JP2014105254A - Organic peroxide-containing polymerizable monomer composition, suspension polymerization composition, and suspension polymer for manufacturing suspension polymerization toner - Google Patents
Organic peroxide-containing polymerizable monomer composition, suspension polymerization composition, and suspension polymer for manufacturing suspension polymerization toner Download PDFInfo
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本発明は、有機過酸化物を含有する懸濁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 polymerizable monomer composition for producing a suspension polymerization toner containing an organic peroxide, a suspension polymerization composition, and a suspension polymerization product.
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。重合トナーには懸濁重合トナー、溶解懸濁トナー、乳化重合凝集トナーがあるが、懸濁重合トナーは、一般的に水系媒体中に、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. Polymerized toner includes suspension polymerization toner, dissolution suspension toner, and emulsion polymerization aggregation toner. Suspension polymerization toner is generally a polymerization composed of a polymerizable monomer and an organic peroxide in an aqueous medium. It is obtained by adding a polymerizable monomer composition containing an initiator and additives such as a colorant, a charge control agent and a release agent to form fine droplets, and then performing a polymerization reaction.
このような懸濁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 suspension polymerization 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 by 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.
懸濁重合トナー中の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。そこで、懸濁重合トナー中の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。 If the amount of residual VOC in the suspension polymerization toner is large, not only the toner performance is deteriorated, but there is a risk that the VOC volatilizes during printing and adversely affects the human body. Therefore, Patent Document 1 below has been proposed as a technique for reducing the VOC residual amount in the suspension polymerization toner.
特許文献１は、トナーの高温保存性に優れ、印字を行った際に悪臭を発生し難い懸濁重合トナーを製造する方法である。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懸濁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１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（１００）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。
（Ｒは炭素数８以下のアルキル基であり、Ｒ’は炭素数６以下のアルキル基である。）
Patent Document 1 is a method for producing a suspension-polymerized toner that is excellent in high-temperature storage stability of a toner and does not easily generate malodor when printing is performed. 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 an aqueous dispersion containing colored polymer particles is obtained. The suspension polymerization toner is obtained through a step of obtaining and a stripping step of injecting air or an inert gas below the surface of the aqueous dispersion while stirring in an evaporator having a gas phase pressure of 5 to 80 kPa. The ether component content is less than 500 ppm. In Patent Document 1, a non-aromatic peroxyester represented by the following general formula (100) having a purity of 90% or more, more preferably 92% or more, and further preferably 95% or more is used as a polymerization initiator. .
(R is an alkyl group having 8 or less carbon atoms, and R ′ is an alkyl group having 6 or less carbon atoms.)
特許文献１の実施例は、上記一般式（１００）のＲがＣＨ（Ｃ２Ｈ５）２、Ｒ’がｔ−Ｂｕの化合物（ｔ−ブチルパーオキシ−２−エチルブタノエート）について記載されている。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ＶＯＣである分解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、ＶＯＣ残留量の低減が十分でない。 Examples of Patent Document 1 describe a compound (t-butylperoxy-2-ethylbutanoate) in which R in the general formula (100) is CH (C 2 H 5 ) 2 and R ′ is t-Bu. Has been. Since the molecular weight of the organic peroxide is relatively small, the molecular weight of the decomposition product, which is a VOC derived from the organic peroxide, is also small, and the removal of VOC in the drying step after polymerization is relatively easy. However, simply reducing the molecular weight of the organic peroxide is not enough to reduce the VOC residue.
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、前記ｔ−ブチルパーオキシ−２−エチルブタノエートと同一の分子量であるにも関わらず、ＶＯＣとなる残留物がさらに少ない有機過酸化物を用いた懸濁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 object is to further provide a residue that becomes VOC even though the molecular weight is the same as that of t-butylperoxy-2-ethylbutanoate. It is an object of the present invention to provide a polymerizable monomer composition, a suspension polymerization composition, and a suspension polymerization product for producing a suspension polymerization toner using a small amount of organic peroxide.
