JPS60226513A - Preparation of nonaqueous based resin dispersion - Google Patents

Abstract

PURPOSE:To obtain a resin dispersion used for coating materials and adhesives without causing rapid crosslinking reaction, by polymerizing a specific monomer with a monomer capable of solvating with a nonaqueous solvent consisting essentially of an aliphatic hydrocarbon in the presence of a polymerization initiator in the nonaqueous solvent. CONSTITUTION:A monomer of the formula (R is H or methyl; X is H, chlorine, bromine or iodine) is polymerized with a monomer, e.g. lauryl methacrylate, capable of solvating with a nonaqueous solvent, e.g. ligroin, consisting essentially of an aliphatic hydrocarbon both before and after polymerization in the presence of a polymerization initiator, e.g. benzoyl peroxide, in the nonaqueous solvent to afford the aimed resin dispersion. EFFECT:Good for environmental sanitation with little danger of fire. The shelf life of the dispersion is good, and deterioration in adhesive power is slight.

Description

DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD The present invention relates to a method for producing a nonaqueous resin dispersion useful for paints, adhesives, toners of electrophotographic liquid developers, and the like.

Prior art A polyhydric alcohol diacrylate such as diethylene glycol dimethacrylate and a polymerizable monomer such as lauryl acrylate are copolymerized in an aromatic hydrocarbon solvent such as toluene, benzene, or xylene in the presence of a polymerization initiator. Methods of producing polymeric resins are known.

The resins thus obtained have been widely used for paints and adhesives. However, since aromatic hydrocarbon solvents are used in these resin (solution) manufacturing methods, crosslinking of the resin tends to proceed, resulting in problems such as gelation of the resin during the polymerization reaction and solidification of the resin during storage. was there. The same applies when this non-aqueous resin is used for paints or adhesives, and assimilation during storage causes a decrease in adhesive strength. In order to solve these problems, it has conventionally been necessary to suppress the amount of polyfunctional acrylic ester such as polyvalent glycol diacrylate to 3 weight or less. Even if the above problems are solved in this way, the resin is soluble in aromatic solvents and is therefore obtained in a dissolved state, so if it is used as is in a paint, the amount of resin adsorbed to the pigment will be It was undesirable, especially when used in electrodeposition paints, because the adhesive strength was insufficient.

Furthermore, the aromatic solvent used in this method is highly toxic and flammable, which not only poses problems in terms of environmental health, but also poses a risk of fire.

Purpose The purpose of the present invention is to use an aliphatic solvent that is almost non-toxic and flammable, has low solubility in the resulting resin, and is photochemically inert, thereby reducing the rapid crosslinking reaction during polymerization and eliminating the sys- tem. By providing a method for producing a non-aqueous resin dispersion that not only makes it easier to control the polymerization process but also improves storage stability, it does not reduce adhesive strength, has fewer environmental health problems, and has less fire risk. be.

Composition The method for producing a non-aqueous resin dispersion according to the present invention is carried out in the presence of a polymerization initiator in a non-aqueous solvent mainly composed of an aliphatic hydrocarbon. , odor, or iodine) and a monomer that is solvated with the solvent both before and after polymerization.

The polymerization reaction of the present invention generally involves heating the non-aqueous solvent,
In this, a mixed monomer solution containing a monomer represented by the general formula I (hereinafter referred to as monomer A), a monomer (hereinafter referred to as monomer B) that is solvated in a non-aqueous solvent before and after polymerization, and a polymerization initiator is added. It is done by dripping. In this polymerization reaction, monomer A, i.e., dicyclopentenyl (meth)acrylate, has a vinyl group in its molecule that easily reacts with other heptamers and a double bond that easily reacts with oxygen atoms, hydrogen atoms, etc. The difference in reactivity between these two functional groups imparts a partially crosslinked structure to the resulting copolymer resin, making it insolubilizable, while 7mer B solvates in non-aqueous solvents even after polymerization, so it improves solubility in the resin. give the result 1
% contributes to the dispersion stability of the resin.

Here, the ratio of monomer A and monomer B is 1:1 to 99.
(weight) is appropriate. In addition, other polymerizable monomers (hereinafter monomer v) may be added to these monomers A and B as necessary.
As -(), polar monomers and other reactive monomers can be added and copolymerized.

In addition, in the above polymerization reaction, silica fine particles and softening point 6
Wax or polyolefin having a temperature of about 0 to 130°C can be added. When fine silica particles are used, it is thought that the resin is obtained with fine silica particles incorporated during crosslinking. In this case, the silica itself does not undergo physical changes such as dissolution during the reaction.

t s −J' h ty l Yi
By preventing gelation of the resin, dispersion stability can be further improved. On the other hand, when wax or polyolefin is used, these are dissolved in the reaction system by heating during the first reaction, but after the first reaction, they are precipitated into fine particles by cooling, and the resin is obtained while being adsorbed to these fine particles. It is considered that the Here, wax or polyethylene has a specific gravity similar to that of the dispersion medium, prevents gelation of the resin, 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. It also helps improve adhesion. The appropriate amount of silica, wax or polyolefin added is about 5 to 50 parts by weight per 100 parts by weight of the resulting resin.

