF58 (silicone oil) 300. was added, polymerized at 90°C for further 4 hours, and then cooled to obtain a resin dispersion with a zero polymerization rate of 98.5%.

This dispersion was stored at 0°C, 20°C, and 50°C for one month, but no sedimentation, phase separation, or aggregation occurred in any case.

Furthermore, the water and oil repellency of the resin was also good.

Example 17 2-ethylhexyl methacrylate 400gTSF
410 100 g Epicron 200 tsg Methacrylic acid 10 g Azobisisobutyronitrile After polymerizing a mixed solution consisting of 3 g at 90°C in a flask for 4 hours, triethylamine 0.1 g and Isopar 6300 g - AC - Polyethylene 6 & 6A
30g was added and the reaction was further carried out at 90°C for 4 hours. As a result, a resin dispersion with a polymerization rate of 99.0% was obtained. This dispersion was stored at 0°C, 20°C, and 50°C for one month, but no sedimentation, aggregation, or phase separation occurred in any case.

Example 18 300 g of silicone oil (KF96L O, 65 cs) was placed in a container equipped with a stirrer, a thermometer, and a reflux condenser.
Heated to 95°C. In this, 150 g of 2-ethylhexyl methacrylate, 50 g of glycidyl methacrylate,
A mixture of 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. Add 15 g of acrylic acid, 0.1 g of hydroquinone, and Ig of lauryl dimethylamine to this and add 9
The reaction was carried out at 0° C. for 15 hours to esterify the copolymer obtained in the above reaction. The degree of esterification was in the range of 25-30% from the measurement of the decrease in acid value. 500% of silicone oil (KF96L O, 65cs) was added to the esterification reaction solution.
50 g of methyl methacrylate and 3 g of azobisisobutyronitrile were added dropwise at a constant rate over 3 hours at 90°C, and the liquid temperature was maintained at the above temperature for about 5 hours to complete the reaction. Furthermore, 300 g of silicone oil (KF96L 0.65 cs) was added to 300 g of this reaction product.
The mixture was heated to 90° C., 50 g of polyethylene (Orizon 805 manufactured by Monsando Chemical Co., Ltd.) was added, and the mixture was heated and dissolved for 1 hour until it became transparent. The resin solution was cooled with tap water while stirring. The results of the adhesion test of the obtained resin dispersion (adhesive composition) are summarized in Table 6.

Example 19 Silicone oil (H5-
200) After taking 400 g and heating it to 95°C, a mixed solution of 150 g of stearyl methacrylate, 30 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 copolymerize. A combination was prepared. Subsequently, 1 g of lauryl dimethylamine, 15 g of methacrylic acid, and 0 of hydroquinone were added to the reaction solution.
．． 1 g was added and the esterification reaction was carried out at 95°C for 10 hours.
The degree of esterification was 30%.

Next, 600 g of isooctane was added to this reaction solution at 95°C.
A mixed solution consisting of 60 g of styrene and 4 g of benzoyl peroxide was added dropwise over a period of 3 hours, and the reaction was continued for a further 5 hours. Silicone oil (
H5-200) 200g was added thereto, and 50g of polyethylene (DYNI manufactured by Union Carbide) was added and dissolved at 95°C, and the mixture was further stirred for 40 minutes and then cooled. The results of the adhesion test of the obtained resin dispersion (adhesive composition) are summarized in Table 6.

Example 20 400 g of silicone oil (TSF4600) was placed in a reactor similar to Example 18, heated to 90°C, and then a mixed solution of 130 g of lauryl methacrylate, 50 g of crotonic acid, and 1 g of benzoyl peroxide was added dropwise over 2 hours. death,
Then, the temperature was maintained for 3 hours to complete the reaction. Lauryl dimethylamine and 30 g of glycidyl methacrylate were added to this reaction solution, and an esterification reaction was carried out at 90° C. for 20 hours. The degree of esterification at this time was 50%. Silicone oil (TSF4600) 600 was added to this reaction solution.
g was added thereto, heated to 90° C., a mixed solution of 40 g of ethyl acrylate and 4 g of benzoyl peroxide was added dropwise over 3 hours, and the reaction was further carried out for 5 hours.

Silicone oil (TSF4) was added to 200 g of this reaction product.
After adding 200 g of polyethylene (DYNI (manufactured by Union Carbide) and dissolving it at 90°C, the mixture was stirred for 1 hour and rapidly cooled. The resulting resin dispersion (
Table 6 summarizes the results of the adhesion test for the adhesive composition.

Example 21 400 g of silicone oil (KF96) was placed in the same reactor as in Example 18, heated to 85°C, and then 120 g of 2-ethylhexyl methacrylate and 60 g of methacrylic acid were added.
and azobisisobutyronitrile (3 g) dropwise over 2 hours, and then maintained at 85°C for 2 hours to complete the reaction. 1. Next, lauryl dimethylamine I was added to the reaction solution.
g and 30 g of glycidyl acrylate at 85°C.
Allow to react for 8 hours. The degree of esterification at this time was 50%. Silicone oil (KF96) is added to this reaction product.
After adding 400g and heating to 90℃, add 30g of vinyl acetate.
A mixed solution of 3 g of azobisisobutyronitrile and 3 g of azobisisobutyronitrile was added dropwise over 3 hours, and the reaction was further carried out for 5 hours.Next, silicone oil (F1a) was added to 200 g of this reaction product.
After adding and dissolving 20 g of polyethylene (Alathon-12 manufactured by DuPont) at 85° C., stirring was continued for 1 hour and then rapidly cooled. The obtained resin dispersion (
Table 6 summarizes the results of the adhesion test for the adhesive composition.

Example 22 Silicone oil (in F1) was placed in a reactor similar to Example 18.
a) After heating 300g to 90℃, add 2-
A mixture of 150 g of ethylhexyl methacrylate, 35 g of glycidyl methacrylate, and benzoyl peroxide was added to the
The mixture was added dropwise over a period of time and maintained at the temperature for 3 hours to complete the reaction. The solid content of the obtained copolymer was 4
It was 0.2%. Further, 1 g of lauryl dimethylamine, 20 g of maleic acid, and 0.05 g of hydroquinone were added to this copolymer and reacted at 90° C. for 15 hours. The acid value of the reaction product was 2.0.

Next, apply silicone oil (KF54) 520 to this product.
After adding g, a mixture of 40 g of vinyltoluene and 3 g of benzoyl peroxide was added dropwise at 90° C. over a period of 3 hours, and the reaction was continued for 5 hours. Add 200 g of silicone oil (KF54) to 200 g of this reaction product, and
After heating, 100 g of polyethylene and resin (Sunwax 131P manufactured by Sanyo Chemical Co., Ltd.) were added and dissolved. After dissolving, the mixture was stirred for 1 hour and rapidly cooled. The results of the adhesion test of the obtained resin dispersion (adhesive composition) are summarized in Table 6.

Example 23 Silicone oil (KF50
) and 50 g of polyethylene resin (Sunwax 171P manufactured by Sanyo Chemical Co., Ltd.) were added and heated to 90°C to form a solution.

A mixed solution of 200 g of stearyl acrylate, 20 g of glycidyl methacrylate, and 3 g of azobisisobutyronitrile was added dropwise over 5 hours, and then stirred at this temperature for about 3 hours. Next, 10.0 g of acrylic acid was added. , lauryl dimethylamine Ig, and 0.5 g of hydroquinone were added and heated to 90°C.
The reaction was carried out for 10 hours. Subsequently, 300 g of silicone oil (KF50) was added, and a mixture of 40 g of styrene monomer and 3 g of azobisisobutyronitrile was added at 95° C. over 3 hours, and the reaction was further carried out for 5 hours.
Add 2 silicone oil (KF50) to 150 g of this reactant.
After stirring at 90° C. for 30 minutes, the mixture was rapidly cooled.

The results of the adhesion test of the obtained resin dispersion (adhesive composition) are summarized in Table 6.

Example 24 In Example 23, paraffin wax manufactured by Junsei Yakuhin Co., Ltd. (melting point 70°C ~
72° C.) to obtain a resin dispersion (adhesive composition). Table 6 summarizes the adhesion test results for this product.
Shown below.

1 to -6 Ning particle size is resin particles.

Regarding the stability, those with no sedimentation separation due to storage at 50'C for 3 months were rated as ○.

