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
Polymerization initiator composition for manufacturing polymerized toner, and polymerizable monomer composition, suspension polymerized composition, and suspension polymer for manufacturing polymerized toner using the same Download PDFInfo
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Abstract
Description
本発明は、重合トナーの製造に有用な重合開始剤組成物と、これを用いた重合トナー製造用の重合性単量体組成物、懸濁重合組成物、及び懸濁重合物に関する。 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.
トナーとは、プリンターや複写機等で使用され、帯電性を持った結着樹脂に、着色剤や離型剤等を含有させた粒子である。トナーの製造方法には、粉砕法トナーおよび重合トナーの2種類がある。重合トナーは、球状粒子を得やすく、かつ粒径制御が容易であり、生産性向上および高解像度形成が可能となる点で注目を集めている。一般的に重合トナーは、水系媒体中に、重合性単量体と、有機過酸化物からなる重合開始剤と、着色剤、帯電制御剤、離型剤等の添加剤とを含有する重合性単量体組成物を加えて微滴形成した後、重合反応を行うことで得られる。 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.
このような重合トナーの製造に求められる項目としては、トナー中の揮発性有機化合物(VOC:Volatile Organic compounds)が少ないことが挙げられる。VOCとは、常温で気化・蒸発する揮発性有機化合物の総称で、沸点が260℃以下のもの(WHO基準)をさす。また、日本では建築材料向けではあるが、厚生労働省生活衛生局生活化学安全対策室から2000年に出された空気質指針策定で、TVOC=n−ヘキサンからn−ヘキサデカンまでの間に見られる化合物となっている。また、必須VOCsリスト化合物及び検出上位10化合物を定量すること、他VOCはトルエン量に換算して定量することとなっている。 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.
トナー中のVOC残留量が多いと、トナー性能を悪化させるばかりか、印刷時にVOCが揮発して人体に悪影響を及ぼす危険性があるからである。そこで、重合トナー中のVOC残留量を低減する技術として、下記特許文献1が提案されている。 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.
特許文献1は、少なくとも着色剤、重合性単量体、有機過酸化物からなる重合開始剤、および25℃における水への溶解度が0.18〜5.0質量%である芳香属化合物としてトルエンを含有する重合性単量体組成物から懸濁重合法によりトナーを製造する方法であって、下記一般式(100)で示される特定の有機過酸化物を重合開始剤として使用している。
(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.)
また、トナーの高温保存性に優れ、印字を行なった際に悪臭を発生し難いトナーとして、下記特許文献2も提案されている。特許文献2は、重合性単量体及び着色剤を含有する重合性単量体組成物を、水系媒体中で、重合開始剤として有機過酸化物の存在下に重合し、着色重合体粒子を含む水系分散液を得る工程と、気相部の圧力が5〜80kPaである蒸発器内において、攪拌しながら水系分散液の液面下に空気又は不活性ガスを注入するストリッピング工程とを経て重合トナーを製造しており、エーテル成分含有量を500ppm未満としている。特許文献2では、重合開始剤として純度90%以上、より好ましくは92%以上、さらに好ましくは95%以上の下記一般式(101)で表される非芳香族系パーオキシエステルを使用している。
(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.)
なお、重合トナーの製造に求められる項目としては、トナー中のVOC残留量低減の他に、乳化微粒子の生成が少ないことも挙げられる。重合トナーの製造過程における乳化微粒子の生成は重合開始剤である有機過酸化物の水への溶解性に起因しており、重合反応後の脱水・濾過工程などに悪影響を及ぼすため、その生成量を低く抑える必要がある。 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.
特許文献1では、特定の有機過酸化物を重合開始剤として使用しながら、トルエンも添加していることで、トナー中のVOC残留量の低減を図っている。しかしながら、重合開始剤として上記一般式(100)におけるR及びR’が第三級アルキル基である有機過酸化物を使用している。当該R及びR’が第三級の有機過酸化物は、10時間半減期温度が比較的低い。そのため、重合温度も比較的低く設定する必要がある。具体的には、初期の重合温度を65℃に設定し、続いて重合後期に80℃まで昇温することでさらに重合を行う、2段階重合反応を行っている。なお、10時間半減期温度とは、熱分解により10時間で半分になる温度をいう。 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.