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

First, examples of monomer A, dicyclopentenyl (meth)acrylate, are listed below. can be manufactured.

Monomer B has the general formula % [where R is hydrogen or a methyl group, A is -COOCnH1n+t, or -0COCnH1n
+* (where n is an integer from 6 to 20), respectively.

] Specific examples thereof include lauryl methacrylate, lauryl acrylate, stearyl methacrylate, stearyl acrylate, 2-
Ethylhexyl methacrylate, 2-ethylhexyl acrylate, dodecyl methacrylate, dodecyl acrylate, hexyl methacrylate, hexyl acrylate, octyl acrylate, octyl methacrylate,
Cetyl methacrylate, cetyl acrylate ゞ・-
There are root, root, etc.

Next, among the monomers C, specific examples of polar monomers include unsaturated carmenic acid, unsaturated carzenic acid anhydride, unsaturated nitrogen-containing compounds, glycidyl group-containing unsaturated compounds, and alkyl acrylate (1 to 5 carbon atoms) ester. and/or alkyl methacrylate (having 1 to 5 carbon atoms) ester. Here, unsaturated carmenic acid and its anhydride include acrylic acid, methacrylic acid, itaconic acid, fumaric acid,
Examples include maleic acid, crotoyic acid, aconitic acid, cinnamic acid, and anhydrides thereof. Further, examples of unsaturated nitrogen-containing compounds include vinylpyrrolidone, 2-vinylpyridine, 4-vinylpyridine, N-vinylpyridine, N-vinylimidazole, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, etc.
Furthermore, examples of alkyl (1 to 5 carbon atoms) esters of acrylic acid, methacrylic acid, and rudic acid include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, and butyl methacrylate. Typical examples of the unsaturated compound containing a glycidyl group include glycidyl acrylate and glycidyl methacrylate.

Among monomers C, other reactive monomers include styrene, vinyltoluene, vinyl acetate, polyhydric alcohol dimethacrylate (e.g. ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol methacrylate, triethylene glycol triacrylate, triethylene glycol trimethacrylate, butanediol diacrylate, butanediol dimethacrylate, l,6-hexanethiol diacrylate),
1.6-hexanethiol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane 2acrylate, tetramethylolmethanetetramethacrylate, dipro2
rangelicol diacrylate, diglobylene glycol dimethacrylate, trimethylolhexane triacrylate, trimethylolhexane/trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate), 1,3-butere/glycol diacrylate, l , 3-zotylene glycol dimethacrylate, trimethylolethane triacrylate, trimethylolethane methacrylate), and the like.

As the polymerization initiator, benzoyl peroxide, t-butyl perbenzoate, cyamyl peroxide, di-t-butyl-7-oxide, lauryl peroxide, and azobisinbutyronitrile can be used.

Further, specific examples of commercially available waxes or polyolefins having a softening point of 60 to 130°C are as follows.

Example of polyethylene Union Carbide (USA) DYNI 1ozDYNF
102 DYNH102 DYNJ 102 DYNK 102 Monsanto (*) 0RLIZON 805 116#
701) 116 # 50 126 FILITSUNOS (US) MARLEX 1005 92 DUPONT (US) ALATHON -31031096 1284 1480 # 16 95 If 20 86 # 22 B4 25 96 ALITE°Kecal@) AC-Polyethylene 1702
98J Goni Product Name - Juku N ■ 9 - Allied Chemical (USA) Ac-Polyethylene 6 & 6A
102615 105 Sanyo Chemical Sunwax 131-P 10g1
51-P 107 161-P 111 165-P 107 # 171-P 105' E-20095 Genuine Chemical Paraffin Wax 60-98 Kobayashi Kako Sarashi Mitsuro 565 Setanol 80 Ice Piece Chemical Sarashi Mitsuro 565 Iron Manufacturing Chemical Frocene 110 Next Petroleum-based aliphatic hydrocarbons or halogenated aliphatic hydrocarbons are used as the non-aqueous solvent.

Specifically, hydroxide, n-hexa7, H-peethane,
n-hebutane, n-octane,! -Octane, l-dodecane, i-nonane (commercially available products include Exxon's Itsuno-H, G, and L.

(Naphtha A6, Shell Sol, manufactured by Shell Oil Co., etc.), carbon tetrachloride, perfluoroethylene, etc. are repelled. These aliphatic hydrocarbons or halogenated aliphatic hydrocarbons have a higher flash point than aromatic solvents such as benzene and toluene, and are also less toxic. The solubility of the resin of the present invention is also lower than that of aromatic media, so during the polymerization reaction or storage,
Another feature is that the resin is unlikely to gel or solidify. These petroleum-based aliphatic hydrocarbons or halogenated aliphatic hydrocarbons have high insulation properties (electrical resistance of 10Ω or more).
, a solvent with a low dielectric constant (dielectric constant of 3 or less). Further, aromatic solvents such as benzene and toluene may be added to these aliphatic solvents in small amounts.

Examples are shown below.

