JPH1045942A - Polymerization catalyst composition and method for producing liquid toner using the same - Google Patents

Abstract

(57) [Problem] To provide a polymerization catalyst composition using an organic peroxide, which is hardly decomposed or exploded even when impurities are mixed therein, has excellent storage stability, and can obtain a high polymerization rate. SOLUTION: It is formed from an oligomer of an organic peroxide and at least an α-olefin. When the composition is used as a polymerization catalyst and the α-olefin oligomer is used as a polymerization solvent, a liquid polymerization toner having a sharp particle size distribution can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a highly safe polymerization catalyst composition containing an organic peroxide.

[0002]

2. Description of the Related Art An organic peroxide has an --O--O-- bond in a molecule, and is thermally decomposed at a relatively low temperature to easily generate free radicals.
That is, it is well known that it is used as a polymerization initiator. In general, this compound is stable at room temperature, and is used for curing of unsaturated polyester in addition to polymerization and copolymerization of olefins and vinyl monomers, but sparks, heating, friction, impact, impurities (acid or alkali) Has the disadvantage that it decomposes or explodes due to the incorporation of it, and the sensitivity to this explosion is much more sensitive than that of picric acid, TNT or the like.

Since the handling of organic peroxide is dangerous, it is diluted with dioctyl phthalate, dibutyl phthalate and the like, and diluted with pure products such as calcium sulfate, calcium carbonate, dibasic calcium phosphate and water. .
However, in the polymerization catalyst composition thus obtained, peroxides gradually decompose over time, and not only a good polymerization rate cannot be obtained, but also a diluent remains in the polymerization product, so that a high-purity product is obtained. Required further purification or drying of the polymerized product.

As a diluent, a method has been proposed in which a peroxide is mixed with a solvent having good solubility and volatility such as toluene, alcohol, and other solvents. Problems, acidity,
When impurities such as alkalis were mixed, there was a problem that the polymerization initiator was decomposed at a stretch.

Also, Japanese Patent Application Laid-Open Nos. 8-48710 and 8-4
The olefin polymerization catalyst described in JP-A-8713 is dangerous because it is a metal powder. Japanese Patent Publication Nos. Hei 8-26082 and Hei 8-26083 disclose examples in which benzoyl peroxide is used without a diluent. However, there are problems such as explosion, flammability due to mixing of impurities, acids and alkalis. Many.

[0006]

SUMMARY OF THE INVENTION In view of the above-mentioned problems, the present invention uses an organic peroxide having a high decomposability and a high risk, and is hardly decomposed or exploded even if impurities are mixed therein. It is an object of the present invention to obtain a polymerization catalyst composition having excellent storage stability and a high conversion.

[0007]

According to the present invention, first, there is provided a polymerization catalyst composition characterized by containing at least an oligomer of an organic peroxide and an α-olefin. Second, in the polymerization catalyst composition described in the first aspect, the α-olefin oligomer has 5 to 1 carbon atoms.
8. A polymerization catalyst composition is provided which is a 2- to 1000-mer of the α-olefin of No. 8. Third, in the polymerization catalyst composition according to the first or second aspect, the oligomer of the organic peroxide and the α-olefin is 20 to 80/8.
A polymerization catalyst composition is provided which is mixed in a weight ratio of 0 to 20. Fourth, using the polymerization catalyst composition according to any one of the above first to third, and using an α-olefin oligomer as a polymerization solvent, a vinyl monomer is polymerized or copolymerized in the presence of at least a colorant. A method for producing a liquid toner characterized by polymerizing is provided. Fifth, a polymer particle is produced by polymerizing or copolymerizing a vinyl monomer using the polymerization catalyst composition according to any of the above first to third, and the obtained polymer particle is subjected to a coloring agent and an α-olefin. A method for producing a liquid toner, characterized by being dispersed in an oligomer of

