JPS6080857A - Composition for manufacturing colored particle for forming color image - Google Patents
Composition for manufacturing colored particle for forming color imageInfo
- Publication number
- JPS6080857A JPS6080857A JP58188422A JP18842283A JPS6080857A JP S6080857 A JPS6080857 A JP S6080857A JP 58188422 A JP58188422 A JP 58188422A JP 18842283 A JP18842283 A JP 18842283A JP S6080857 A JPS6080857 A JP S6080857A
- Authority
- JP
- Japan
- Prior art keywords
- colored particles
- weight
- meth
- latex
- color image
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08726—Polymers of unsaturated acids or derivatives thereof
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08726—Polymers of unsaturated acids or derivatives thereof
- G03G9/08728—Polymers of esters
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08793—Crosslinked polymers
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はカラー複写電送機器、各種複写機器などのカラ
ー画像形成に用いられる着色粒子製造用組成物に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition for producing colored particles used for color image formation in color copying and transmission equipment, various types of copying equipment, and the like.
本発明の組成物で製造されるカラー画像形成用着色粒子
は、例えば特公昭５５−２７３４０に示される様に原稿
からの光を該着色粒子をフィルターとして色分解し、該
粒子中の昇華性もしくは熱移行性の無色ロイコ染料の伝
染によって画像を形成するようなシステムに用いられる
。このような／ステムに用いられる着色粒子に要求され
る性能は平均粒子径５〜１００μの範囲において、真球
に近いことと、光の透過率が高いことと、かつ耐ブロッ
キング性（貯蔵時および使用時において着色粒子同志か
伺着して、凝集塊を生成しない）がすぐれていることで
ある。従来、カラー画像形成着色粒子は、樹脂状重合体
を粒子形成用樹脂として用い、有機溶剤の溶液として顔
料、その他の成分と十分混合した後、噴霧乾慄などの造
粒法により製造されていた。The colored particles for color image formation produced using the composition of the present invention are produced by color-separating light from an original using the colored particles as a filter, as shown in Japanese Patent Publication No. 55-27340, and Used in systems where images are formed by the transfer of heat-transferable colorless leuco dyes. The performance required of the colored particles used in such/stem is that they should be close to a true sphere in the average particle size range of 5 to 100μ, have high light transmittance, and have blocking resistance (during storage and It is excellent in that colored particles do not stick together and form agglomerates during use. Conventionally, color image-forming colored particles have been produced by using a resinous polymer as a particle-forming resin, thoroughly mixing it with pigments and other ingredients as a solution of an organic solvent, and then using a granulation method such as spray drying. .
しかしながら、上記の方法では造粒工程で所定の粒径を
得るためには使用する配合物の粘度を低くするために固
形分濃度を下げる心安かあり、その結果有機溶剤を多量
に使用するために製造コストが高くなるとともに環境汚
染上の問題点があった。However, in the above method, in order to obtain a predetermined particle size in the granulation process, it is necessary to lower the solid content concentration in order to lower the viscosity of the formulation used, and as a result, a large amount of organic solvent is used. In addition to increasing manufacturing costs, there were also problems with environmental pollution.
かかる背景に鑑み、上記の問題点を解決すべく鋭意検討
した結果、特定の重合体ラテックスを粒子形成用物質と
して用いることにより、真球に近く５光透過率が高く、
かつ耐ブロッキング性にすぐれた着色粒子が得られるこ
とを見い出し本発明を完成した。すなわち、本発明は着
色顔料と粒子形成用物質とから成るカラー画像形成着色
粒子製造用組成物において、重合体鎖中に（１１０，５
〜ＩＯ重量ヂの少なくとも一種のエチレン性不飽和酸、
（２＋ ０．３〜１５重量％の少なくとも一種の共重合
可能な自己架橋性単量体ならびに＋３） ８０〜９９．
２重量％の、少なくとも共役ジエンを含む前記の各単量
体と共重合可能な単量体を含有するガラス転移温度が一
１０℃以上で、かつゲル含有量が４００重量％上である
自己架橋性重合体のラテックスを粒子形成用物質として
使用するカラー画像形成着色粒子製造用組成物を提供す
るものである。In view of this background, as a result of intensive studies to solve the above problems, we have found that by using a specific polymer latex as a particle forming material, it is possible to obtain particles that are close to true spheres and have high light transmittance.
The present invention was completed based on the discovery that colored particles with excellent blocking resistance could be obtained. That is, the present invention provides a composition for producing color image-forming colored particles comprising a colored pigment and a particle-forming substance, in which (110,5
~IO weight of at least one ethylenically unsaturated acid,
(2+ 0.3-15% by weight of at least one copolymerizable self-crosslinking monomer and +3) 80-99.