一般的に重合温度が高いほど重合速度は増加し、重合温度が低いと重合速度は低下することが知られている。重合温度が低いと、重合時間を長くしたり、重合の前後半で温度を変える必要があり、生産性および作業性の面で難がある。よって、トナーの生産性を上げるためには、重合温度をできるだけ高くして1生産当たりの所要時間を短縮することが求められる。しかしながら、特許文献1では有機過酸化物の10時間半減期温度が比較的低いため、重合温度を上げると重合初期に有機過酸化物が多量に分解することでラジカル失活が起こり、開始剤効率が低下してしまう。これにより、重合開始剤量が減少し、十分にモノマーを重合させることができなくなる。このため、残存モノマー量が増加し、その結果VOC残留量が増加してしまう。 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.
一方、特許文献2では、有機過酸化物の分子量が比較的小さいことで、有機過酸化物由来の副生成物の分子量も小さくなり、重合後の乾燥工程におけるVOCの除去が比較的容易になる。しかしながら、有機過酸化物の分子量を単に小さくするだけでは、有機過酸化物の水への溶解性が増し、水層中に溶けた有機過酸化物によって乳化重合が起こってしまう。このため、本来目的としない粒径を持つ微粒子の生成が多くなり、重合反応後の脱水・濾過工程に影響を及ぼす。 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.
そこで、本発明は上記課題を解決するものであって、その目的は、比較的高い温度で重合してもVOCとなる残留物が少なく、且つ有機過酸化物の水への溶解性に起因する乳化微粒子の生成も少ない重合トナー製造用の重合開始剤組成物と、これを用いた重合トナー製造用の重合性単量体組成物、懸濁重合組成物、及び懸濁重合物を提供することにある。 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.
上記課題を解決するため、本発明は次の手段を採る。
(1)下記一般式(1)で表される有機過酸化物100質量部に対して、トルエンを5〜50質量部含む、重合トナー製造用の重合開始剤組成物。
(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.
本発明によれば、重合開始剤として一般式(100)および(101)で示される構造中のRが第二級のアルキル基、R’が第三級のアルキル基で構成される有機過酸化物を使用しているので、これの10時間半減期温度は比較的高い。したがって、比較的高い温度(例えば70℃以上)で重合しても、本発明における有機過酸化物は急速に分解し難いことから、ラジカル失活に起因する開始剤効率の低下を避けることができる。これにより、比較的高い温度で重合することで重合速度を向上しながらVOC残留量の増大を避けることができ、重合トナーの生産性を向上することができる。 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.
また、本発明によれば、分子量の比較的低い特定の有機過酸化物を使用するが、同時にトルエンを使用することで、有機過酸化物の水への溶解を抑制することができる。これにより、水層中に溶けた有機過酸化物による乳化重合も抑制され、本来目的としない粒径を持つ乳化微粒子の生成が抑制できる。 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.
以下、本発明について詳細に説明する。
[I]重合開始剤組成物
本発明の(B)重合開始剤組成物は、プリンターや複写機等で使用されるトナーを懸濁重合法により製造する際に使用されるものであって、(A)有機過酸化物と、トルエンとを含有する。詳しくは、有機過酸化物にトルエンを混合分散してなる。その含有割合は、有機過酸化物100質量部に対してトルエンを5〜50質量部とし、好ましくは10〜35質量部とする。有機過酸化物100質量部に対してトルエンの含有量が5質量部未満では、有機化酸化物の水への溶解性が高くなり過ぎて、乳化微粒子が生じやすくなる。一方、有機過酸化物100質量部に対してトルエンの含有量が50質量部を超えると、VOC残存量が増える傾向にある。
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.
有機過酸化物としては、下記一般式(1)に示す構造を持つパーオキシエステルを用いることができる。
(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.)