Rumored adhesive strength of polyethylene surface Example 25 After stirring, 3, O equipped with a thermometer, cooling pipe and dropping funnel
Silicone oil (KF9611cs) in the ff flask
) Pour SOOg, heat to 80°C, and add 100g of lauryl acrylate as component A to the mixture while stirring.
A monomer solution consisting of 50 g of the monomer of the following formula (1) as component B and 5 g of methacrylic acid Log and azobisisobutyronitrile as component C was added dropwise over 2 hours. Thereafter, polymerization was carried out at this temperature for 4 hours. As a result, 1 polymerization rate was 97%, viscosity was 120 cp, and particle size was 0.1-
A resin dispersion of 0.211 Im was obtained.

Example 26 Silicone oil (KF) was added to the flask used in Example 25.
58) Take 400g and heat to 90°C, and while stirring add 95g of 2-ethylhexyl methacrylate as the ^ component and 25g of the monomer of the following formula (2) as the B component.
, Glycidylpropyl acrylate Lo as component C
g. Similarly as component C, a monomer solution consisting of 5 g of acrylic acid and 2 g of azobisisobutyronitrile was added dropwise over 1 hour, followed by a polymerization reaction at this temperature for 6 hours.

As a result, the polymerization rate was 98.8%, the viscosity was 220 cp, and the particle size was 0.
．． 01-0.12. A resin dispersion was obtained. The electrical resistance of the resin was 1°0×10 14 Ω·1.

Example 27 Silicone oil (H5-
200) Take 400g and heat it to 90℃, add 20% of cyclohexyl acrylate as component A to it while stirring.
0 g, 10 g of the monomer of the following formula (3) as the B component, 5 g of methacrylic acid as the C component, glycinyl methacrylate Log as the C component, and 3 g of penzoyl bar ohside were added, and the mixture was heated at the above temperature for 4 hours. After carrying out the polymerization reaction, 0.1 g of vinylpyridine was added thereto and esterification was carried out at 80° C. for 10 hours. As a result, a resin dispersion having a polymerization rate of 98%, a viscosity of 320 cp, and a particle size of 0.05 to 1.0 was obtained.

This product had little odor, and the resin had good heat resistance and cold resistance.

Example 28 Silicone oil (KF) was added to the flask used in Example 25.
9610cs) and polyethylene (AC polyethylene 1105 manufactured by Allied Chemical Co., Ltd.) and heated to 90°C.
The polyethylene was heated to dissolve the polyethylene. This contains 100 g of stearyl methacrylate as the A component, 200 g of the following formula (4) as the B component, 1 g of acrylic acid as the C component, and 8 g of glycidyl acrylate and azobisisobutyronitrile Log as the C component. The monomer solution was added dropwise using a dropping funnel over 2 hours, and the polymerization reaction was carried out at the above temperature for 6 hours while stirring. Next, 100 g of methyl methacrylate and 5 g of t-butyl peroxide were added as component C, and the mixture was further heated at 130°C. By carrying out a polymerization reaction while stirring for 6 hours, the polymerization rate was 98.6%, the viscosity was 260 cp, and the particle size was 0.
A resin dispersion of 1 to 0.2 was obtained.

Examples 29-34 Silicone oil, A component, B component shown in Table-7.

A resin dispersion was obtained in the same manner as in Example 25 using component C and component C. These resins have a high contact angle with water,
It showed good water repellency.

(Left below) Example 35 Carbon black 10g (Laben 100 manufactured by Columbia Carbon) Resin dispersion obtained in Example 25 Sog silicone oil (K
F96L 1cs) 100g was dispersed in a kedimir for 6 hours to obtain a concentrated toner with a viscosity of 30cp, and the log was dispersed in KF96L (Ics) 1M to prepare a resin dispersion (liquid developer for electrostatic photography).

Subsequently, this developer was placed in a commercially available electrophotographic copying machine and copies were made on commercially available zinc oxide sensitized paper. Many copies with good single image density, single image fixing properties, and drying properties were obtained.

In addition, after storing this developer at 50°C for 3 months to forcefully deteriorate it, copying was performed in the same manner as above to determine the image density, and almost no temperature drop was observed.
It was confirmed that there was no deterioration.

Example 36 Place 300 g of silicone oil (KF96L 3.Ocs) in a container equipped with a stirrer, thermometer, and reflux condenser, and add 9
Heated to 5°C. A mixture of 200 g of 2-ethylhexyl methacrylate, Log glycidyl methacrylate, and 3 g of azobisisobutyronitrile was added dropwise to the mixture at a constant rate over 3 hours, and the mixture was further stirred for 1 hour to complete the reaction. Add 5 g of acrylic acid, 0.1 g of hydroquinone, and Ig of lauryl dimethylamine to this and bring to 90°C.
The copolymer obtained in the above reaction was esterified by reacting for 15 hours. The degree of esterification is determined by measuring the decrease in acid value.
It was in the range of 5-30%. Next, 500 g of silicone oil (KF96L 3.Ocs) was added to the esterification reaction solution.
and 50 g of methyl methacrylate at 90°C.

3 g of azobisisobutyronitrile was 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, this reaction product 300
After adding 300g of KF96L (3,Ocs) to g, 90
℃ and polyethylene (Oriz manufactured by Monsando Chemical Co., Ltd.).
On805) 50g was added and dissolved by heating for 1 hour until it became transparent.

Next, vinylpyridine Log and 1 g of azobisisobutyronitrile were added to the solution of the graft copolymer having polyethylene as the core, and the mixture was reacted at 90° C. for 3 hours. When the resulting resin solution is rapidly cooled with tap water while stirring, the solid content decreases to 1.
A milky resin dispersion with a particle size of 8.3% and a particle size of 0.3 to 1 pm was obtained.

Example 37 A milky resin dispersion was prepared in the same manner as in Example 36 except that maleic acid was used instead of acrylic acid to esterify the 2-ethylhexyl methacrylate-turglycidyl methacrylate copolymer.

Example 38 400 g of H5-Zoo was placed in the same reactor as in Example 36 and heated to 95°C, and then a mixed solution of 200 g of stearyl methacrylate, glycidyl acrylate Log and benzoyl peroxide was added dropwise over 1 hour, and then The reaction was completed by stirring at 95°C for an hour to prepare a copolymer. Subsequently, 1 g of lauryl dimethylamine, 3 g of methacrylic acid, and 0.1 g of hydroquinone were added to the reaction solution.
The esterification reaction was carried out at ℃ for 10 hours. The degree of esterification was 30%.Next, 600g of silicone oil 15-200 was added to this reaction solution while maintaining the temperature at 95°C.
60 g of styrene and 4 g of benzoyl peroxide over 3 hours.
A mixed solution consisting of g was added dropwise, and the graft reaction was further carried out for 5 hours. Silicone oil H5-20 is added to this reaction product.
After adding 200g of paraffin wax (softening point 70-72℃) and melting at 95℃,
The reaction was carried out at 95° C. for 0 minutes. Subsequently, 5 g of N-vinylpyrrolidone and 1 g of benzoyl peroxide were added to this resin solution and polymerization was carried out at 95°C for 3 hours, and then cooled with tap water while stirring to obtain a solid content of 21% and a particle size of 0.1 to 0. A milky resin dispersion of 2 tones was obtained.

Example 39 400 g of KF58 was placed in a reactor similar to Example 36,
200g lauryl methacrylate after heating to 90℃
A mixture of 3 g of crotonic acid and 1 g of benzoyl peroxide was added dropwise over 2 hours, and the temperature was maintained for 3 hours to complete the reaction. To this reaction solution, 1 g of lauryl dimethylamine was added and an esterification reaction was carried out at 90° C. for 20 hours. The degree of esterification at this time was 50%. Add 58,600 g of KF to this reaction solution, heat to 90°C, and add 3 g of a mixture of 40 g of ethyl acrylate and 4 g of benzoyl peroxide.
The mixture was added dropwise over a period of time, and the reaction was further carried out for 5 hours. 200 g of Aituno Dai-L was added to 200 g of this reaction product, and the mixture was heated to 90°C using polyethylene (Union Carbide D).
20 g of YNH) was added and dissolved, 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, and then cooled with tap water while stirring, resulting in a solid content of 12.1% and a particle size of 0.
A milky resin dispersion of 3-0.5 AIs was obtained.

Example 40 400 g of TSF410 was placed in a reactor similar to Example 36, heated to 85°C, and then a mixed solution of 200 g of 2-ethylhexyl methacrylate, 5 g of methacrylic acid, and 3 g of azobisisobutyronitrile was added over a period of 2 hours. and drip.