Hereinafter, the present invention will be described in detail. As described above, the polymerization catalyst composition of the present invention is composed of an oligomer of an organic peroxide and an α-olefin, and the organic peroxide is mixed and diluted with the oligomer of the α-olefin. The α-olefin oligomer used in the present invention is preferably an α-olefin having 5 to 18 carbon atoms, preferably a dimer to 1000 mer, and a 3 to 100 mer having 9 to 13 carbon atoms. Is more preferred. Thus, the polymerization catalyst composition of the present invention comprises an organic peroxide,
Non-flammable, non-volatile, odorless, inert substance is dispersed in an α-olefin oligomer, so even during storage, peroxides do not decompose for a long time, and acids, alkalis, and other impurities The peroxide is not decomposed even by the incorporation of, and storage stability can be improved in handling. According to the polymerization catalyst composition of the present invention, resin particles and toner particles having a small average particle size and a sharp particle size distribution can be produced. Furthermore, it was found that the polymerization rate and the grafting rate of the monomer could be improved. Furthermore, since the α-olefin oligomer as the diluent is well compatible in the polymer, even if a small amount of the oligomer remains in the polymer, the decrease in electric resistance and the strength does not occur. In addition, the foaming properties are low.

[0009]

Embodiments of the present invention will be described below. First, examples of the organic peroxide include benzoyl peroxide, cumene peroxide, hydroperoxide, diacyl peroxide, dialkyl peroxide, peroxyketal, and alkyl peresters.

Examples of the α-olefin oligomer include the following. (1) 1-pentene 10-mer (2) 2-methyl-1-butene 20-mer (3) 2-methyl-2-butene pentamer (4) 1-hexene 9 100-mer ( 5) 500-mers of 2,3-dimethyl-2-butene (6) 15-mers of 1-heptene (7) 85-mers of 1-octene (8) 1000-mers of 1-nonene (9) 1- Decene trimer (10) 1-Dodecylene pentamer (12) 1-Stearylene dimer

In the composition of the present invention, the mixing ratio of the organic peroxide and the α-olefin oligomer is 20% by weight.
~ 80/80 ~ 20, preferably 30 ~ 70/70 ~ 3
0 is appropriate. If the amount of the α-olefin oligomer is less than 20 parts by weight, it cannot be uniformly mixed with the organic peroxide, resulting in poor storage stability. Decomposition is likely to occur due to mixing of acids, alkalis and impurities. The composition of the present invention can be applied to emulsion polymerization, bulk polymerization, solution polymerization, and the like. In this case, the amount used is usually preferably 0.01 to 5 parts by weight based on the monomer. .

Polymerized particles for toner can be prepared by using the composition of the present invention as a polymerization catalyst. As monomers to be used, those generally used for toner as described below can be preferably used. Styrene such as styrene, p-chlorostyrene, vinyltoluene and its substituted products, styrene / p-chlorostyrene, styrene / vinyltoluene, styrene / vinylnaphthalene, styrene / methyl acrylate, styrene / ethyl acrylate, styrene / acrylic acid Butyl, styrene / octyl acrylate, styrene / methyl methacrylate, styrene / ethyl methacrylate, styrene / butyl methacrylate, styrene / α-
Copolymerized monomers such as styrene and substituted products thereof such as methyl chloromethacrylate or styrene and acrylic monomers.

Particularly, the composition of the present invention is used as a polymerization catalyst, the α-olefin oligomer is used as a polymerization solvent, and the above-mentioned vinyl monomer is polymerized or copolymerized in the presence of a colorant such as carbon bon black. By polymerizing or polymerizing or copolymerizing a vinyl monomer using the composition of the present invention as a polymerization catalyst to prepare polymer particles, and dispersing the obtained polymer particles in a colorant and an oligomer of the α-olefin. A liquid toner having a uniform particle size can be manufactured.

[0014]

The present invention will be described more specifically with reference to the following examples. All parts are based on weight.

Example 1 A polymerization catalyst composition A was prepared by uniformly mixing the following components. <Polymerization catalyst composition A> BPO benzoyl peroxide 50 parts 15-mer 1-heptene 50 parts <Preparation of polymer particles> Next, 500 g of isododecane was placed in a 1000 ml four-necked flask and heated to 80 ° C. 100 g of styrene, lauryl methacrylate 15
g, 5 g of methacrylic acid, and 10 g of the polymerization catalyst composition A, and added dropwise with stirring for 2 hours. After the dropping of the monomer, polymerization was carried out for a further 6 hours while stirring at 80 ° C. The polymerization rate of the obtained polymer particles was 98.9%, the average particle size of the particles was as small as 0.50 μm, and the particle size distribution was 0.1%.
The distribution was sharp, 5 μm or less and 10 μm or more and 10% or less. No foaming was caused by stirring.