具体的には、t−ブチルパーオキシイソブチレート(R1:メチル基、R2:メチル基)、t−ブチルパーオキシ−2−メチルブタノエート(R1:メチル基、R2:エチル基、又はR1:エチル基、R2:メチル基)、t−ブチルパーオキシ−2−エチルブタノエート(R1:エチル基、R2:エチル基)が挙げられる。中でも、一般式(1)中のR1がメチル基であり、R2がエチル基であるt−ブチルパーオキシ−2−メチルブタノエートが好ましい。 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]重合性単量体組成物
上記(B)重合開始剤組成物に対して(C)重合性単量体を混合分散することで、(D)重合性単量体組成物とすることができる。重合性単量体とは、重合可能な化合物を指し、主成分としてモノビニル単量体を使用する。本発明では、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を使用する。
[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.
重合開始剤組成物と重合性単量体との混合割合(含有割合)は、重合性単量体100質量部に対して重合開始剤組成物を0.5〜15質量部、好ましくは0.6〜12質量部とする。重合性単量体100質量部に対して重合開始剤組成物の含有量が0.5質量部未満では、重合不足となってVOC残存量が増加する。一方、重合性単量体100質量部に対して重合開始剤組成物の含有量が15質量部を超えると、過剰な重合開始剤が残存することで、VOC残存量が増加する傾向にある。また、スチレンおよびn−ブチルアクリレートの含有割合は、スチレンの含有量を70〜90質量部とし、n−ブチルアクリレートの含有量を10〜30質量部とすることが好ましい。 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]懸濁重合組成物
さらに、予め調整してある水系媒体に対して上記(D)重合性単量体組成物を混合分散することで、(F)懸濁重合組成物とすることができる。水系媒体とは、水を主成分とする媒体であって、これに分散安定剤を添加して成る。分散安定剤としては、酸又はアルカリ金属塩、金属酸化物、水溶性高分子および各種界面活性剤が単独または2種以上を組み合わせて用いられる。
[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.
酸又はアルカリ金属塩としては、例えばリン酸カルシウム等のリン酸塩、硫酸バリウム等の硫酸塩、炭酸マグネシウム等の炭酸塩、水酸化マグネシウム等のアルカリ金属塩などが挙げられる。 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.
金属酸化物としては、例えば酸化チタン、酸化アルミニウムなどが挙げられる。 Examples of the metal oxide include titanium oxide and aluminum oxide.
水溶性高分子としては、例えばポリビニルアルコール、デンプン、ヒドロキシエチルセルロースなどが上げられる。 Examples of the water-soluble polymer include polyvinyl alcohol, starch, and hydroxyethyl cellulose.
界面活性剤としては、例えばアルキルベンゼンスルホン酸塩、アルキル硫酸エステル塩、脂肪酸塩等のアニオン界面活性剤、アルキルアミン塩等のカチオン界面活性剤、多価アルコール誘導体等の非イオン界面活性剤、アラニン等の両性界面活性剤などが上げられる。 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.
分散安定剤は、水100質量部に対して0.2〜20.0質量部程度混合すればよい。また、水系媒体と重合性単量体組成物との混合割合(含有割合)としては、1:1〜1:10が好ましく、重合中粒子同士の凝集が起こらないように設定する必要がある。 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]懸濁重合物
本発明の懸濁重合物は、上記(F)懸濁重合組成物を所定温度で重合し、次いで重合体粒子を含む水系分散液を酸洗浄、水洗浄、濾過および乾燥を行うことで得ることができる。詳しくは、(B)重合開始剤組成物、(C)重合性単量体、水系媒体とを混合し、TKホモミキサーなどによって液滴形成させる。その後、反応容器内を窒素置換した後、所定の重合温度まで昇温して重合を行い、得られた重合体粒子を含む水系分散液を洗浄、濾過など行えばよい。
[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.
本発明において、重合温度は好ましくは70℃以上であり、さらに好ましくは80〜120℃である。一般的に、重合温度が高いほど重合速度が増加するからである。但し、重合温度が120℃を超えると、有機過酸化物が急激に分解することによる製造時の危険性、ラジカルの失活による重合効率の低下、又は生成ポリマー分子量の低下等を招く可能性がある。重合時間は2〜20時間が好ましく、さらに好ましくは3〜15時間である。重合時間を長くし過ぎると生産性を落とすため、大きなメリットはない。 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.