Thereafter, the temperature was maintained at 85° C. for 2 hours to complete the reaction.

Next, 1 g of lauryl dimethylamine and 5 g of glycidyl acrylate were added to the reaction solution and reacted at 85° C. for 18 hours. The degree of esterification at this time was 50%.

After adding 400 g of TSF410 to this reaction product and heating it to 90°C, a mixed solution of 30 g of vinyl acetate and 3 g of azobisisobutyronitrile was added dropwise over 3 hours, and
After a time reaction, 8200 g of Isopar was added to 200 g of this reaction product, and polyethylene (
20 g of Alathon-12) manufactured by DuPont was added and dissolved, and reacted for 1 hour. Furthermore, 6 g of diethylaminoethyl methacrylate and 0.5 g of azobisisobutyronitrile were added to this solution, polymerized at 85° C. for 5 hours, and cooled with tap water while stirring to obtain a solid content of 14.1%.

A milky resin dispersion with a particle size of 0.6-0.9 m was obtained.

Comparative Examples 5 to 9 Five types of latex (Comparative Examples 5 to 9) were made in the same manner as in Examples 36 to 40, except that toluene was used instead of silicone oil.

Table 8 shows the water repellency, oil repellency, and electrical resistance of the resins of Examples 36 to 40 and Comparative Examples 5 to 9 obtained as described above.

Table 8 Example 41 K in a four-loop flask equipped with a thermometer, stirrer and condenser
After taking 200 g of F58 and heating it to 90°C on an oil bath, 8100 parts of stearicita methacrylate, 30 parts of glycidyl methacrylate, and 5 parts of azobisisobutyronitrile were added, and a copolymerization reaction was carried out at this temperature for 5 hours. . Next, 0.5 parts of hydroquinone, 20 parts of β-methacryloxyethylic acid sophthalate, and 0.02 parts of lauryldimethylamine were added, and an esterification reaction was carried out at 85° C. for 5 to 10 hours. Furthermore, 50 parts of styrene and 1 part of benzoyl peroxide were added to carry out graft polymerization.

AC polyethylene 6 was added to the obtained graft copolymer dispersion.
Add 50 parts of A (manufactured by Allied Chemical Co.), 80-9
It was kept in solution for 4 hours at 0°C. Then, the oil bath was removed and the mixture was cooled with water to obtain a non-aqueous resin dispersion.

Example 42 KF96L (2,0 cs
), and heated to 90°C on an oil bath, then added 100 parts of cetyl methacrylate, 20 parts of β-methacryloroxyethyl acid hexahydrophthalate and 3 parts of benzoyl peroxide, and heated at 100°C for 4 hours. After the copolymerization reaction, 1 part of hydroquinone, 10 parts of glycidyl methacrylate, and 0.0 parts of dodecylamine were added.
1 part was added and the esterification reaction was carried out at 80°C for 10 hours. Furthermore, 30 parts of methyl methacrylate and 0.05 part of azobisisobutyronitrile were added, and graft polymerization was carried out at 90° C. for 3 hours.

Sunwax E20 was added to the obtained graft copolymer dispersion.
0 (manufactured by Sanyo Chemical Co., Ltd., low molecular weight polyethylene) was added thereto, and the mixture was heated at 90° C. for 1 hour to obtain a non-aqueous resin dispersion.

Example 43 300 parts of KF54 was taken in the same flask as in Example 41,
After heating to 80°C, 100 parts of lauryl methacrylate, 25 parts of glycidyl acrylate, and 3 parts of lauroyl peroxide were added, and a copolymerization reaction was carried out at the same temperature for 5 hours. Furthermore, 0.1 part of hydroquinone, 0.001 part of lauryldimethylamine, and 20 parts of a compound of the following formula (8) were added, and an esterification reaction was carried out at the above temperature for 10 hours. Furthermore, 30 parts of vinyl acetate was added to this to obtain a graft copolymer dispersion.

Comparative Example 10 A dispersion was prepared by following the method of Example 41, except that toluene was used instead of KF58.

Comparative Example 11 A dispersion was prepared in the same manner as in Example 42, except that toluene was used instead of KF96L (2.0 cs).

Comparative Example 12 A dispersion was prepared by following the method of Example 43, except that toluene was used instead of KF54.

Esterification rate of the product obtained as above.

The polymerization rate, particle size 1 dispersion stability, and water repellency of the resin are as follows:
9.

(The above is a blank space) Example 44 In the same flask as in Example 41, 300 g of dimethyl silicone oil (viscosity 1.5 cs) was placed and heated to 95°C.

In this, 150 g of 2-ethylhexyl methacrylate,
After adding a mixture of 50 g of glycidyl methacrylate and 3 g of azobisisobutyronitrile dropwise over 1 hour, the mixture was left for another 4 hours9.
Hydroquinone 0°5g, β was reacted at 5°C.
- 820g of methacryloxyethylic acid phthalate - 0.1g of pyridine was added and esterified at 80°C for 15 hours.

Furthermore, 100 g of methyl methacrylate and 3 g of azobisisobutyronitrile were added, and graft polymerization was carried out at 90° C. for 4 hours. The obtained resin was purified by reprecipitating it with methanol and then dissolving it in toluene three times.

For comparison, polymerization and purification were carried out in the same manner except that toluene was used as the polymerization solvent instead of dimethyl silicone oil.

The polymerization rate, water repellency, oil repellency, and electrical resistance of each purified resin are shown in Table 10 below.

Table 10 Example 45 Put 300 g of dimethyl silicone oil (viscosity 1, 5 cs) in a container equipped with a stirrer, thermometer, and reflux condenser.
Heated to 95°C. In this, 200 g of 2-ethylhexyl methacrylate, glycidyl methacrylate Log,
A mixture of 3 g of abbisisobutyronitrile was added dropwise at a constant rate over 1 hour, and the mixture was further stirred for 1 hour to complete the reaction. Add 5 g of acrylic acid, 0.1 g of hydroquinone, and 1 g of lauryl dimethylamine to this and add 90
Esterification was carried out by reacting at °C for 15 hours.

The degree of esterification was 36% due to the reduction in acid value.

Next, 55% of dimethyl silicone oil was added to the esterification reaction solution.
00 g was added thereto, and at 90° C., 50 g of methyl methacrylate and 3 g of azobisisobutyronitrile were added dropwise at a constant rate over 5 hours, and the liquid temperature was maintained at the above temperature for about 5 hours to complete the reaction. Furthermore, 300 g of Isopar G was added to 300 g of this reaction product, and the mixture was heated to 90°C and made of polyethylene (Orizon 805 manufactured by Monsando Chemical Co., Ltd.) 50
Add g and heat to dissolve for 1 hour until it becomes transparent. The resin solution is cooled with tap water while stirring. The obtained product has a polymerization rate of 94.2%, water repellency of 25°6 degrees, and oil repellency of 28.3 degrees.
It was 0 degrees.

Example 46 400 g of dimethyl silicone (viscosity 3.Ocs) was placed in the same reactor as in Example 45, heated to 95°C, and a mixed solution of 200 g of stearyl methacrylate, glycidyl acrylate Log, and benzoyl peroxide was added in 1 hour. The mixture was added dropwise and then stirred at 95° C. for 3 hours to complete the reaction and prepare a copolymer. Subsequently, 1 g of lauryl dimethylamine, 3 g of methacrylic acid, and 0 of hydroquinone were added to the reaction solution.
．． 1 g was added, and the esterification reaction was carried out at 95° C. for 10 hours. The degree of esterification was 32.5%. Next, 600 g of the silicone oil was added to this reaction solution, and while maintaining the temperature at 95° C., a mixed solution consisting of 60 g of styrene and 6 g of benzoyl peroxide was added dropwise over 3 hours. The reaction was then continued for an additional 5 hours. 200 g of the silicone oil was added to this reaction product, and 50 g of polyethylene (DYNI manufactured by Union Carbide) was added and dissolved at 95°C. The mixture was stirred for an additional 40 minutes, and then cooled to form a paste-like resin dispersion. Obtained.

This product has a polymerization rate of 92.8% and a grafting rate of 51.0%.
, water repellency was 29 degrees.

Example 47 400g of silicone oil (TSF400) was added to Example 4.
A mixture of 200 g of lauryl methacrylate, 3 g of crotonic acid and 1 g of benzoyl peroxide was added dropwise over 2 hours, and the temperature was then maintained for 3 hours to react. complete.