上記課題を解決するため、本発明は次の手段を採る。
（１）下記構造式（１）で表される有機過酸化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、懸濁重合トナー製造用の重合性単量体組成物。
（２）有機過酸化物の含有量が、重合性単量体１００質量部に対して０．５〜１０質量部である、（１）に記載の懸濁重合トナー製造用の重合性単量体組成物。
（３）（２）に記載の重合性単量体組成物と、水系媒体とを含有する、懸濁重合トナー製造用の懸濁重合組成物。
（４）（３）に記載の懸濁重合組成物を重合して得られる、懸濁重合トナー製造用の懸濁重合物。
（５）７０℃以上の温度で重合して得られる、（４）に記載の懸濁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 polymerizable monomer composition for producing a suspension polymerization toner, comprising an organic peroxide represented by the following structural formula (1) and styrene and n-butyl acrylate as polymerizable monomers.
(2) The polymerizable single amount for producing the suspension polymerization toner according to (1), wherein the content of the organic peroxide is 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Body composition.
(3) A suspension polymerization composition for producing a suspension polymerization toner, comprising the polymerizable monomer composition according to (2) and an aqueous medium.
(4) A suspension polymer for producing a suspension polymerization toner obtained by polymerizing the suspension polymerization composition as described in (3).
(5) The suspension polymer for producing a suspension polymerization toner according to (4), obtained by polymerization at a temperature of 70 ° C. or higher.
本発明によれば、構造式（１）の有機過酸化物を用いることで、ｔ−ブチルパーオキシ−２−エチルブタノエートと同一の分子量であるにも関わらず、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。そして、開始剤効率の低下を抑制することにより、ＶＯＣである未反応の重合性単量体の量を低減することができるため、製造される懸濁重合トナー中のＶＯＣ残留量をさらに低減することができる。 According to the present invention, by using the organic peroxide of the structural formula (1), the molecular weight is the same as that of t-butylperoxy-2-ethylbutanoate, but it is caused by radical deactivation. A decrease in initiator efficiency can be avoided. Further, by suppressing the decrease in initiator efficiency, the amount of unreacted polymerizable monomer that is VOC can be reduced, so that the remaining amount of VOC in the produced suspension polymerization toner is further reduced. be able to.
以下、本発明について詳細に説明する。本発明の重合性単量体組成物は、有機過酸化物と重合性単量体とを含有する。 Hereinafter, the present invention will be described in detail. The polymerizable monomer composition of the present invention contains an organic peroxide and a polymerizable monomer.
［有機過酸化物］
（Ａ）有機過酸化物は、高分子を合成する重合反応を開始させるための重合開始剤の一種であり、重合開始剤の中でもラジカル開始剤に分類される。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は、（Ａ）有機過酸化物が一般に用いられる。本発明においては、（Ａ）有機過酸化物として下記構造式（１）で示されるｔ−アミルパーオキシ−２−メチルブタノエートが用いられる。
(A) An organic peroxide is a kind of polymerization initiator for initiating a polymerization reaction for synthesizing a polymer, and is classified as a radical initiator among the polymerization initiators. When a toner used in a printer or a copying machine is produced by a suspension polymerization method, (A) an organic peroxide is generally used. In the present invention, (A) t-amylperoxy-2-methylbutanoate represented by the following structural formula (1) is used as the organic peroxide.
［重合性単量体］
（Ｂ）重合性単量体とは重合可能な化合物を指し、懸濁重合トナーの製造においてはモノビニル単量体が主成分として用いられる。本発明では、（Ｂ）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が用いられる。
[Polymerizable monomer]
(B) The polymerizable monomer refers to a polymerizable compound, and a monovinyl monomer is used as a main component in the production of a suspension polymerization toner. In the present invention, styrene and n-butyl acrylate are used as the polymerizable monomer (B).