2% by weight of a monomer copolymerizable with each of the above-mentioned monomers containing at least a conjugated diene, a self-crosslinking product having a glass transition temperature of 110° C. or more and a gel content of 400% by weight or more. The object of the present invention is to provide a composition for producing colored particles for forming color images, using a latex of a polymer as a particle-forming substance.
本発明で使用する粒子形成用重合体ラテックスはガラス
転移温度が一１０°Ｃ以上でゲル含有量が４０重量％以
上のエチレン性不飽和酸、自己架橋性単量体及び共役ジ
エンを必須成分とする単量体は０．５〜１０重量係であ
り、０．５重量％未満では重合体ラテックスの機椋的安
定性か悪くなり、造粒工程でスプレー等のノズル等か詰
まる欠点があり、また１００重量％超えるとアルカリで
ラテックスを中和するとラテックスの粘度が高くなり、
己架橋性単量体の含有量は０．３〜１５重量％であり、
０．３重量％未満では着色粒子の耐ブロッキング性が悪
く、１５重量％を超えても着色粒子としての性能はほと
んど変らなくなり、経済的でない。The particle-forming polymer latex used in the present invention contains as essential components an ethylenically unsaturated acid with a glass transition temperature of 110°C or higher and a gel content of 40% by weight or higher, a self-crosslinking monomer, and a conjugated diene. The amount of the monomer to be used is 0.5 to 10% by weight, and if it is less than 0.5% by weight, the mechanical stability of the polymer latex will be poor, and there will be problems such as clogging of spray nozzles during the granulation process. Also, if it exceeds 100% by weight, the viscosity of the latex will increase if you neutralize it with an alkali.
The content of self-crosslinking monomer is 0.3 to 15% by weight,
If it is less than 0.3% by weight, the blocking resistance of the colored particles will be poor, and if it exceeds 15% by weight, the performance of the colored particles will hardly change, making it uneconomical.
好ましくは０．５〜１０重量饅である。Preferably it is 0.5 to 10 weight rice cakes.
エチレン性不飽和酸としてはアクリル酸、メタクリル酸
、イタコン酸、マレイン酸；イタコン酸モノエチルエス
テル、マレイン酸モノブチルエステルなどの不飽和ジカ
ルボン酸のモノアルキルエステル；アクリル酸スルフオ
ニチルＮＦｌ塩、メタクリル酸スルフオプロピルＮａ塩
、アクリルアミド―プロハンスルフオン酸などの不飽和
カルボン酸、不飽和スルフォン酸などが例示される。こ
れらの不飽和酸をアルカリ金属塩、アンモニウム塩など
の塩として使用しても良い。エチレン性不飽和酸は一種
あるいは二種以上組合わせて使用される。Examples of ethylenically unsaturated acids include acrylic acid, methacrylic acid, itaconic acid, and maleic acid; monoalkyl esters of unsaturated dicarboxylic acids such as itaconic acid monoethyl ester and maleic acid monobutyl ester; Examples include phopropyl Na salt, unsaturated carboxylic acids such as acrylamide-prohanesulfonic acid, and unsaturated sulfonic acids. These unsaturated acids may be used as salts such as alkali metal salts and ammonium salts. Ethylenically unsaturated acids may be used singly or in combination.