To this reaction solution, 1 g of lauryl dimethylamine and 10 g of glycidyl methacrylate were added, and an esterification reaction was carried out at 90° C. for 20 hours. The degree of esterification at this time was 542. Add silicone oil TSF400600 to this reaction solution.
g was added thereto, heated to 90° C., a mixed solution of 40 g of ethyl acrylate and 6 g of benzoyl peroxide was added dropwise over 3 hours, and the reaction was continued for an additional 5 hours. This reaction product 20
After adding 200 g of Isopar L to 0 g and dissolving 20 g of polyethylene (DYNH manufactured by Union Carbide) at 90° C., the mixture was stirred for 1 hour and rapidly cooled to obtain a resin dispersion. This product has a polymerization rate of 93.2%, a grafting rate of 38%,
Water repellency was 24 degrees.

Example 48 400g of silicone oil (TSF404) was added to Example 4.
2-ethylhexyl methacrylate, methacrylic acid 5.
A mixture of g 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, 1 g of lauryl dimethylamine and 5 g of glycidyl acrylate were added to the reaction solution. Add 1 at 85℃
Allow to react for 8 hours. The degree of esterification at this time was 52%. Add 400 g of the silicone oil to this reaction product.
was added and heated to 90°C, a mixture of 30 g of vinyl acetate and 3 g of azobisisobutyronitrile was added dropwise over 3 hours, and the reaction was continued for an additional 5 hours. Add 200g of H and heat at 85°C to polyethylene (Nucrel N-599 manufactured by DuPont)
After adding and dissolving 20 g, stirring was continued for 1 hour and then rapidly cooled to obtain a resin dispersion. This product had a polymerization rate of 95% and water repellency and oil repellency of 31 degrees and 26 degrees, respectively.

Example 49 Silicone oil (H5-
200) 3J: After taking a JOg and heating it to 90°C, a mixed solution of 200 g of 2-ethylhexyl methacrylate, 10 g of glycidyl methacrylate, and benzoyl peroxide was added dropwise into the JOg over 2 hours.1. The temperature was maintained for an additional 3 hours to complete the reaction. The solid content of the obtained copolymer was 41.1%. Furthermore, lauryl dimethylamine Ig, 3 g of maleic acid, and 0.05 g of hydroquinone were added to this copolymer and reacted at 90° C. for 15 hours. The acid value of the reaction product was 2.0.

Next, 520 g of isooctane was added to this product, and then a mixture of 40 g of vinyltoluene and 3 g of benzoyl peroxide was added dropwise at 90° C. over 3 hours, and the reaction was continued for 5 hours. The resulting resin dispersion had a polymerization rate of 92.5%.
, water repellency and oil repellency were 31 degrees and 30 degrees, respectively.

Example 50 300 g of dimethyl silicone oil (viscosity 1.5 cs) was placed in a reactor similar to Example 45 and heated to 95°C.

In this, 150 g of 2-ethylhexyl methacrylate,
A mixture of 50 g of glycidyl methacrylate and 3 g of azobisisobutyronitrile was added dropwise over 1 hour, and the polymerization reaction was further carried out at 95° C. for 4 hours. Furthermore, 5g of methacrylic acid is added to this.
, 0.1 g of hydroquinone and 0.5 g of lauryldimethylamine were added, and esterification was carried out at 80° C. for 20 hours. The degree of esterification was 32 stones. Next, 500 g of the dimethyl silicone oil was added to the esterification reaction solution, and 90 g of the dimethyl silicone oil was added.
50 g of methyl methacrylate and 3 g of azobisisobutyronitrile were added at °C, and a polymerization reaction was carried out for 3 hours. The obtained resin was purified by reprecipitating it with methanol and then dissolving it in toluene three times.

For comparison, polymerization and purification were carried out in the same manner except that toluene was used instead of dimethyl silicone oil.

Polymerization rate and water repellency of each purified resin.

The resistance is shown in Table 11 below.

Table 11 Oil repellency and electricity Example 51 Into a 2Q flask equipped with a stirrer, thermometer and reflux condenser, 800 g of KF960 (viscosity 1.5 cs) was placed,
Heated to 0°C. In this, lauryl methacrylate 17
A solution consisting of 0 g, diethylene glycol dimethacrylate 80 g and benzoyl peroxide was added dropwise over 2 hours to cause a polymerization reaction, and then to complete the reaction,
Stir at 95°C for 2 hours, with a polymerization rate of 97% and a viscosity of 270 cp.
A resin dispersion was obtained. The gel content (insoluble content in tetrahydrofuran) of this resin was 25% by weight. Example 52 250 g of the resin dispersion obtained in Example 51 was mixed with 20 g of polyethylene (DYNF manufactured by Union Carbide) in a flask. After heating and dissolving at 110° C. for 8 hours, the mixture was cooled to obtain a polyethylene-containing resin dispersion having a viscosity of 100 cp. Note that the particle size of this resin was 3 to 5 AIs.

Example 53 Take 800 g of H3-200 in the same container as Example 51,
6 heated to 95°C, then add 1 cetyl methacrylate to this
70g, methacrylic acid 3g, dipropylene glycol methacrylate 50g and azobisisobutyronitrile 5g
A solution consisting of g was added dropwise over 1 hour to cause a polymerization reaction, and the reaction was completed by further heating at 95° C. for 8 hours. In this way, a resin dispersion with a polymerization rate of 99% and a viscosity of 320 cp was obtained. The gel content of this resin was 32% by weight.

Example 54 250 g of the resin dispersion obtained in Example 53 was mixed with 18 g of bleached beeswax in a flask, heated and stirred at 100°C for 2 hours, and then cooled to obtain a bleached beeswax-containing resin dispersion with a viscosity of 110 cp. Prepared. The particle size of this resin is 2.
It was 0 to 3.8 habit.

Example 55 In the same container as in Example 5I, 800 g of TSF40 and log of silica powder with a particle size of 0.5 to 1 tone were taken and heated to 95°C.

In this, 150 g of 2-ethylhexyl methacrylate,
A solution consisting of 50 g of trimethylolpropane triacrylate and 5 g of azobisisobutyronitrile was added dropwise over 2 hours to cause a polymerization reaction, and the reaction was further stirred at 95° C. for 2 hours to complete the reaction. Thus, the polymerization rate is 98
A resin dispersion having a viscosity of 120 cρ was obtained. The particle size of this resin was 1-8 pa.

Example 56 800 g of KF5g and 50 g of polyethylene (Sunwax 181-P) were placed in the same flask as in Example 51 and heated to 95°C. Next, 150 g of stearyl methacrylate, 3 g of dimethylaminoethyl methacrylate, and tetramethylol were placed in the same flask as in Example 51. A solution consisting of 21 g of methane tetramethacrylate and 5 g of lauryl peroxide was added dropwise at the above temperature to cause a polymerization reaction, and then the reaction was completed by further heating at the same temperature for 8 hours. In this way, a resin dispersion with a polymerization rate of 96% and a viscosity of 95 cp was obtained. The particle size of this resin was 8-4 pm.

Example 57 In the same container as in Example 51, 300 g of dimethyl silicone oil (viscosity 1, 5 cs) was placed and heated to 95°C.

In this, 150 g of 2-ethylhexyl methacrylate,
5 g of ethylene glycol dimethacrylate, 3 g of methacrylic acid, 20 g of styrene, 5 g of glycidyl methacrylate
0 g of azobisisobutyronitrile and 3 g of azobisisobutyronitrile.
After the dropwise addition, the polymerization reaction was carried out at 95° C. for an additional 4 hours. The obtained resin was purified by reprecipitating it with methanol and then dissolving it in toluene three times.

For comparison, polymerization and purification were carried out in the same manner except that toluene was used as the polymerization solvent instead of dimethyl silicone oil.

The performance of these purified resins is shown in Table 12 below.

Table 12 Example 58 In a 212 flask equipped with a stirrer, a thermometer, and a reflux condenser, 30 g of dimethyl silicone oil (viscosity 1.5 cs) was added.
0 g was taken and heated to 95°C. In this, 150 g of 2-ethylhexyl methacrylate and 5 g of divinylbenzene.
, 190g of styrene, 50g of glycidyl methacrylate
A mixture of 3 g of azobisisobutyronitrile and 3 g of azobisisobutyronitrile was added dropwise over 1 hour, and the polymerization reaction was further carried out at 95° C. for 4 hours.

The obtained resin was purified by reprecipitating it with methanol and then dissolving it in toluene three times.

