JP2013189594A - Polymerization initiator composition for manufacturing polymerized toner, and polymerizable monomer composition, suspension polymerized composition, and suspension polymer for manufacturing polymerized toner using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a suspension polymer for manufacturing a polymerized toner using a polymerization initiator composition which allows little VOC residue even when polymerized at a relatively high temperature and which produces few emulsion particles.SOLUTION: A polymerization initiator composition containing 100 pts.mass organic peroxide represented by general formula (1) and 5-50 pts.mass toluene is mixed at a proportion of 0.5-15 pts.mass with respect to 100 pts.mass polymerizable monomer, and polymerized at a temperature of 70°C or higher. (In the formula, Rand Rrepresent a methyl group and/or an ethyl group).

Description

  The present invention relates to a polymerization initiator composition useful for producing a polymerized toner, and a polymerizable monomer composition, a polymerized suspension composition, and a suspension polymer for producing a polymerized toner using the composition.

  The toner is a particle that is used in a printer, a copier, or the like and contains a coloring agent, a release agent, or the like in a binder resin having charging properties. There are two types of toner manufacturing methods: pulverized toner and polymerized toner. Polymerized toner is attracting attention because it is easy to obtain spherical particles and the particle size can be easily controlled, and productivity can be improved and high-resolution formation is possible. In general, a polymerized toner contains a polymerizable monomer, a polymerization initiator composed of an organic peroxide, and an additive such as a colorant, a charge control agent, and a release agent in an aqueous medium. It can be obtained by adding a monomer composition to form fine droplets and then performing a polymerization reaction.

  An item required for the production of such a polymerized toner is that there are few volatile organic compounds (VOC) in the toner. VOC is a general term for volatile organic compounds that vaporize and evaporate at room temperature, and refers to those having a boiling point of 260 ° C. or less (WHO standard). In Japan, a compound found in TVOC = n-hexane to n-hexadecane in the air quality guidelines formulated in 2000 from the Life Chemical Safety Office of the Ministry of Health, Labor and Welfare, Health Sanitation Bureau, although it is for building materials. It has become. In addition, the essential VOCs list compound and the top 10 detection compounds are quantified, and other VOCs are quantified in terms of the amount of toluene.

  This is because if the residual amount of VOC in the toner is large, not only the toner performance is deteriorated, but also the VOC is volatilized during printing and there is a risk of adversely affecting the human body. Therefore, Patent Document 1 below has been proposed as a technique for reducing the VOC residual amount in the polymerized toner.

（式中、Ｒ及びＲ’は炭素数６以下の第三級アルキル基である。） Patent Document 1 discloses toluene as an aromatic compound having a solubility in water of 0.18 to 5.0% by mass at least at a colorant, a polymerizable monomer, an organic peroxide, and water at 25 ° C. In which a specific organic peroxide represented by the following general formula (100) is used as a polymerization initiator.

(In the formula, R and R ′ are tertiary alkyl groups having 6 or less carbon atoms.)

（式中、Ｒは炭素数６以下のアルキル基であり、Ｒ’は炭素数８以下のアルキル基である。） Further, Patent Document 2 below has been proposed as a toner that is excellent in high-temperature storage stability and does not easily generate bad odor when printing is performed. In Patent Document 2, a polymerizable monomer composition containing a polymerizable monomer and a colorant is polymerized in an aqueous medium in the presence of an organic peroxide as a polymerization initiator, and colored polymer particles are obtained. Through a step of obtaining an aqueous dispersion containing the liquid and a stripping step of injecting air or an inert gas under the liquid surface of the aqueous dispersion while stirring in an evaporator having a gas phase pressure of 5 to 80 kPa. Polymerized toner is manufactured, and the ether component content is less than 500 ppm. In Patent Document 2, a non-aromatic peroxyester represented by the following general formula (101) having a purity of 90% or more, more preferably 92% or more, and further preferably 95% or more is used as a polymerization initiator. .