［重合性単量体組成物］
（Ｃ）重合性単量体組成物は、（Ａ）有機過酸化物と（Ｂ）重合性単量体とを含有しており、本発明においては、（Ａ）有機過酸化物であるｔ−アミルパーオキシ−２−メチルブタノエートに対して、（Ｂ）重合性単量体であるスチレン及びｎ−ブチルアクリレートを混合することで作成することができる。
[Polymerizable monomer composition]
(C) The polymerizable monomer composition contains (A) an organic peroxide and (B) a polymerizable monomer, and in the present invention, (t) is (A) an organic peroxide. -It can produce by mixing styrene and n-butyl acrylate which are (B) polymerizable monomers with respect to amyl peroxy-2-methylbutanoate.
（Ａ）有機過酸化物と（Ｂ）重合性単量体との混合割合（含有割合）は、（Ｂ）重合性単量体１００質量部に対して、（Ａ）有機過酸化物であるｔ−アミルパーオキシ−２−メチルブタノエートが０．５〜１０質量部であることが好ましい。重合性単量体１００質量部に対してｔ−アミルパーオキシ−２−メチルブタノエートの含有量が０．５質量部未満では、重合不足となり、ＶＯＣであるスチレンが未反応のまま残存するため、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ｔ−アミルパーオキシ−２−メチルブタノエートの含有量が１０質量部を超えると、ＶＯＣであるｔ−アミルパーオキシ−２−メチルブタノエートの分解物の量が増加するため、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、両者の合計が１００質量部となる範囲で、スチレンの含有量を６０〜９０質量部とし、ｎ−ブチルアクリレートの含有量を１０〜４０質量部とすることが好ましい。 The mixing ratio (content ratio) of (A) organic peroxide and (B) polymerizable monomer is (A) organic peroxide with respect to 100 parts by mass of (B) polymerizable monomer. It is preferable that t-amyl peroxy-2-methylbutanoate is 0.5-10 mass parts. When the content of t-amylperoxy-2-methylbutanoate is less than 0.5 parts by mass with respect to 100 parts by mass of the polymerizable monomer, the polymerization is insufficient and styrene as VOC remains unreacted. Therefore, the remaining amount of VOC increases. On the other hand, when the content of t-amylperoxy-2-methylbutanoate exceeds 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer, t-amylperoxy-2-methylbutanoate which is VOC is used. Since the amount of ate decomposition products increases, the residual amount of VOC tends to increase. The content ratio of styrene and n-butyl acrylate is such that the total of both is 100 parts by mass, the content of styrene is 60 to 90 parts by mass, and the content of n-butyl acrylate is 10 to 40 parts by mass. It is preferable that
また、（Ｃ）重合性単量体組成物には添加剤を加えることもできる。添加剤の例としては、着色剤、帯電制御剤、離型剤などが挙げられ、その目的に応じて一種又は複数種を添加することができる。 Moreover, an additive can also be added to the (C) polymerizable monomer composition. Examples of the additive include a colorant, a charge control agent, a release agent, and the like, and one or more kinds can be added depending on the purpose.
［懸濁重合組成物］
さらに、予め調整してある（Ｄ）水系媒体に対して上記（Ｃ）重合性単量体組成物を混合分散することで、（Ｅ）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。
[Suspension polymerization composition]
Furthermore, (E) a suspension polymerization composition can be obtained by mixing and dispersing the (C) polymerizable monomer composition in (D) an aqueous medium that has been adjusted in advance. 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等が上げられる。 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、質量基準で（Ｃ）重合性単量体組成物：（Ｄ）水系媒体＝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. The mixing ratio (content ratio) of the aqueous medium and the polymerizable monomer composition is (C) polymerizable monomer composition: (D) aqueous medium = 1: 1 to 1:10 on a mass basis. Is preferable, and it is necessary to set so that aggregation of particles does not occur during polymerization.