For comparison, polymerization and purification were carried out in the same manner except that toluene was used as the polymerization solvent instead of dimethyl silicone oil.

The performance of these purified resins is shown in Table 13 below.

Table 13 Example 59 300 g of H5-200 and 30 g of colloidal silica were placed in the same flask as in Example 58, and heated to 90°C. A solution consisting of 150 g of 2-ethylhexyl methacrylate, 15 g of glycidyl methacrylate, 20 g of p-divinylbenzene, 40 g of methyl methacrylate, and 6.3 g of lauroyl peroxide was added dropwise to this, and the mixture was further stirred at the above temperature for 4 hours to undergo a polymerization reaction. Do this.

Polymerization rate 98.2%, viscosity 100cp1 particle size 0.5-2.
A 0- resin dispersion was obtained.

Example 60 300 g of KF54 and 60 g of polyethylene (AC-6 manufactured by Allied Chemical Co., Ltd.) were placed in the same flask as in Example 58, and heated to 95°C.Next, 180 g of stearyl methacrylate and 40 g of lauryl methacrylate were added thereto.

A solution consisting of 3 g of fumaric acid, 20 g of o-nonyldivinylbenzene, and 4 g of lauryl peroxide was added dropwise over 3 hours, and the mixture was further stirred at the above temperature for 3 hours to carry out a polymerization reaction. Diameter 0.3
A resin dispersion of ~0.5 strands was obtained.

Example 61 In the same flask as Example 58, 300 g of TSF4440,
Cetyl methacrylate 180g, dodecyl acrylate 40g, p-divinylbenzene 15g, acrylic acid 5
g and 3 g of benzoyl peroxide were taken and stirred at 90°C for 6 hours to perform a polymerization reaction, and the polymerization rate was 96.4% and the viscosity was 16.
A resin dispersion with a gel content of 0 cp and a gel content of 32% by weight was obtained.

Example 62 3, O equipped with stirrer, thermometer, cooling tube and dropping funnel
Pour 500 g of KF96L (1, Ocs) into flask Q, heat to 80°C, and add 100 g of lauryl acrylate, 50 g of the compound of the following formula (9), 10 g of methacrylic acid, and 5 g of azobisisobutyronitrile while stirring. A monomer solution consisting of the following was added dropwise over 2 hours. Thereafter, polymerization was carried out at this temperature for 4 hours. As a result, 1 polymerization rate was 96%, viscosity was 160 cp, and particle size was 0.2-0.
3. A resin dispersion was obtained.

Example 63 400 g of H5-200 was placed in the flask used in Example 62, heated to 90°C, and while stirring, 95 g of 2-ethylhexyl methacrylate, 25 g of the compound of the following formula (10), 10 g of glycidylpropyl acrylate, A monomer solution consisting of 5 g of acrylic acid and 2 g of azobisisobutyronitrile was added dropwise over a period of 1 hour, followed by a polymerization reaction at this temperature for 6 hours.

As a result, the polymerization rate was 99%, the viscosity was 276 cp, and the particle size was 0.1.
A resin dispersion of -0°2- was obtained.

Example 64 400 g of MS-200 was placed in the same flask as in Example 62, heated to 90°C, and while stirring, 200 g of cyclohexyl acrylate and compound 10 of the following formula (11) were added thereto.
g, methacrylic acid 5g, glycidyl methacrylate 10
After adding a monomer solution consisting of g and 3 g of benzoyl peroxide and carrying out a polymerization reaction at the above temperature for 4 hours,
To this was added 0.1 g of vinylpyridine and esterification was carried out at 80°C for 10 hours. As a result, the polymerization rate was 97% and the viscosity was 29%.
A resin dispersion having a particle size of 0.2 to 0.3 was obtained.

Example 65 In the flask used in Example 62, 200 g of TSF434 and 50 g of polyethylene (AC polyethylene 1l106 manufactured by Allied Chemical Co., Ltd.) were placed and heated to 90° C. to dissolve the polyethylene. A monomer solution consisting of 100 g of stearyl methacrylate, 200 g of the compound of the following formula (12), 1 g of acrylic acid, 8 g of glycidyl acrylate, and 10 g of azobisisobutyronitrile was added dropwise to this solution over a period of 2 hours using a dropping funnel, while stirring. The polymerization reaction was carried out at the above temperature for 6 hours. Next, 100 g of methyl methacrylate and 5 g of t-butyl peroxide were added, and the polymerization reaction was further carried out at 130°C for 6 hours with stirring, resulting in a polymerization rate of 99% and a viscosity of 300 c.
p, particle size 0.05-0. A resin dispersion of ll1a was obtained.

Example 66 In the same flask as in Example 62, 300 g of dimethyl silicone oil (viscosity 1.5 cs) was placed and heated to 95°C.

In this, 150 g of 2-ethylhexyl methacrylate,
A mixture of 1.5 g of methacrylic acid, 5.3 g of a compound represented by the following formula (13)%, 5 g of glycidyl methacrylate, and 3 g of azobisisobutyronitrile was added dropwise over 1 hour, and the mixture was further reacted at 95° C. for 4 hours. Furthermore, 0 pyridine
．． After adding 5 g and carrying out a polymerization reaction for 2 hours, 30 g of methyl methacrylate and 2 g of azobisisobutyronitrile were added and a polymerization reaction was carried out at 80°C for 5 hours.

The obtained resin was purified by reprecipitating it with methanol and then dissolving it in toluene three times.

For comparison, polymerization and purification were carried out in the same manner except that toluene was used as the polymerization solvent instead of dimethyl silicone oil.

The performance of these purified resins is shown in Table 14 below.

Example 67 300 g of KF58 was placed in a 2Q flask equipped with a stirrer, a thermometer, and a reflux condenser, and heated to 90°C.

Then, in a nitrogen stream, lauryl methacrylate 1
70 g, a solution consisting of 30 g of the compound of the following formula (14) and 3 g of benzoyl peroxide was added dropwise over 2 hours to cause a polymerization reaction, and then to complete the reaction, the mixture was stirred at 95° C. for 2 hours, resulting in a polymerization rate of 96%.
A resin dispersion with a viscosity of 240 cp was obtained.6 The particle size of this resin was 3 to 4, and the gel content was 36 weight.

Example 68 250 g of the resin dispersion obtained in Example 67 was mixed with 20 g of polyethylene (Union Carbide Co., Ltd. $1 DYNF) in a flask, heated and dissolved at 110°C for 3 hours, and then cooled to obtain a polyethylene-containing resin dispersion with a viscosity of 100 cp. I got the liquid. In addition, the particle size of this resin was 1-21.

Example 69 In the same container as Example 67, KF-96L (viscosity 1, 5c
s) 300g was taken and heated to 90°C. Next, a solution consisting of 170g of cetyl methacrylate, 20g of the compound of the following formula (15), 10g of N-vinylpyridine and 5g of azobisisobutyronitrile was added to it for 1 hour. The mixture was added dropwise to cause a polymerization reaction, and the reaction was completed by further heating at 95° C. for 3 hours. In this way, the polymerization rate was 98.1% and the viscosity was 7.
A 1 cp resin dispersion was obtained. The particle size of this resin is 1~
The gel content was 26.3% by weight.

Example 70 250 g of the resin dispersion taken in Example 69 was mixed with 18 g of bleached beeswax in a flask, heated and stirred at 100°C for 2 hours, and then cooled to obtain a bleached beeswax-containing resin dispersion with a viscosity of 200 cp. Prepared. Note that the particle size of this resin is 0.
It was 5-1 pm.

Example 71 In the same container as in Example 67, 300 g of KS-200 and 10 g of silica powder with a particle size of 1 to 2 were placed and heated to 95°C. In this, 150g of 2-ethylhexyl methacrylate
A solution consisting of 15 g of the compound of the following formula (16), 28 g of glycidyl methacrylate, 125 g of styrene and 5 g of azobisisobutyronitrile was added dropwise over 2 hours to cause a polymerization reaction, and then stirred at 95°C for 2 hours. The reaction was completed. In this way, a resin dispersion with a polymerization rate of 97.8% and a viscosity of 162 cp was obtained. The particle size of this resin was 2 to 5 tones, and the gel content was 48.3% by weight.

Example 72 Take 300 g of KF58 in the same container as Example 69, and add 95
heated to ℃. A mixture of 50 g of 2-ethylhexyl methacrylate, 130 g of styrene, 20 g of the compound of the following formula (17), 50 g of glycidyl methacrylate, and 3 g of azobisisobutyronitrile was added dropwise to the solution over 1 hour, and then polymerized at 95°C for 4 hours. Made it react. The obtained resin was purified by reprecipitating it with methanol and then dissolving it in toluene three times.