(In the formula, R is an alkyl group having 6 or less carbon atoms, and R ′ is an alkyl group having 8 or less carbon atoms.)

  In addition to the reduction in the amount of VOC remaining in the toner, items required for the production of the polymerized toner include a small amount of emulsified fine particles. The generation of emulsified fine particles in the production process of the polymerized toner is caused by the solubility of the organic peroxide, which is the polymerization initiator, in water, which adversely affects the dehydration and filtration processes after the polymerization reaction. Must be kept low.

JP 2005-106939 A JP 2007-232775 A

  In Patent Document 1, a specific organic peroxide is used as a polymerization initiator and toluene is also added to reduce the VOC residual amount in the toner. However, an organic peroxide in which R and R 'in the general formula (100) are tertiary alkyl groups is used as a polymerization initiator. The organic peroxides in which R and R 'are tertiary have a relatively low 10-hour half-life temperature. Therefore, it is necessary to set the polymerization temperature relatively low. Specifically, a two-stage polymerization reaction is performed in which the initial polymerization temperature is set to 65 ° C., and further polymerization is performed by raising the temperature to 80 ° C. in the latter stage of the polymerization. In addition, 10-hour half life temperature means the temperature which becomes half in 10 hours by thermal decomposition.

  In general, it is known that the higher the polymerization temperature, the higher the polymerization rate, and the lower the polymerization temperature, the lower the polymerization rate. If the polymerization temperature is low, it is necessary to lengthen the polymerization time or to change the temperature before and after the polymerization, which is difficult in terms of productivity and workability. Therefore, in order to increase the productivity of the toner, it is required to increase the polymerization temperature as much as possible to shorten the required time per production. However, in Patent Document 1, since the 10-hour half-life temperature of the organic peroxide is relatively low, radical deactivation occurs due to decomposition of the organic peroxide in a large amount at the initial stage of polymerization when the polymerization temperature is raised, and the initiator efficiency Will fall. As a result, the amount of the polymerization initiator is reduced, and the monomer cannot be sufficiently polymerized. For this reason, the residual monomer amount increases, and as a result, the VOC residual amount increases.

  On the other hand, in Patent Document 2, since the molecular weight of the organic peroxide is relatively small, the molecular weight of the by-product derived from the organic peroxide is also small, and it becomes relatively easy to remove VOC in the drying step after polymerization. . However, merely reducing the molecular weight of the organic peroxide increases the solubility of the organic peroxide in water, and emulsion polymerization occurs due to the organic peroxide dissolved in the aqueous layer. For this reason, the production | generation of the microparticles | fine-particles with the particle size which is not aimed originally increases, and it has influence on the spin-drying | dehydration and filtration process after a polymerization reaction.

  Therefore, the present invention solves the above-mentioned problems, and its purpose is that there are few residues that become VOC even when polymerized at a relatively high temperature, and the organic peroxide is soluble in water. PROBLEM TO BE SOLVED: To provide a polymerization initiator composition for producing a polymerized toner with less generation of emulsified fine particles, and a polymerizable monomer composition, a suspension polymerized composition and a suspension polymer for the production of polymerized toner using the same. It is in.

（式中Ｒ１、Ｒ２は、メチル基及び／又はエチル基である。）
（２）前記一般式（１）中のＲ１がメチル基であり、Ｒ２がエチル基である有機化酸化物を含有する、（１）に記載の重合トナー製造用の重合開始剤組成物。
（３）（１）または（２）に記載の重合開始剤組成物と、重合性単量体としてスチレンおよびｎ−ブチルアクリレートとを含有する、重合トナー製造用の重合性単量体組成物。
（４）前記重合開始剤組成物の含有量が、前記重合性単量体１００質量部に対して０．５〜１５質量部である、（３）に記載の重合トナー製造用の重合性単量体組成物。
（５）（３）または（４）に記載の重合性単量体組成物と、水系媒体とを含有する、重合トナー製造用の懸濁重合組成物。
（６）（５）に記載の懸濁重合組成物を重合して得られる、重合トナー製造用の懸濁重合物。
（７）７０℃以上の温度で重合して得られる、（６）に記載の重合トナー製造用の懸濁重合物。 In order to solve the above problems, the present invention employs the following means.
(1) A polymerization initiator composition for producing a polymerized toner, comprising 5 to 50 parts by mass of toluene with respect to 100 parts by mass of an organic peroxide represented by the following general formula (1).