以下、本発明を実施例に基づき説明するが、本発明はこれらの実施例に限定されるものではない。なお、実施例および比較例中に記載される「部」および「%」は、全て質量基準である。また、有機化酸化物(A)としては、次のものを使用した。
有機化酸化物(I):t−ブチルパーオキシ−2−メチルブタノエート(日油製「パーブチルMB」、一般式(1)中のR1=エチル基、R2=メチル基)
有機化酸化物(II):t−ブチルパーオキシイソブチレート(日油製「パーブチルIB」、一般式(1)中のR1=メチル基、R2=メチル基)
有機化酸化物(III):t−ブチルパーオキシ−2−エチルブタノエート(日油製「パーブチルEB」、一般式(1)中のR1=エチル基、R2=エチル基)
有機過酸化物(IV):下記一般式(2)で表されるt−ブチルパーオキシピバレート(日油製「パーブチルPV」)
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)
<重合開始剤組成物(B)の製造>
(実施例I−1〜I−5、II−1、III−1)
表1に示す有機過酸化物(A)100質量部に対して、表1に示す量(質量部)のトルエンを加え、混合分散させ重合開始剤組成物(B)を製造した。
<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).
(比較例I−1〜I−2、II−1〜II−2、III−1、比較例1)
表2に示す有機化酸化物を使用して表2に示すトルエン量(質量部)に変更したこと以外は、実施例I−1と同様にして重合開始剤組成物(B)を製造した。
(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.
<懸濁重合物の製造>
(実施例IV−1)
室温下にて、重合反応容器中にイオン交換水148質量部、1wt%ポリビニルアルコール溶液40質量部、10%リン酸カルシウム溶液15質量部を加えた後、TKホモミキサーを用いて11000rpmにて30秒間撹拌し、水系媒体(E)を調整した。この水系媒体(E)203質量部中に、重合性単量体組成物(D)として、実施例I−1の重合開始剤組成物(B)5.0質量部と、重合性単量体(C)であるスチレン80質量部及びn−ブチルアクリレート20質量部とを加えた後、TKホモミキサーを用いて11000rpmにて1分間撹拌し、懸濁重合組成物(F)を得た。その後、反応容器内を窒素置換し、90℃まで昇温した後、10時間重合反応を行った。反応終了後に冷却した後、pHが酸性になるまで硝酸を加え洗浄を行った。さらに、水300質量部を用いて洗浄・濾過を行った後、乾燥させ懸濁重合物を得た。
<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.
(実施例IV−2〜IV−9)
実施例I−2〜I−5、II−1、III−1の重合開始剤組成物(B)を、表1に示す種類と量(質量部)で使用したこと以外は、実施例IV−1と同様にして懸濁重合物を得た。なお、表1の上段に示す実施例I−2〜I−5、II−1、III−1は、表1の下段に示す実施例IV−2〜IV−9において使用した重合開始剤組成物(B)を示している。
(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.
(比較例IV−1〜IV−8)
各実施例及び比較例の重合開始剤組成物(B)を、表2に示す種類と量(質量部)に変更したこと以外は、実施例IV−1と同様にして懸濁重合物を得た。なお、表2の上段に示す実施例及び比較例は、表2の下段に示す比較例IV−1〜IV−8において使用した重合開始剤組成物(B)を示している。
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.
