JPH01263108A - Non-aqueous resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a non-aqueous resin composition useful for paints, adhesives, electrostatographic liquid developers, and the like.

It is well known that polyfunctional acrylic esters or polyfunctional methacrylic esters can be polymerized by a polymerization initiator such as an organic peroxide, heat, ultraviolet rays, or radiation, resulting in a cured product with a three-dimensional structure. ing. Furthermore, there is a known method of copolymerizing these monomers with other monomers such as acrylic acid, acrylic acid ester, and styrene by utilizing these properties to produce a crosslinked resin composition (dispersion) (Unexamined Japanese Patent Publication No. (Sho 57-73746). However, this method uses benzene,
Since an aromatic hydrocarbon solvent such as toluene is used, there are problems with toxicity and flammability, and the dispersion stability of the resin is also poor. Furthermore, when the composition thus obtained was used, for example, as a paint, it had poor dispersibility in pigments, and the gloss, film-forming properties, adhesion, etc. of the coating film were also insufficient.

An object of the present invention is to provide a non-aqueous resin composition that is low in toxicity and flammability, and also has good dispersion stability of the resin, dispersibility for pigments, etc., glossiness of the coating film, film formability, and adhesiveness. It is to be.

The non-aqueous resin composition of the present invention is prepared in the presence of a polymerization initiator in a non-aqueous solvent containing a petroleum-based aliphatic hydrocarbon as a main component. , R2 is H or C11, R1 is H or an alkyl group having 1 to 20 carbon atoms, m is an integer of 1 to 20, and n is a repeating unit.

) is obtained by copolymerizing a polymer monomer A shown in the following formula with a monomer B selected from the group consisting of polyfunctional acrylic esters and polyfunctional methacrylic esters.

This polymerization reaction is carried out while heating the solvent to reflux. Through this reaction, a copolymer resin having a three-dimensional structure in which the polymer monomer A and the monomer B component are crosslinked to each other in the form of a network is obtained.

Here, monomer B itself has the property that it is solvated with a petroleum-based resin aliphatic hydrocarbon solvent before polymerization, but is not solvated with this solvent after polymerization. On the other hand, the polymer monomer A itself has the property of being solvated with the solvent both before and after polymerization. Therefore, it is considered that the resulting resin is dispersed in a solvent in a state in which the monomer B component and the polymeric monomer A component solvated with the solvent are bonded around it. The polymer monomer component A in the resin contributes to dispersion stability (including dispersion stability to other substances such as pigments) and adhesiveness.

Further, the ratio of monomer B to polymer monomer A is 0.
Approximately 01 to 1:1 (by weight) is appropriate.

In the present invention, carbon or silica fine particles, wax with a softening point of about 60 to 180°C, polyolefin, ethylene copolymer, etc. can be added during the manufacturing process of the resin composition. When carbon or silica fine particles are used, it is thought that the resin is obtained with these fine particles incorporated in its network structure. In this case, the carbon or silica itself does not undergo physical changes such as dissolution during one reaction. In any case, in the case of carbon or silica, the specific gravity is similar to that of aliphatic hydrocarbon or its halide as a dispersion medium, and by preventing gelation of the resin,
Dispersion stability can be further improved. On the other hand, when wax, polyolefin, etc. are used, they are dissolved in the reaction system by heating during the polymerization reaction, but after the reaction, they are precipitated into fine particles by cooling, and the resin is obtained in a state that is adsorbed to these fine particles. considered to be a thing. Here, wax, polyolefin, etc. have a specific gravity similar to that of the dispersion medium, prevent gelation of the resin, and have a molecular structure similar to that of the dispersion medium, so they not only help improve dispersion stability, but also have a low softening point. , which also helps improve adhesion. The appropriate amount of addition of Naoribon, silica, wax, polyolefin, etc. is about 5 to 50 parts by weight per 100 parts by weight of the resin.

Next, the materials used in the present invention will be explained.

Petroleum aliphatic hydrocarbons used in the present invention include groin, n-hexane, n-pentane, n-hebutane,
n-octane, i-octane, i-dodecane, i-nonane (commercially available products include Exxon's Isopar H,
G, L, (Naphtha Na 6, Shell Sol, manufactured by Shell Oil Co., etc.), carbon tetrachloride, perfluoroethylene, etc. These aliphatic hydrocarbons have a higher flash point than aromatic solvents such as benzene and toluene, and are also less toxic. Since the solubility of the resin of the present invention is poorer than that of aromatic solvents, it also has the advantage that the resin does not gel or solidify during the polymerization reaction or during storage. These petroleum-based aliphatic hydrocarbons have high insulation properties (electrical resistance of 1010Ω).
・011 or higher), a solvent with a low dielectric constant (dielectric constant 3 or lower). Furthermore, aromatic solvents such as benzene and toluene may be added to these aliphatic solvents in small amounts.

Specific examples of the polymer monomer A represented by the above general formula include the following.

(Molecular weight: 6.200) These polymeric monomers A are easily available as commercial products.

Examples of monomer B include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol methacrylate, triethylene glycol triacrylate, triethylene glycol trimethacrylate, butanediol diacrylate, butanediol dimethacrylate, 1,6- hexanediol diacrylate,
1,6-hexanediol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethanetetraacrylate, tetramethylolmethanetetramethacrylate, dipropylene glycol diacrylate , dipropylene glycol dimethacrylate, trimethylolhexane triacrylate, trimethylolhexane trimethacrylate,
Examples include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, 1°3-butylene glycol diacrylate, 1°3-butylene glycol dimethacrylate, trimethylolethane triacrylate, and trimethylolethane methacrylate.