(In the formula, R1 and R2 are a methyl group and / or an ethyl group.)
(2) The polymerization initiator composition for producing a polymerized toner according to (1), comprising an organized oxide in which R1 in the general formula (1) is a methyl group and R2 is an ethyl group.
(3) A polymerizable monomer composition for producing a polymerized toner, comprising the polymerization initiator composition according to (1) or (2) and styrene and n-butyl acrylate as polymerizable monomers.
(4) The polymerizable monomer for producing a polymerized toner according to (3), wherein the content of the polymerization initiator composition is 0.5 to 15 parts by mass with respect to 100 parts by mass of the polymerizable monomer. A meter composition.
(5) A suspension polymerization composition for producing a polymerized toner, comprising the polymerizable monomer composition according to (3) or (4) and an aqueous medium.
(6) A suspension polymer for producing a polymerized toner, obtained by polymerizing the suspension polymerization composition as described in (5).
(7) The suspension polymer for producing a polymerized toner according to (6), obtained by polymerization at a temperature of 70 ° C. or higher.

  According to the present invention, as a polymerization initiator, R in the structure represented by the general formulas (100) and (101) is a secondary alkyl group, and R ′ is a tertiary alkyl group. Since the product is used, its 10 hour half-life temperature is relatively high. Therefore, even if the polymerization is performed at a relatively high temperature (for example, 70 ° C. or higher), the organic peroxide in the present invention is not easily decomposed rapidly, so that a decrease in initiator efficiency due to radical deactivation can be avoided. . Thereby, it is possible to avoid the increase in the residual amount of VOC while improving the polymerization rate by polymerizing at a relatively high temperature, and it is possible to improve the productivity of the polymerized toner.

  In addition, according to the present invention, a specific organic peroxide having a relatively low molecular weight is used. However, by simultaneously using toluene, dissolution of the organic peroxide in water can be suppressed. Thereby, the emulsion polymerization by the organic peroxide dissolved in the aqueous layer is also suppressed, and the production of emulsified fine particles having a particle size which is not originally intended can be suppressed.

Hereinafter, the present invention will be described in detail.
[I] Polymerization initiator composition The (B) polymerization initiator composition of the present invention is used when a toner used in a printer, a copying machine, or the like is produced by a suspension polymerization method. A) Contains an organic peroxide and toluene. Specifically, toluene is mixed and dispersed in an organic peroxide. The content ratio is 5 to 50 parts by mass, preferably 10 to 35 parts by mass, with respect to 100 parts by mass of the organic peroxide. When the content of toluene is less than 5 parts by mass with respect to 100 parts by mass of the organic peroxide, the solubility of the organicated oxide in water becomes too high and emulsified fine particles are likely to be generated. On the other hand, when the content of toluene exceeds 50 parts by mass with respect to 100 parts by mass of the organic peroxide, the VOC residual amount tends to increase.

（式中Ｒ１、Ｒ２は、メチル基及び／又はエチル基である。） As the organic peroxide, a peroxy ester having a structure represented by the following general formula (1) can be used.

(In the formula, R1 and R2 are a methyl group and / or an ethyl group.)