Comparative Example 1 The procedure of Example 1 was repeated except that toluene was used instead of 15-mer 1-heptene.
In the same manner as in the above, polymer particles were obtained. The polymerization rate is 86.2.
%, The average particle size of the particles was as large as 5.4 μm, and the particles were easy to settle.

Example 2 A polymerization catalyst composition B was prepared by uniformly mixing the following components. <Polymerization catalyst composition B> Methyl ethyl ketone peroxide 85 parts 85mer 1-octene 15 parts <Preparation of polymer particles> Polymerization was carried out in the same manner as in Example 1 except that B was used instead of polymerization catalyst composition A. Was. The polymerization rate of the obtained polymer particles is 92.5%, the average particle size of the particles is 1.25 μm, the particle size distribution is 0.1 μm or less 2%,
It was 1.0 μm or more and 21%, and the particle size distribution was relatively uniform.

Example 3 A polymerization catalyst composition C was prepared by uniformly mixing the following components. <Polymerization catalyst composition C> 15 parts of succinic acid peroxide 85 parts of trimer 1-decene <Preparation of polymer particles and liquid toner> The same procedure as in Example 1 was carried out except that C was used in place of polymerization catalyst composition A. To carry out polymerization. The polymerization rate of the obtained polymer particles is 95.2.
%, The average particle size of the particles is 0.82 μm, and the particle size distribution is 0.1
The average particle size distribution was 8% or less and 1.0 μm or more and 10.5% or less. Next, the polymer particles were dispersed in carbon black and pentamer dodecylene to prepare a liquid toner. Using this liquid toner, Recopy SP-35
(Ricoh copier), image density 1.30 and fixability 85% were obtained.

Example 4 <Preparation of Liquid Toner> 500 g of tetramer α-decane was placed in a 1000 ml four-necked flask, and heated to 85 ° C., and 50 g of carbon black, 20 g of styrene, and 20 g of vinyl toluene were added. , 2-ethylhexyl methacrylate 5
0 g, acrylic acid 2 g, dispersant (nonionic surfactant) 5
g, 10 g of polymerization catalyst composition C, and mix uniformly.
Dropped in time. Polymerization was further performed with stirring for 4 hours to produce a polymerized liquid toner. Foaming during polymerization was small.
The average particle size of the obtained toner particles is 0.90 μm.
The particle size distribution was 0.5 to 1.3 μm, and the liquid toner was a negatively charged liquid toner having a uniform particle size distribution. Next, using this toner, a copy was made with a Ricopy FT-400i (copier made by Ricoh Co., Ltd.).
mm, gradation of 7 steps, and fixability of 82%, a high quality image was obtained.

Comparative Example 2 A polymerized liquid toner was prepared in the same manner as in Example 4 except that isododecane was used instead of tetramer α-decane. The average particle diameter of the obtained toner particles was 5.6 μm, and the particles became non-uniform and aggregation occurred.

<Preservation property of polymerization catalyst composition> The polymerization catalysts A, B, and C obtained in the above Examples are all stable even after 12 months, and Even after months, it could be reproduced as it is.

[0022]

As described above, according to the polymerization catalyst composition of the present invention comprising an oligomer of an organic peroxide and an α-olefin, the safety and the storage stability are high, and the polymerization rate is high.
Polymer particles having a uniform and small particle size can be obtained. Also,
This is suitable for producing a liquid polymerized toner.

Claims (5)

[Claims] 1. A polymerization catalyst composition comprising at least an oligomer of an organic peroxide and an α-olefin. 2. The polymerization catalyst composition according to claim 1, wherein the α-olefin oligomer is a 2- to 1000-mer of an α-olefin having 5 to 18 carbon atoms. 3. The polymerization catalyst composition according to claim 1, wherein the organic peroxide and the α-olefin oligomer are mixed in a weight ratio of 20 to 80/80 to 20. 4. A polymerization or copolymerization of a vinyl monomer in the presence of a colorant, using the polymerization catalyst composition according to claim 1 and an α-olefin oligomer as a polymerization solvent. A method for producing a liquid toner. 5. A polymer particle is produced by polymerizing or copolymerizing a vinyl monomer using the polymerization catalyst composition according to claim 1, and the obtained polymer particle is mixed with a colorant and α- A method for producing a liquid toner, comprising dispersing in an olefin oligomer.