For comparison, polymerization and purification were carried out in the same manner except that toluene was used as the polymerization solvent instead of silicone oil.

The performance of these purified resins is shown in Table 15 below.

Table 15 Example 73 500 g of KF96L (viscosity 2.Ocs) in a 3Q flask equipped with a stirrer, thermometer, condenser and dropping funnel.
The mixture was heated to 85° C., and 100 g of lauryl acrylate, 50 g of the compound of formula (18) below, and 5 g of azobisisobutyronitrile were added dropwise to the mixture over 2 hours using a dropping funnel while stirring. Thereafter, the polymerization reaction was carried out at this temperature for 4 hours with stirring, and then 3 g of di-t-butyl peroxide was added and the polymerization reaction was further carried out at 110°C for 6 hours, resulting in a polymerization rate of 96.5% and a viscosity of 210°C.
A resin dispersion of p was obtained. The gel content of the resin was 28% by weight.

Example 74 400 g of H5-200 was placed in the flask used in Example 73, heated to 60°C, and while stirring, 95 g of lauryl methacrylate, 120 g of styrene, 25 g of the compound of the following formula (19), and 2 g of azobisisobutyronitrile were added. The mixture was added dropwise over 1 hour using a dropping funnel. Thereafter, a polymerization reaction was carried out at this temperature for 6 hours. Next, 4 g of benzoyl peroxide was added and the polymerization reaction was carried out at 90°C for an additional 4 hours with stirring, resulting in a polymerization rate of 97.0% and a viscosity of 210 cp.
A resin dispersion was obtained. The gel content of the resin was 34.2% by weight.

Example 75 400g of KF54 was placed in the flask used in Example 73, heated to 90°C, and 100g of styrene was added while stirring.
20 g of n-butyl acrylate, 20 g of stearyl methacrylate, 10 g of the compound represented by the following formula (20), and 3 g of benzoyl peroxide were added dropwise through a dropping funnel over 4 hours. Next, 30 g of styrene and 3 g of benzoyl peroxide were added and a polymerization reaction was carried out at the above temperature for 4 hours with stirring, resulting in a 3-polymerization rate of 94.
% and a viscosity of 280 cρ was obtained. The gel content of the resin was 42% by weight.

Example 76 In the flask used in Example 73, 200 g of KF56 and polyethylene (AC polyethylene 1 manufactured by Allied Chemical Co., Ltd.) were added.
1106) 50 was taken and heated to 90°C to dissolve the polyethylene. Among these, compound 20 of the following formula (21)
0 g of azobisisobutyronitrile and 10 g of azobisisobutyronitrile were added dropwise over 2 hours using a dropping funnel, and the polymerization reaction was carried out at the above temperature for 6 hours with stirring. Next, 100 g of cetyl methacrylate and 5 g of 1-butyl peroxide were added, and a polymerization reaction was further carried out at 130°C for 6 hours with stirring to obtain a polyethylene-containing resin dispersion having a polymerization rate of 97.1% and a viscosity of 420 cp. The gel content of the resin was 26% by weight.

Example 77 AC polyethylene 6 was added to the resin dispersion obtained in Example 74.
13 g of No. 10 was added and dissolved by heating at 90° C. for 2 hours, and then allowed to cool to produce a polyethylene-containing resin dispersion having a viscosity of 260 cp.

Example 78 40g of Sunwax 131-P was added to the polyethylene-containing resin dispersion obtained in Example 76, and the mixture was heated and dissolved at 90°C for 2 hours, and then allowed to cool to form a wax and polyethylene-containing resin dispersion with a viscosity of 480 cp. Manufactured.

Example 79 KF96L (viscosity 1.0
cs) 300g was taken and heated to 95°C. In this 2-
15g of ethylhexyl methacrylate, 100g of styrene
g, a mixture of 20 g of the compound of the following formula (22), 50 g of glycidyl methacrylate, and 3 g of azobisisobutyronitrile was added dropwise over 1 hour, and the polymerization reaction was further carried out at 95° C. for 4 hours. The obtained resin was purified by reprecipitating it with methanol and then dissolving it in toluene three times.

For comparison, polymerization and purification were carried out in the same manner except that toluene was used as the polymerization solvent instead of silicone oil.

The performance of these purified resins is as shown in Figure 16 below.

Table 16 Example 80 KF96L (viscosity 2.Ocs) 300 in a 2,0Q four-loaf flask equipped with a stirrer, thermometer and reflux condenser
g was taken and heated to 95°C. A solution consisting of 190 g of dodecyl methacrylate, 10 g of the compound represented by the following formula (23), and 6 g of azobisisobutyronitrile was added dropwise to the solution over a period of 3 hours, and the mixture was further stirred at the above temperature for 4 hours to carry out a polymerization reaction. A resin dispersion having a polymerization rate of 97% and a viscosity of 210 cp was obtained. In addition, the particle size of the resin is 0.20-0.30. The gel content was 34.2% by weight.

Example 81 300 g of the resin dispersion obtained in Example 80 was mixed with colloidal silica TOG in a flask, heated at 100° C. for 3 hours, and then cooled to give a viscosity of 240 cp and a particle size of 1 to 3 pm.
A colloidal silica-containing resin dispersion was obtained.

Example 82 300 g of F56 was taken in the same flask as in Example 80,
Heated to 90°C. Next, 300 g of lauryl methacrylate, 5 g of N-vinylpyridine, and the following formula (24
) and 3 g of benzoyl peroxide were added dropwise over 1.5 hours, followed by stirring at the above temperature for 4 hours to carry out a polymerization reaction, resulting in a polymerization rate of 95% and a viscosity of 180 cp.
A resin dispersion was obtained. Incidentally, the particle size of the resin is 0.5 to 1.
0 pm, and the gel content was 29.3% by weight.

Example 83 300 g of the resin dispersion obtained in Example 82 was mixed with 20 g of bleached beeswax in a flask, stirred at 95°C for 22 hours, and then cooled to give a viscosity of 240 cp and a particle size of 0.5 to 0.9. A beeswax-containing resin dispersion was obtained.

Example 84 In the same flask as Example 80, add KF96L (viscosity 1.O
cs) and 30 g of colloidal silica,
Heated to 0°C. In this, 150 g of 2-ethylhexyl methacrylate, 15 g of glycidyl methacrylate, 20 g of the compound of the following formula (25), 4 methyl methacrylate
After adding dropwise a solution consisting of 0 g and 6.3 g of lauroyl peroxide, the mixture was further stirred at the above temperature for 4 hours to carry out a polymerization reaction to obtain a resin dispersion having a polymerization rate of 93% and a viscosity of 225 cp. The particle size of the resin is 0.5-1. OIJrM
The gel content was 48% by weight.

Example 85 In the same flask as Example 80, add KF96L (viscosity 1.5c).
s) 300 g and 60 g of polyethylene (AC-6 manufactured by Allied Chemical Co., Ltd.) were heated to 95° C. Next, 180 g of stearyl methacrylate, 40 g of lauryl methacrylate, 3 g of fumaric acid, and 20 g of the compound of the following formula (26) were added. A solution consisting of 4 g of lauryl peroxide and 4 g of lauryl peroxide was added dropwise over 3 hours, and the polymerization reaction was carried out by further stirring at the above temperature for 3 hours. The polymerization rate was 97.1% and the viscosity was 26.
A resin dispersion liquid of 0 cp was obtained. In addition, the particle size of the resin is 0.8
~1.2I1m, gel content was 28% by weight.

Example 86 In the same flask as in Example 80, 300 g of H5-200, 180 g of cetyl methacrylate, 4 dodecyl acrylate
0g, 15g of the compound of the following formula (27), 5g of acrylic acid, and 3g of benzoyl peroxide were taken and stirred at 90°C for 6 hours to perform a polymerization reaction to obtain a resin dispersion with a polymerization rate of 96.0% and a viscosity of 43cp. Ta. In addition, the particle size of the resin is 0.2 to 0.6 tones, and the gel content is 31
It was 2% by weight.