  Specifically, t-butylperoxyisobutyrate (R1: methyl group, R2: methyl group), t-butylperoxy-2-methylbutanoate (R1: methyl group, R2: ethyl group, or R1) : Ethyl group, R2: methyl group), t-butylperoxy-2-ethylbutanoate (R1: ethyl group, R2: ethyl group). Among them, t-butylperoxy-2-methylbutanoate in which R1 in the general formula (1) is a methyl group and R2 is an ethyl group is preferable.

[II] Polymerizable monomer composition (D) A polymerizable monomer composition is prepared by mixing and dispersing the (C) polymerizable monomer in the (B) polymerization initiator composition. Can do. A polymerizable monomer refers to a polymerizable compound, and a monovinyl monomer is used as a main component. In the present invention, styrene and n-butyl acrylate are used as the polymerizable monomer.

  The mixing ratio (content ratio) of the polymerization initiator composition and the polymerizable monomer is 0.5 to 15 parts by mass, preferably 0.00 with respect to 100 parts by mass of the polymerizable monomer. 6 to 12 parts by mass. When the content of the polymerization initiator composition is less than 0.5 parts by mass with respect to 100 parts by mass of the polymerizable monomer, the polymerization becomes insufficient and the VOC residual amount increases. On the other hand, when the content of the polymerization initiator composition exceeds 15 parts by mass with respect to 100 parts by mass of the polymerizable monomer, an excess polymerization initiator remains, so that the VOC residual amount tends to increase. The content ratio of styrene and n-butyl acrylate is preferably 70 to 90 parts by mass of styrene and 10 to 30 parts by mass of n-butyl acrylate.

[III] Suspension polymerization composition Furthermore, (F) Suspension polymerization composition can be obtained by mixing and dispersing the (D) polymerizable monomer composition in a preliminarily prepared aqueous medium. it can. An aqueous medium is a medium containing water as a main component, and a dispersion stabilizer is added to the medium. As the dispersion stabilizer, acids or alkali metal salts, metal oxides, water-soluble polymers, and various surfactants may be used alone or in combination of two or more.

  Examples of the acid or alkali metal salt include phosphates such as calcium phosphate, sulfates such as barium sulfate, carbonates such as magnesium carbonate, and alkali metal salts such as magnesium hydroxide.

  Examples of the metal oxide include titanium oxide and aluminum oxide.

  Examples of the water-soluble polymer include polyvinyl alcohol, starch, and hydroxyethyl cellulose.

  Examples of the surfactant include anionic surfactants such as alkylbenzene sulfonates, alkyl sulfate esters and fatty acid salts, cationic surfactants such as alkylamine salts, nonionic surfactants such as polyhydric alcohol derivatives, alanine and the like. Amphoteric surfactants and the like.

  What is necessary is just to mix a dispersion stabilizer about 0.2-20.0 mass parts with respect to 100 mass parts of water. Further, the mixing ratio (content ratio) of the aqueous medium and the polymerizable monomer composition is preferably 1: 1 to 1:10, and needs to be set so that the particles do not aggregate during polymerization.

[IV] Suspension Polymer The suspension polymer of the present invention is obtained by polymerizing the suspension polymerization composition (F) at a predetermined temperature, and then subjecting the aqueous dispersion containing polymer particles to acid washing, water washing, filtration and It can be obtained by drying. Specifically, (B) a polymerization initiator composition, (C) a polymerizable monomer, and an aqueous medium are mixed, and droplets are formed by a TK homomixer or the like. Thereafter, after the inside of the reaction vessel is purged with nitrogen, the temperature is raised to a predetermined polymerization temperature for polymerization, and the aqueous dispersion containing the obtained polymer particles may be washed and filtered.

  In this invention, polymerization temperature becomes like this. Preferably it is 70 degreeC or more, More preferably, it is 80-120 degreeC. This is because the polymerization rate generally increases as the polymerization temperature increases. However, if the polymerization temperature exceeds 120 ° C., there is a possibility of causing a danger during production due to rapid decomposition of the organic peroxide, a decrease in polymerization efficiency due to radical deactivation, or a decrease in the molecular weight of the generated polymer. is there. The polymerization time is preferably 2 to 20 hours, more preferably 3 to 15 hours. If the polymerization time is too long, the productivity is lowered, so there is no great advantage.

EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are all based on mass. Moreover, the following were used as the organic oxide (A).
Organized oxide (I): t-butyl peroxy-2-methylbutanoate (“Perbutyl MB” manufactured by NOF, R1 = ethyl group, R2 = methyl group in general formula (1))
Organized oxide (II): t-butyl peroxyisobutyrate (“Perbutyl IB” manufactured by NOF, R1 = methyl group, R2 = methyl group in general formula (1))
Organized oxide (III): t-butylperoxy-2-ethylbutanoate (“Perbutyl EB” manufactured by NOF, R1 = ethyl group, R2 = ethyl group in general formula (1))
Organic peroxide (IV): t-butyl peroxypivalate represented by the following general formula (2) (“Perbutyl PV” manufactured by NOF Corporation)

<Production of polymerization initiator composition (B)>
(Examples I-1 to I-5, II-1, III-1)
To 100 parts by mass of the organic peroxide (A) shown in Table 1, an amount (parts by mass) of toluene shown in Table 1 was added and mixed and dispersed to produce a polymerization initiator composition (B).

(Comparative Examples I-1 to I-2, II-1 to II-2, III-1, Comparative Example 1)
A polymerization initiator composition (B) was produced in the same manner as in Example I-1, except that the amount of toluene (part by mass) shown in Table 2 was changed using the organic oxide shown in Table 2.

<Production of suspension polymer>
(Example IV-1)
At room temperature, 148 parts by mass of ion-exchanged water and 40 parts by mass of 1 wt% polyvinyl alcohol solution and 15 parts by mass of 10% calcium phosphate solution were added to the polymerization reaction vessel, and then stirred at 11000 rpm for 30 seconds using a TK homomixer. The aqueous medium (E) was adjusted. In 203 parts by mass of this aqueous medium (E), 5.0 parts by mass of the polymerization initiator composition (B) of Example I-1 as a polymerizable monomer composition (D), and a polymerizable monomer After adding 80 parts by mass of styrene and 20 parts by mass of n-butyl acrylate as (C), the mixture was stirred for 1 minute at 11000 rpm using a TK homomixer to obtain a suspension polymerization composition (F). Thereafter, the inside of the reaction vessel was replaced with nitrogen, and the temperature was raised to 90 ° C., followed by carrying out a polymerization reaction for 10 hours. After cooling after completion of the reaction, washing was performed by adding nitric acid until the pH became acidic. Furthermore, after washing | cleaning and filtration using 300 mass parts of water, it was made to dry and the suspension polymer was obtained.

(Examples IV-2 to IV-9)
Example IV-, except that the polymerization initiator compositions (B) of Examples I-2 to I-5, II-1, and III-1 were used in the types and amounts (parts by mass) shown in Table 1. In the same manner as in Example 1, a suspension polymer was obtained. Examples I-2 to I-5, II-1, and III-1 shown in the upper part of Table 1 are the polymerization initiator compositions used in Examples IV-2 to IV-9 shown in the lower part of Table 1. (B) is shown.

(Comparative Examples IV-1 to IV-8)
A suspension polymer was obtained in the same manner as in Example IV-1, except that the polymerization initiator compositions (B) in each Example and Comparative Example were changed to the types and amounts (parts by mass) shown in Table 2. It was. In addition, the Example and comparative example which are shown in the upper part of Table 2 have shown the polymerization initiator composition (B) used in Comparative Examples IV-1 to IV-8 which are shown in the lower part of Table 2.

  Subsequently, each physical property of the suspension polymer of each of the above Examples and Comparative Examples was evaluated. In addition, the measuring method and evaluation method of each physical property are as follows.