続いて、上記各実施例及び比較例の懸濁重合物の各物性を評価した。なお、各物性の測定方法及び評価方法は、次の通りである。 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測定>
スクリュー管瓶中に懸濁重合物を0.1g(1mgまで精秤)入れた後、塩化メチレン18mlを加え一晩抽出した。抽出終了後の溶液に、塩化メチレンで希釈したクメン(内部標準物質)を2ml加え、0.45μlのメンブランフィルターで濾過した後、測定した。検量線は、トルエンと内部標準物質クメンを塩化メチレンで希釈し5点で求めた。
<分析条件>
GC :Shimadzu GC-17A
カラム :HR−1、信和化工社製、15m 内径0.53mm 膜厚1.0μm
カラム温度:40℃で10分間保持→190℃まで毎分10℃の昇温→190℃到達後5分間保持
INJ :100℃
DET :250℃
<VOC評価基準>
本評価における評価基準は、厚生労働省生活衛生局生活化学安全対策室から2000年に出された空気質指針策定に基づき、n−ヘキサンからn−ヘキサデカンまでの間に見られるVOC量をトルエン量に換算し、定量された値に応じて下記のように評価した。
0.00%以上0.20%未満の場合:◎
0.20%以上0.30%未満の場合:○
0.30%以上0.40%未満の場合:△
0.40%以上の場合:×
<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: ×
<乳化微粒子測定>
懸濁重合終了後の水系分散液を酸洗浄した後、300gのイオン交換水を用いて洗浄・濾過(140mesh)を行っている。この時、得られる分離液について粒度分布測定を行った(使用装置:Shimadzu SALD-2100)。なお、測定によって得られた結果の中で、5μm以下の粒子の全体に占める割合が多い程、乳化微粒子が多いと判断できる。
<乳化微粒子評価基準>
全体に占める5μm以下の粒子割合に応じて下記のように評価した。
40.0%未満 の場合:◎
40.0%以上47.5%未満の場合:○
47.5%以上50.0%未満の場合:△
50.0%以上の場合:×
<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: ×
表1及び表2の結果から、重合開始剤として比較的分子量の低い特定の有機化酸化物を使用しなければ、重合トナーの生産性に悪影響があることが確認された。また、当該有機過酸化物100質量部に対してトルエンを5〜50質量部含む重合開始剤組成物を使用すれば、重合温度70℃以上にて生産性良く重合トナーを製造できることが確認された。そのためには、重合性単量体100質量部に対して重合開始剤組成物を0.5〜15質量部としなければならないことも確認された。
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)
(式中R1、R2は、メチル基及び/又はエチル基である。) 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.)
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.
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Cited By (2)
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JP2014105254A (en) * | 2012-11-27 | 2014-06-09 | Nof Corp | Organic peroxide-containing polymerizable monomer composition, suspension polymerization composition, and suspension polymer for manufacturing suspension polymerization toner |
WO2019125066A1 (en) * | 2017-12-21 | 2019-06-27 | 주식회사 엘지화학 | Initiator composition for preparing vinyl chloride-based polymer, method for preparing vinyl chloride-based polymer by using same, and vinyl chloride-based polymer prepared thereby |
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JPH07120971A (en) * | 1993-10-22 | 1995-05-12 | Mitsubishi Rayon Co Ltd | Toner binder resin and its production |
JPH1020548A (en) * | 1996-07-08 | 1998-01-23 | Nippon Zeon Co Ltd | Production of polymerized toner |
JP2005106939A (en) * | 2003-09-29 | 2005-04-21 | Canon Inc | Toner and method for manufacturing toner |
JP2009014763A (en) * | 2007-06-29 | 2009-01-22 | Nippon Zeon Co Ltd | Method of manufacturing toner for electrostatic image development |
JP2009063969A (en) * | 2007-09-10 | 2009-03-26 | Canon Inc | Toner, image forming method, image forming apparatus and developing device |
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JPH07120971A (en) * | 1993-10-22 | 1995-05-12 | Mitsubishi Rayon Co Ltd | Toner binder resin and its production |
JPH1020548A (en) * | 1996-07-08 | 1998-01-23 | Nippon Zeon Co Ltd | Production of polymerized toner |
JP2005106939A (en) * | 2003-09-29 | 2005-04-21 | Canon Inc | Toner and method for manufacturing toner |
JP2009014763A (en) * | 2007-06-29 | 2009-01-22 | Nippon Zeon Co Ltd | Method of manufacturing toner for electrostatic image development |
JP2009063969A (en) * | 2007-09-10 | 2009-03-26 | Canon Inc | Toner, image forming method, image forming apparatus and developing device |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2014105254A (en) * | 2012-11-27 | 2014-06-09 | Nof Corp | Organic peroxide-containing polymerizable monomer composition, suspension polymerization composition, and suspension polymer for manufacturing suspension polymerization toner |
WO2019125066A1 (en) * | 2017-12-21 | 2019-06-27 | 주식회사 엘지화학 | Initiator composition for preparing vinyl chloride-based polymer, method for preparing vinyl chloride-based polymer by using same, and vinyl chloride-based polymer prepared thereby |
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