［懸濁重合物］
本発明の懸濁重合物は、上記（Ｅ）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、（Ａ）有機過酸化物、（Ｂ）重合性単量体、（Ｄ）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。
[Suspension polymer]
The suspension polymer of the present invention is obtained by polymerizing the above (E) suspension polymerization composition at a predetermined temperature, and then subjecting the aqueous dispersion containing the polymer particles to acid washing, water washing, filtration and drying. Can do. Specifically, (A) an organic peroxide, (B) a polymerizable monomer, and (D) 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、質量基準である。また、（Ａ）有機過酸化物としては、次のものを使用した。
有機化酸化物（Ｉ）：ｔ−アミルパーオキシ−２−メチルブタノエート、（構造式１）
有機化酸化物（ＩＩ）：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」）
EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to these Examples. In addition, “parts” and “%” described in Examples and Comparative Examples are based on mass. Moreover, the following were used as (A) organic peroxide.
Organized oxide (I): t-amylperoxy-2-methylbutanoate (Structural Formula 1)
Organized oxide (II): t-butyl peroxy-2-ethylbutanoate (NOF "Perbutyl EB")
＜懸濁重合物の製造＞
（実施例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、（Ｄ）水系媒体を調製した。この（Ｄ）水系媒体２０３質量部中に、（Ａ）重合開始剤であるｔ−アミルパーオキシ−２−メチルブタノエート４．０質量部と重合性単量体（Ｂ）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（Ｃ）重合性単量体組成物として加えた後、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（Ｅ）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 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. (D) An aqueous medium was prepared. In 203 parts by mass of this (D) aqueous medium, (A) 4.0 parts by mass of t-amylperoxy-2-methylbutanoate as a polymerization initiator and styrene 80 as a polymerizable monomer (B). After adding a mass part and 20 mass parts of n-butyl acrylate as (C) polymerizable monomer composition, it stirs at 11000 rpm for 1 minute using TK homomixer, and suspension polymerization composition (E) is carried out. Obtained. 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２、３）
（Ａ）有機過酸化物を、表１に示す量（質量部）で使用したこと以外は、実施例１と同様にして懸濁重合物を得た。
(Examples 2 and 3)
(A) A suspension polymer was obtained in the same manner as in Example 1 except that the organic peroxide was used in the amount (parts by mass) shown in Table 1.
（比較例１、２）
（Ａ）有機過酸化物を、表１に示す量（質量部）で使用したこと以外は、実施例１と同様にして懸濁重合物を得た。
（比較例３）
（Ａ）有機過酸化物としてｔ−ブチルパーオキシ−２−エチルブタノエートを使用したこと以外は、実施例１と同様にして懸濁重合物を得た。
(Comparative Examples 1 and 2)
(A) A suspension polymer was obtained in the same manner as in Example 1 except that the organic peroxide was used in the amount (parts by mass) shown in Table 1.
(Comparative Example 3)
(A) A suspension polymer was obtained in the same manner as in Example 1 except that t-butylperoxy-2-ethylbutanoate was used as the organic peroxide.
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。
０．３０％未満の場合：○
０．３０％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.
When less than 0.30%: ○
When 0.30% 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４５．０％未満の場合：○
４５．０％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 45.0%: ○
In the case of 45.0% or more and less than 50.0%:
In case of 50.0% or more: ×
表１の結果から、重合開始剤としてｔ−ブチルパーオキシ−２−エチルブタノエートを用いた場合と比べて、開始剤効率の高いｔ−アミルパーオキシ−２−メチルブタノエートを使用することにより、残留するＶＯＣを低減することができた。また、重合性単量体１００質量部に対して重合開始剤を０．５〜１０質量部としなければＶＯＣの残留量が増大することも確認された。
From the results in Table 1, t-amylperoxy-2-methylbutanoate having higher initiator efficiency is used as compared with the case where t-butylperoxy-2-ethylbutanoate is used as the polymerization initiator. As a result, the remaining VOC could be reduced. It was also confirmed that the residual amount of VOC increased unless the polymerization initiator was 0.5 to 10 parts by mass relative to 100 parts by mass of the polymerizable monomer.