<VOC measurement>
After 0.1 g (precisely weighed 1 mg) of the suspension polymer in a screw tube, 18 ml of methylene chloride was added and extracted overnight. To the solution after completion of extraction, 2 ml of cumene diluted with methylene chloride (internal standard substance) was added, filtered through a 0.45 μl membrane filter, and measured. The calibration curve was determined at 5 points by diluting toluene and the internal standard substance cumene with methylene chloride.
<Analysis conditions>
GC: Shimadzu GC-17A
Column: HR-1, manufactured by Shinwa Kako Co., Ltd., 15 m, inner diameter 0.53 mm, film thickness 1.0 μm
Column temperature: Hold at 40 ° C. for 10 minutes → Increase to 10 ° C. per minute up to 190 ° C. → Hold for 5 minutes after reaching 190 ° C. INJ: 100 ° C.
DET: 250 ° C
<VOC evaluation criteria>
The evaluation standard in this evaluation is that the amount of VOC seen from n-hexane to n-hexadecane is converted to toluene based on the air quality guidelines formulated in 2000 by the Ministry of Health, Labor and Welfare. It converted and evaluated as follows according to the quantified value.
In the case of 0.00% or more and less than 0.20%: ◎
When 0.20% or more and less than 0.30%: ○
When 0.30% or more and less than 0.40%: △
When 0.40% or more: ×

<Measurement of emulsified fine particles>
The aqueous dispersion after completion of suspension polymerization is acid-washed and then washed and filtered (140 mesh) using 300 g of ion-exchanged water. At this time, particle size distribution measurement was performed on the obtained separated liquid (apparatus used: Shimadzu SALD-2100). In addition, it can be judged that among the results obtained by the measurement, the larger the proportion of particles of 5 μm or less in the whole, the more emulsified fine particles.
<Emulsion fine particle evaluation criteria>
Evaluation was made as follows according to the proportion of particles of 5 μm or less in the whole.
If less than 40.0%: ◎
In the case of 40.0% or more and less than 47.5%: ○
When 47.5% or more and less than 50.0%: △
In case of 50.0% or more: ×

From the results of Tables 1 and 2, it was confirmed that the productivity of the polymerized toner is adversely affected unless a specific organic oxide having a relatively low molecular weight is used as the polymerization initiator. Further, it was confirmed that a polymerized toner can be produced with high productivity at a polymerization temperature of 70 ° C. or higher by using a polymerization initiator composition containing 5 to 50 parts by mass of toluene with respect to 100 parts by mass of the organic peroxide. . For that purpose, it was also confirmed that the polymerization initiator composition had to be 0.5 to 15 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

Claims (7)

A polymerization initiator composition for producing a polymerized toner, comprising 5 to 50 parts by mass of toluene with respect to 100 parts by mass of an organic peroxide represented by the following general formula (1).

(In the formula, R1 and R2 are a methyl group and / or an ethyl group.)   2. The polymerization initiator composition for producing a polymerized toner according to claim 1, comprising an organic oxide in which R1 in the general formula (1) is a methyl group and R2 is an ethyl group.   A polymerizable monomer composition for producing a polymerized toner, comprising the polymerization initiator composition according to claim 1 or 2 and styrene and n-butyl acrylate as polymerizable monomers.   The polymerizable monomer composition for producing a polymerized toner according to claim 3, wherein the content of the polymerization initiator composition is 0.5 to 15 parts by mass with respect to 100 parts by mass of the polymerizable monomer. object.   A suspension polymerization composition for producing a polymerized toner, comprising the polymerizable monomer composition according to claim 3 or 4 and an aqueous medium.   A suspension polymer for polymerized toner production, obtained by polymerizing the suspension polymerization composition according to claim 5. The suspension polymer for producing a polymerized toner according to claim 6, which is obtained by polymerization at a temperature of 70 ° C or higher.