Example 1 Isooctane 300I was placed in a No. 2,01 four-hole flask equipped with a stirrer, a thermometer, and a reflux condenser, and heated to 95°C. In this, dodecyl methacrylate) 190j',
A solution consisting of 10p of the compound A4 and azobisisobutyronitrile 6II was added dropwise over 3 hours, and the mixture was further stirred at the above temperature for 4 hours to carry out a polymerization reaction, resulting in a polymer with a polymerization rate of 95.5% and a viscosity of 3200p. A resin dispersion was obtained.

Note that the particle size of the resin was 0.1θ to 0.20μ.

Example 2 300 g of the resin dispersion obtained in Example 1 were mixed with colloidal silica IOJ' in a flask.

After heating at 100℃ for 3 hours, cool to a viscosity of 360ep.
A colloidal silica-containing resin dispersion with a particle size of 0.15 to 0.26 μm was obtained.

Example 3 Isododecane 00I was placed in the same flask as in Example 1 and heated to 90°C. Next, a solution consisting of lauryl methacrylate 30 (1,N-vinylpyridine 5/1, compound 25J' of A5 above and benzoyl peroxide 311) was added to this for 1.5 hours, and the mixture was stirred at the above temperature for 4 hours. The polymerization reaction was carried out at a polymerization rate of 96.0 and a viscosity of 35.
0 (lp.

A resin dispersion having a particle size of 0.07 to 0.18 μm was obtained.

Example 4 300 g of the resin dispersion obtained in Example 3 was mixed with exposed 520F in a 7 flask, stirred at 95° C. for 22 hours, and then cooled to give a viscosity of 430 ap and a particle size of 0.10 to 0.0. 30
A resin dispersion containing μ exposed and exposed 5 was obtained.

Example 5 Aitsuno #-0300I and colloidal silica 309 were placed in the same flask as in Example 1 and heated to 90°C. In this, 2-ethylhexyl methacrylate 1-OJI,
glycidyl methacrylate) 1551. After adding dropwise a solution consisting of Compound 20I of Mu S, methyl methacrylate 409 and 6.3 g of lauroyl oxide, the polymerization reaction was carried out by further stirring at the above temperature for 4 hours. A resin dispersion having a particle size of .degree.p and a particle size of .mu.

Example 6 Isopar L 30θg and polyethylene (AC-6 manufactured by Allied Chemical Co., Ltd.) 60Jl were added to the same flannel as in Example 1.
was added and heated to 95°C. Next, stearyl methacrylate 18011. lauryl methacrylate 40
．． f, 3 Jl of fumaric acid.

A solution consisting of 20 g of the compound A4 and 4 g of lauryl/(-oxide 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, resulting in a polymerization rate of 97°.
%, a viscosity of 260 ep and a particle size of 0.20 to 0.40 μm was obtained.

Example 7 In the same flask as in Example 1, Isopar H3O0I and Cedermethacrylate 180Ji1. dodecyl acrylate
) 40 J, compound 15JiJ of the above A5.

Take 5 g of acrylic acid and 3I benzoyl peroxide, and add 90
The polymerization reaction was carried out by stirring at ℃ for 6 hours.

Polymerization rate 9&8%, viscosity 220cp, particle size 0.20~0.
A 40μ resin dispersion was obtained.

Examples 8 to 15 Resin dispersions having the properties shown in Table 2 were prepared in the same manner as in Example 7, except that the materials shown in Table 1 below and the reaction conditions shown in Table 2 below were used.

(Left below) Example 16 The same reaction as in Example 1. Inoctane 300I, lauryl methacrylate 100I1. Compound 50J of Saiya 5
' and benzoyl peroxide 5Ii were taken at 90°C.
After heating and polymerizing for 10 hours, a solution consisting of 50 g of 2-ethylhexyl methacrylate, 10.9 g of glycidyl methacrylate, and 19 g of benzoyl peroxide was added dropwise at the above temperature for 2 hours. Stir at temperature for 3 hours and further polymerization reaction, 1 polymerization rate 910%, viscosity 600 cp9 particle size 0.30-0.5
A resin dispersion liquid of 0μ was obtained.

Example 17 The same method as Example 16 was used except that 2-ethylhexyl methacrylate was used instead of lauryl methacrylate and methacrylic acid was used instead of glycidyl methacrylate, with a viscosity of 520 op and a particle size of 0.50 to 1.00 μ. A resin dispersion was obtained. The polymerization rate was 96.0.

Effects As described above, since the method of the present invention uses an aliphatic solvent as a reaction solvent, rapid crosslinking during one polymerization is eliminated, making it easier to control the polymerization process, and also improving storage stability and reducing adhesive strength. Moreover, the working environment is improved and the risk of fire is reduced.

Claims (1)

[Scope of Claims] 1. Presence of a polymerization initiator in a non-aqueous solvent mainly composed of aliphatic hydrocarbons, the general formula below (where R is hydrogen or a methyl group, and X is hydrogen, chlorine, bromine or iodine) 1. A method for producing a non-aqueous resin dispersion, which comprises polymerizing a seven-mer compound represented by the formula and a monomer that solvates with the solvent both before and after polymerization.