上記課題を解決するため、本発明は次の手段を採る。
（１）下記構造式（１）で表される有機過酸化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し、有機過酸化物の含有量が、重合性単量体１００質量部に対して０．５〜１０質量部である、懸濁重合トナー製造用の重合性単量体組成物。
（２）（１）に記載の重合性単量体組成物と、水系媒体とを含有する、懸濁重合トナー製造用の懸濁重合組成物。
（３）（２）に記載の懸濁重合組成物を重合して得られる、懸濁重合トナー製造用の懸濁重合物。
（４）７０℃以上の温度で重合して得られる、（３）に記載の懸濁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) An organic peroxide represented by the following structural formula (1) and styrene and n-butyl acrylate as a polymerizable monomer are contained , and the content of the organic peroxide is a polymerizable monomer 100. A polymerizable monomer composition for producing a suspension polymerization toner , which is 0.5 to 10 parts by mass with respect to part by mass .
( 2 ) A suspension polymerization composition for producing a suspension polymerization toner, comprising the polymerizable monomer composition according to ( 1 ) and an aqueous medium.
( 3 ) A suspension polymer for producing a suspension polymerization toner obtained by polymerizing the suspension polymerization composition as described in ( 2 ).
( 4 ) The suspension polymer for suspension polymerization toner production according to ( 3 ), obtained by polymerization at a temperature of 70 ° C. or higher.
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、質量基準である。また、（Ａ）有機過酸化物としては、次のものを使用した。
有機過酸化物（Ｉ）：ｔ−アミルパーオキシ−２−メチルブタノエート、（構造式１）
有機過酸化物（ＩＩ）：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」）
EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to these Examples. In addition, “parts” and “%” described in Examples and Comparative Examples are based on mass. Moreover, the following were used as (A) organic peroxide.
Organic peroxide (I): t-amylperoxy-2-methylbutanoate (Structural Formula 1)
Organic peroxide (II): t-butyl peroxy-2-ethylbutanoate (NOF "Perbutyl EB")
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| JP2015132757A (en) * | 2014-01-15 | 2015-07-23 | 日本ゼオン株式会社 | Manufacturing method of polymerized toner |
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| JP2007052039A (en) * | 2005-07-19 | 2007-03-01 | Nippon Zeon Co Ltd | Process for producing polymerized toner |
| JP2009014763A (en) * | 2007-06-29 | 2009-01-22 | Nippon Zeon Co Ltd | Method of manufacturing toner for electrostatic image development |
| JP2013189594A (en) * | 2012-03-15 | 2013-09-26 | Nof Corp | Polymerization initiator composition for manufacturing polymerized toner, and polymerizable monomer composition, suspension polymerized composition, and suspension polymer for manufacturing polymerized toner using the same |
| WO2013145877A1 (en) * | 2012-03-29 | 2013-10-03 | 日本ゼオン株式会社 | Toner for electrostatic image development and production method therefor |
| WO2013146048A1 (en) * | 2012-03-27 | 2013-10-03 | 日本ゼオン株式会社 | Method for producing toner |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007052039A (en) * | 2005-07-19 | 2007-03-01 | Nippon Zeon Co Ltd | Process for producing polymerized toner |
| JP2009014763A (en) * | 2007-06-29 | 2009-01-22 | Nippon Zeon Co Ltd | Method of manufacturing toner for electrostatic image development |
| JP2013189594A (en) * | 2012-03-15 | 2013-09-26 | Nof Corp | Polymerization initiator composition for manufacturing polymerized toner, and polymerizable monomer composition, suspension polymerized composition, and suspension polymer for manufacturing polymerized toner using the same |
| WO2013146048A1 (en) * | 2012-03-27 | 2013-10-03 | 日本ゼオン株式会社 | Method for producing toner |
| WO2013145877A1 (en) * | 2012-03-29 | 2013-10-03 | 日本ゼオン株式会社 | Toner for electrostatic image development and production method therefor |
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| JP2015132757A (en) * | 2014-01-15 | 2015-07-23 | 日本ゼオン株式会社 | Manufacturing method of polymerized toner |
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