Example 87 Add 300 g of KF58 to the same flask as Example 80.9
Heated to 5°C. In this, 150 g of 2-ethylhexyl methacrylate, 18 g of the compound of the following formula (28), 50 g of vinyltoluene, 50 g of glycidyl methacrylate, and 3 g of azobisisobutyronitrile.
After dropping a mixture of g over 1 hour, the polymerization reaction was further carried out at 95° C. for 4 hours. The obtained resin was purified by reprecipitating it with methanol and then dissolving it in toluene three times.

For comparison, polymerization and purification were carried out in the same manner except that toluene was used as the polymerization solvent instead of the silicone oil.

The performance of these purified resins is shown in Table 17 below.

Table 17 Example 88 Silicone oil (F58) 100 in a 2,0Q fourth flask equipped with a stirrer, thermometer and reflux condenser.
g was taken and heated to 95°C. In this, 190 g of dodecyl methacrylate, 10 g of methacrylic acid, the following formula (29
) and 6 g of azobisisobutyronitrile
After dropping the above solution over 3 hours, the mixture was further stirred at the above temperature for 4 hours to carry out a polymerization reaction to obtain a resin dispersion with a polymerization rate of 95% and a viscosity of 180 cp. The particle size of the resin was 1 to 3-3, and the gel content was 40.5% by weight.

Example 89 300 g of the resin dispersion obtained in Example 88 was mixed with colloidal silica Log in a flask, heated at 100°C for 3 hours, and then cooled to form a colloid with a viscosity of 200 cp and a particle size of 3 to 6. A silica-containing resin dispersion was obtained.

Example 90 KF96L (2, Ocs) in the same flask as Example 88
300g was taken and heated to 90°C. Next, add 300g of lauryl methacrylate and 5g of N-vinylpyridine to this.
, a solution consisting of 25 g of the compound below and 3 g of benzoyl peroxide was added dropwise over 1.5 hours, and the polymerization reaction was carried out by stirring at the above temperature for 4 hours, resulting in a polymerization rate of 96.0% and a viscosity of 2.
A resin dispersion of 40 cp was obtained. In addition, the particle size of the resin is 3-
There were 4 voices, and the gel content was 28% by weight.

Example 91 300 g of the resin dispersion obtained in Example 90 was mixed with 20 g of bleached beeswax in a flask, stirred at 95°C for 22 hours, and then cooled to produce bleached honey with a viscosity of 250 cp and a particle size of 5 to 8 tones. A wax-containing resin dispersion was obtained.

Example 92 KF96L (viscosity 1.5
cs) and 30 g of colloidal silica,
Heated to 0°C. In this, 150 g of 2-ethylhexyl methacrylate, 15 g of glycidyl methacrylate, 20 g of the compound of the following formula (31), 4 methyl methacrylate
After adding dropwise a solution consisting of 0 g and 6.3 g of lauroyl peroxide, the mixture was further stirred at the above temperature for 4 hours to carry out a polymerization reaction to obtain a resin dispersion having a polymerization rate of 98f and a viscosity of 260 cp. In addition, the particle size of the resin is 1 to 3, and the gel content is 25.
% by weight.

Example 93 Take 300 g of KF58 in the same flask as Example 88,
Heated to 95°C. A mixture of 150 g of 2-ethylhexyl methacrylate, 31 g of the compound of the following formula (32), 50 g of glycidyl methacrylate, and 3 g of azobisisobutyronitrile was added dropwise to the solution over 1 hour, and then a polymerization reaction was carried out at 95°C for 4 hours. . The obtained resin was purified by reprecipitating it with methanol and then dissolving it in toluene three times.

For comparison, polymerization and purification were carried out in the same manner except that toluene was used as the polymerization solvent instead of the silicone oil.

The performance of these purified resins is shown in Table 18 below.

Table 18 Example 94 500 g of KF96F (viscosity 2.Ocs) in a 3Q flask equipped with a stirrer, thermometer, condenser and dropping funnel.
was charged, heated to 85°C, and while stirring, 100 g of lauryl acrylate, 50 g of the compound of the following formula (33)% ((33) (2) and 5 g of azobisisobutyronitrile were added using a dropping funnel. It was added dropwise over 2 hours.Then, the polymerization reaction was carried out at this temperature for 4 hours while stirring, and then 3 g of di-t-butyl peroxide was added, and the polymerization reaction was further carried out at 110°C for 6 hours, resulting in a polymerization rate of 95. .0%1 particle size 4
A resin dispersion having a viscosity of 280 cp and a gel content of 29% by weight was obtained.

Example 95 400 g of H5-200 was placed in the flask used in Example 94, heated to 60°C, and while stirring, 95 g of stearyl methacrylate, 25 g of the compound of the following formula (h4), 10 g of glycidyl methacrylate, and 2 g of azobisisobutyronitrile were added. 1 by dropping funnel
The mixture was added dropwise over a period of time, and then a polymerization reaction was carried out at this temperature for 6 hours. Next, 4 g of benzoyl peroxide was added and a polymerization reaction was carried out at 90° C. for further 4 hours with stirring to obtain a resin dispersion having a polymerization rate of 96% and a viscosity of 250 cp. The particle size of the resin was 4 to 8 mm, and the gel content was 39 percent by weight.

Example 96 400 g of KF54 was placed in the flask used in Example 94, heated to 90°C, and while stirring, 200 g of lauryl methacrylate, 5 g of vinylpyridine, 10 g of the compound of the following formula (35), and 3 g of benzoyl peroxide were added using a dropping funnel. The mixture was added dropwise over 4 hours. Next, styrene 3
0 g and 3 g of benzoyl peroxide were added and a polymerization reaction was carried out at the above temperature for 4 hours with stirring to obtain a resin dispersion with a polymerization rate of 95% and a viscosity of 190 cp.

The particle size of the resin was 4 to 8, and the gel content was 26% by weight.

Example 97 In the flask used in Example 94, 100 g of H5-200 and 50 g of polyethylene (AC polyethylene 1l106, manufactured by Allied Chemical Co., Ltd.) were placed and heated to 90°C to dissolve the polyethylene. In this, 200 g of the compound of the following formula (36) (% formula %) (36) and 10 g of azobisisobutyronitrile
g was added dropwise over 2 hours using a dropping funnel, and the polymerization reaction was carried out at the above temperature for 6 hours while stirring. Next, 100 g of cetyl methacrylate and 5 g of 1-butyl peroxide
A polyethylene-containing resin dispersion having a polymerization rate of 95% and a viscosity of 520 cp was obtained by further carrying out a polymerization reaction at 130° C. for 6 hours with stirring. In addition, the gel content of the resin is 3
It was 8% by weight.

Example 98 AC polyethylene 6 was added to the resin dispersion obtained in Example 95.
18 g of No. 15 was added and dissolved by heating at 90° C. for 2 hours, and then allowed to cool to produce a polyethylene-containing resin dispersion having a viscosity of 320 cp.

Example 99 40g of Sunwax 131-P was added to the polyethylene-containing resin dispersion obtained in Example 97, and after heating and melting at 90°C for 2 hours, the mixture was allowed to cool to form a wax and polyethylene-containing resin dispersion with a viscosity of 580 cp. Manufactured.

Example io.

Pour 8300g of KFS into the same container as in Example 94 and heat at 95°C.
heated to. A mixture of 150 g of 2-ethylhexyl methacrylate, 15 g of the compound of the following formula (37), 50 g of glycidyl methacrylate, and 3 g of azobisisobutyronitrile was added dropwise to this solution over 1 hour, and the polymerization reaction was further carried out at 95°C for 4 hours. . The obtained resin was purified by repeating the procedure of reprecipitation with methanol and washing with toluene three times.

For comparison, polymerization and purification were carried out in the same manner except that toluene was used as the polymerization solvent instead of the silicone oil.

The performance of these purified resins is shown in Table 19 below.

Table 19 Example 101 500 g of KF96L (viscosity 1.5 cs) in a 3Q flask equipped with a stirrer, thermometer, condenser and dropping funnel.
The mixture was heated to 85° C., and 100 g of lauryl acrylate, 50 g of the compound of formula (38) below, and azobisisobutyronitrile were added dropwise to the mixture over 2 hours using a dropping funnel while stirring. After that, the polymerization reaction was carried out at this temperature for 4 hours with stirring, and then 3 g of di-t-butyl peroxide was added, and the polymerization reaction was further carried out at 110°C for 6 hours, resulting in a polymerization rate of 9 brocades and a gel content of 25% by weight. A resin dispersion was obtained.