In addition, the above-mentioned polymeric monomers A and monomers B include lauryl methacrylate, lauryl acrylate, stearyl methacrylate, stearyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, dodecyl methacrylate, dodecyl acrylate, and hexyl methacrylate. , hexyl acrylate, octyl methacrylate, octyl acrylate, cetyl methacrylate, cetyl acrylate,
Monomers such as vinyl laurate and vinyl stearate can be used in combination.

As the polymerization initiator, benzoyl peroxide, 1-butyl perbenzoate, cyamyl peroxide, di-t-butyl peroxide, lauryl peroxide, azobisisobutyronitrile, etc. can be used.

Specific examples of commercially available waxes or polyolefins used for dispersion in non-aqueous resin compositions are as follows.

Union Carbide (USA) DYNE
102DYNF 102 DYNH102 DYNJ 102 DYNK 102 Monsanto (USA) 0RLIZON805
1160RLIZON705 116 0RLIZON 50 126 Philips (US) MARLEX 10
05 92 Dupont (US) ALAT
HON~3103ALATHON-1096 ALATHON-1284 ALATHON-1480 ALATHON-1695 ALATHON-2086 ALATHON-2284 DuPont (USA) ALATHON-25
966&6A AC-Polyethylene 105 Sanyo Chemical Sunwax 131-P
108 Sunwax 151. -P 107 Sunwax 161-P 111 Sunwax 165-13 107 Sunwax 17]-P 105 Sunwax E-20095 Genuine chemical paraffin wax 60
~98 Similarly, as the ethylene copolymer dispersed in the non-aqueous resin composition, ethylene-vinyl acetate copolymer;
Ethylene-acrylic acid (or methacrylic acid) copolymer, ethylene-ethyl acrylate (or ethyl methacrylate) copolymer, ethylene-ethyl acrylate (
or ethyl methacrylate) to acrylic acid copolymers.

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

Example 1 300 g of Isopar was placed in a 2Q flask equipped with a stirrer, a thermometer, and a reflux condenser, and heated to 90°C. Among these, No. (1) polymer monomer A 170
g, a solution consisting of 80 g of diethylene glycol dimethacrylate and 3 g of 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 94% and a viscosity of 400 cp.
A resin composition was obtained. The particle size of this resin is 3 to 5.
It was μ.

Example 2 250 g of the resin composition obtained in Example 1 was mixed with 20 g of polyethylene (DYNF manufactured by Union Carbide) in a flask, heated and dissolved at 110°C for 3 hours, and then cooled to obtain a polyethylene-containing resin with a viscosity of 120 cp. A composition was obtained. Note that the particle size of this resin was 1 to 2 μm.

Example 3 300 g of isooctane was taken in the same container as in Example 1, and 9
Heated to 5°C. Next, a solution consisting of 170 g of polymer monomer A of Nu(2), 50 g of dipropylene glycol dimethacrylate, and 5 g of azobisisobutyronitrile was added dropwise to this for 1 hour to cause a polymerization reaction, and the mixture was further heated at 95°C for 3 The reaction was completed by heating for an hour. In this way, a resin composition with a polymerization rate of 98% and a viscosity of 400 cp was obtained. The particle size of this resin was 1 to 3 microns.

Example 4 250 g of the resin composition obtained in Example 3 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 composition with a viscosity of 300 cp. Prepared. Note that the particle size of this resin was 2 to 4.

Example 5 In the same container as Example 1, 300 g of isooctane and particle size 0
．． 10 g of 5-1 μm silica powder was taken and heated to 95°C. In this, 150 2-ethylhexyl methacrylate
A solution consisting of 30 g of polymer monomer A of No. g, No. (5), 50 g of trimethylolpropane triacrylate, and 5 g of azobisisobutyronitrile was added dropwise over 2 hours to cause a polymerization reaction, and then stirred for further 2 hours at 95°C. was carried out to complete the reaction. In this way, the polymerization rate was 96% and the viscosity was 1.
A resin composition of 20 cp was obtained. The particle size of this resin is 2
It was ~4μ.

Example 6 50 g of carbon and sog of polyethylene (Sunwax 131-P) were placed in the same flask as in Example 1, and 9
Heated to 5°C. Next, stearyl methacrylate is added to this.
h150g, No (7) polymer monomer A100g,
A solution consisting of 21 g of tetramethylolmethanetetramethacrylate and 5 g of lauryl peroxide was added dropwise at the above temperature for 1 hour to cause a polymerization reaction, and then 0 g of Isopar H3O was added. The reaction was further completed by heating at the same temperature for 3 hours. In this way, the polymerization rate was 96% and the viscosity was 200c.
A resin composition of p was obtained. The particle size of this resin is 0.5~2μ
Met.

Effects The resin composition of the present invention can be produced in an aliphatic hydrocarbon solvent with low toxicity and flammability, and has excellent dispersion stability of the resin, dispersibility for pigments, etc., glossiness of the coating film, film forming property, and adhesive property. It also has excellent features such as paints, adhesives,
It is extremely useful as a liquid developer for electrostatic photography.

Patent applicant Rico Co., Ltd.

Claims (1)

[Claims] 1. In a non-aqueous solvent containing petroleum-based aliphatic hydrocarbon as the main component,
In the presence of a polymerization initiator, the general formula: ▲Mathematical formulas, chemical formulas, tables, etc. group, m is an integer of 1 to 20, and n represents a repeating unit.) A polymer monomer A represented by the following formula is copolymerized with a monomer B selected from the group consisting of polyfunctional acrylic esters and polyfunctional methacrylic esters. A non-aqueous resin composition made of