Example 102 400 g of KF58 was placed in the flask used in Example 101, heated to 60°C, and while stirring, 95 g of 2-ethylhexyl methacrylate, 25 g of the compound of the following formula (39), and 2 g of azobisisobutyronitrile were added. was added dropwise over a period of 1 hour using a dropping funnel, and then a polymerization reaction was carried out at this temperature for 6 hours. Next, 4 g of benzoyl peroxide was added, and the polymerization reaction was carried out at 90°C for an additional 4 hours with stirring, resulting in a polymerization rate of 96.2% and a gel content of 32.
A resin dispersion of % by weight was obtained.

Example 103 Add 400 g of H5-200 to the flask used in Example 101.
200 g of cyclohexyl acrylate and the log of the compound of the following formula (40) were taken at 90° C. and heated to 90° C. while stirring.
, 3 g of benzoyl peroxide was added using a dropping funnel.
It was dripped over time. Next, 30 g of styrene and 3 g of benzoyl peroxide were added and a polymerization reaction was carried out at the above temperature for 4 hours with stirring, and the polymerization rate was 95.8%.
A 35% by weight resin dispersion was obtained.

Example 104 200% TSF401 was added to the flask used in Example 101.
50 g of polyethylene (AC polyethylene 1106, manufactured by Allied Chemical Co., Ltd.) were taken and heated to 90° C. to dissolve the polyethylene. In this, the following formula (41)
200 g of the compound and 10 g of azobisisobutyronitrile
100 g of cetyl methacrylate and 55 g of t-butyl peroxide were added dropwise through a dropping funnel over 2 hours and polymerized at the same temperature for 6 hours with stirring.
A resin dispersion liquid having a polymerization rate of 98.0% and a viscosity of 250 cp was obtained by adding 10 g of the resin and carrying out a polymerization reaction at 130° C. for 6 hours with stirring.

Example 105 300 g of dimethyl silicone oil (viscosity 1, 5 cs) was placed in the flask used in Example 101 and heated to 95°C. In this, 2-ethylhexyl methacrylate 1
50g, 20g of the compound of formula (38), 15 styrene
0 g of azobisisobutyronitrile and 3 g of azobisisobutyronitrile.
After the dropwise addition, the polymerization reaction was further carried out at 95° C. for 4 hours.

The obtained resin was purified by reprecipitating it with methanol and then dissolving it in toluene three times.

For comparison, polymerization and purification were carried out in the same manner except that toluene was used as the polymerization solvent instead of dimethyl silicone oil.

The performance of these Sei H resins is shown in Table 20 below.

Table 20 Example 106 H
Take 200 parts of 5-200 and heat it to 90°C on an oil bath, then add 100 parts of stearyl acrylate, 3 parts of ethylene glycol methacrylate, 30 parts of glycidyl methacrylate and 5 parts of azobisisobutyronitrile, and at this temperature. The copolymerization reaction was carried out for 5 hours. Next, 0.5 part of hydroquinone, 520 parts of β-methacryloxyethylic acid rafthale, and 0.02 parts of lauryl dimethylamine.
of the mixture was added, and the esterification reaction was carried out at 85° C. for 10 hours. Furthermore, 50 parts of styrene and 1 part of benzoyl peroxide were added to carry out graft polymerization.

AC polyethylene 6 was added to the obtained graft copolymer dispersion.
Add 50 parts of A (manufactured by Allied Chemical Co., Ltd.) to 80-90
It was kept in solution for 4 hours at °C. Then, the oil bath was removed and the mixture was cooled with water to obtain a resin dispersion.

Example 107 200 parts of KFS8 was placed in the flask used in Example 106, heated to 90°C on an oil bath, and then 100 parts of cetyl methacrylate, 5 parts of 1,3-butylene glycol diacrylate, and β-methacryloxyethylic acid were added. 20 parts of hexahydrophthalate and 3 parts of benzoyl peroxide were added, and a copolymerization reaction was carried out at 100°C for 4 hours.

Next, 1 part of hydroquinone, 810 parts of glycidyl methacrylate and 0.01 part of dodecylamine were added to this,
The esterification reaction was carried out at 80°C for 10 hours.

Furthermore, 30 parts of methyl methacrylate and 0.05 part of azobisisobutyronitrile were added, and graft polymerization was carried out at 90° C. for 3 hours.

Sunwax E20 was added to the obtained graft copolymer dispersion.
0 (manufactured by Sanyo Chemical Co., Ltd., low weight polyethylene) was added thereto, and the mixture was heated at 90° C. for 1 hour to obtain a resin dispersion.

Example 108 In the same flask as in Example 106, 300 parts of F54 was added.

After heating to 80°C, 100 parts of lauryl methacrylate, 8 parts of tetramethylolmethanetetraacrylate, 25 parts of glycidyl acrylate, and 3 parts of lauroyl peroxide were added, and a copolymerization reaction was carried out at the same temperature for 5 hours. Further, 0.1 part of hydroquinone, o and oot parts of lauryl dimethylamine, and 20 parts of a compound of the following formula (42) were added, and an esterification reaction was carried out at the above temperature for 10 hours. Furthermore, 30 parts of vinyl acetate was added to this to obtain a graft copolymer dispersion.

Comparative Example 13 Example 10 except that toluene was used instead of MS-200
A resin dispersion was prepared by repeating method 6.

Comparative Example 14 A resin dispersion was prepared by repeating the method of Example 107, except that toluene was used instead of KF58.

Comparative Example 15 A resin dispersion was prepared by repeating the method of Example 108, except that toluene was used instead of KF54.

The esterification rate, polymerization rate, particle size, dispersion stability, and water repellency of the resins obtained in Examples 106 to 108 and Comparative Examples 13 to 15 are shown in Table 21 below.

Example 109 In the same container as Example 106, dimethyl silicone oil (
(viscosity: 1.5 cs) was taken and heated to 95°C.

In this, 150 g of 2-ethylhexyl methacrylate,
After dropping a mixture of 5 g of ethylene glycol dimethacrylate, 50 g of glycidyl methacrylate, and 3 g of azobisisobutyronitrile over 1 hour, the mixture was heated at 95°C for another 4 hours.
810 g of zero-order β-methacryloxyethylic acid raftale and 0.0 g of pyridine. After adding Ig and esterifying at 80°C for 12 hours, 50g of styrene and 3g of benzoyl peroxide were added and a polymerization reaction was carried out at 90°C for 3 hours.

The obtained resin was purified by reprecipitating it with methanol and then dissolving it in toluene three times.

For comparison, polymerization and purification were carried out in the same manner except that toluene was used as the polymerization solvent instead of dimethyl silicone oil.

The performance of these purified resins is as shown in Cloth-22 below.

Table 22 [Effects of the Invention] According to the resin polymerization method of the present invention, an odorless and highly safe resin can be obtained, ■ the polymerization rate of the resin can be increased, and ■ the water repellency, oil repellency, and electrical insulation of the resin can be improved. ■ Easily or improve the separation or dispersion stability between the polymerization solvent and the resin, ■ The temperature during polymerization can be freely selected, and ■ Improves the coating properties and gloss of the resin. ■Improvement of preservation quality such as heat resistance and cold resistance, and many other effects can be expected.

Claims (8)

[Claims] (1) A method for producing a resin, which comprises dissolving or dispersing a polymerizable vinyl monomer in a polymerization solvent containing silicone oil as a main component, and then polymerizing it in the presence of a polymerization catalyst. (2) The silicone oil has the general formula (I)▲mathematical formula,
There are chemical formulas, tables, etc.▼...(I) [However, R^1, R^2, R^3, R^4, R^5, R^
6, R^7, R^8 are -C_nH_2_n_+_1(n
:1 to 20), which may be the same or different. Moreover, x is an integer of 0 or 1 or more. ] Claim 1 is a dialkyl silicone oil represented by
The method for producing the resin described in . (3) The viscosity of the silicone oil at 25°C is 0.
．． 3. The method for producing a resin according to claim 2, wherein the resin has a particle diameter of 0.01 to 1,000,000 centistokes. (4) The method for producing a resin according to claim 1, wherein the silicone oil is a cyclic polydialkylsiloxane or a cyclic polyalkylphenylsiloxane. (5) The method for producing a resin according to claim 1, wherein the silicone oil is an alkylphenylsiloxane. (6) The method for producing a resin according to claim 1, wherein in the polymerization step, graft polymerization is performed. (7) The manufacturing method according to claim 1, characterized in that a crosslinking agent is present during the polymerization step. (8) The method for producing a resin according to claim 7, wherein the crosslinking agent is a divinyl monomer.