自己架橋性単量体としてはＮ−メチロールアクリルアミ
ド、Ｎ−メチロールメタクリルアミド、Ｎ、 Ｎ’−ジ
メチロールイタコン酸ジアミド、Ｎ−イソブトキシメチ
ルアクリルアミドなどのエチレン性不飽和酸のＮ−アル
ギロールアミド及びＮ−アルコキシアルキルアミド；グ
リシジルアクリレート、グリシジルメタクリレート、ア
リルレグリンジルエーテル等のグリシジル基含有単量体
；アリルアルコール、２−ヒドロキシエチルアクＩＪ
Ｌ／−１・、２−ヒドロキシエチルメタクリレート等の
水酸基含有単量体； Ｎ、 Ｎ’−ジメチルアミノエチ
ルアクリレート等のアミノ基含有単量体；マレインアミ
ド等のアミド基含有単量体；ジビニルベンゼン等のジビ
ニル基含有芳香族系単量体等が例示さ成分は少なくとも
共役ジエンが含まれる８０〜９９．２重量％の前記三種
σ戸１／、 ｆｉｊ体と共重合可能な単量体で、本発明
の重合体のガラス転移温度が一１０℃以上となる単量体
であれば特に制限はな重量係である。本発明の重合体の
ガラス転移温度が一１０℃未満では真球に近い粒子か得
られにくく、又耐ブロッキング性も低下する。好ましく
は−５℃以上である。ガラス転移温度は高い程耐ブロッ
キング性は良（なるか、造ね時の乾燥工程ての水の蒸発
速度の調節が困難となるので１００°Ｃ以下が好ましい
。第三成分の単量体としては１．：３−フクシエン、イ
ングレノ、１．）−ペックジエン、クロロフレン等の共
役ジエン；スチレン、α−メチルスチレン等の芳香族ビ
ニル単量体；アクリロニトリル、メタクリレートリル等
の不飽和二トリル単量体；メチルメタクリレート等のメ
タクリル酸エステル；エチルアクリレート、ブチルアク
リレ−１・等のアクリル酸エステル等が例示される。Examples of self-crosslinking monomers include N-argyrolamide of ethylenically unsaturated acids such as N-methylolacrylamide, N-methylolmethacrylamide, N,N'-dimethylolitaconic acid diamide, and N-isobutoxymethylacrylamide; N-alkoxyalkylamides; glycidyl group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, and allyl regrindyl ether; allyl alcohol, 2-hydroxyethylac IJ
Hydroxyl group-containing monomers such as L/-1., 2-hydroxyethyl methacrylate; Amino group-containing monomers such as N, N'-dimethylaminoethyl acrylate; amide group-containing monomers such as maleamide; divinylbenzene Examples of the component include divinyl group-containing aromatic monomers such as conjugated diene and the like. As long as the polymer of the present invention is a monomer having a glass transition temperature of 110° C. or higher, there is no particular restriction on weight. If the glass transition temperature of the polymer of the present invention is less than 110° C., it will be difficult to obtain particles that are close to true spheres, and the blocking resistance will also decrease. Preferably it is -5°C or higher. The higher the glass transition temperature, the better the blocking resistance (although it is difficult to control the evaporation rate of water during the drying process during manufacturing, so it is preferably 100°C or less. As the monomer of the third component, 1.: Conjugated dienes such as 3-fuchsien, ingleno, 1.)-pec diene and chlorophrene; Aromatic vinyl monomers such as styrene and α-methylstyrene; Unsaturated nitrile monomers such as acrylonitrile and methacrylaterile; Examples include methacrylic esters such as methyl methacrylate; acrylic esters such as ethyl acrylate and butyl acrylate-1.
本発明の重合体ラテックスは前記の要件と共に重合体の
ゲル含有量が４０重量係以上であることも不可欠である
。ゲル含有量が７ＩＯ重量係未満では優れた耐ブロッキ
ング性が得られない。好ましくは５０重量％以上である
。ゲル含有量は実施例１に記載した方法でめた値である
。本発明の重合体ラテックスの製造法自体は特に制限さ
れず、公知の乳化重合の手法により製造される。通常、
重合開始剤としては、有機過酸化物、レドックス触媒系
、過硫酸カリ、過硫酸アンモニウム等の過硫酸塩等が使
用される。乳化剤としては、アニオン系界面活性剤、非
イオン系界面活性剤等が単独あるいは二種以上で用いら
れる。重合温度は０〜１００℃であり、重合方式も連続
重合、バッチ重合等が挙げられる。In addition to the above-mentioned requirements, the polymer latex of the present invention must also have a gel content of 40% by weight or more. If the gel content is less than 7IO weight coefficient, excellent blocking resistance cannot be obtained. Preferably it is 50% by weight or more. The gel content is the value determined by the method described in Example 1. The method for producing the polymer latex of the present invention is not particularly limited, and the polymer latex can be produced by a known emulsion polymerization method. usually,
As the polymerization initiator, organic peroxides, redox catalyst systems, persulfates such as potassium persulfate, ammonium persulfate, etc. are used. As the emulsifier, anionic surfactants, nonionic surfactants, etc. may be used alone or in combination of two or more. The polymerization temperature is 0 to 100°C, and the polymerization methods include continuous polymerization, batch polymerization, and the like.
本発明の組成物を用いたカラー画像形成用着色粒子は、
前記の重合体ラテックスを粒子形成用物質とし、通常、
有機着色顔料、充てん剤、染料等と混合して、噴霧乾燥
等の造粒工程を経て、所定の粒径の着色粒子とされたも
のである。本発明においては、使用する着色顔料、充て
ん剤、染料等は特公昭５５−２７３４０．昭５５−２７
３４１等で示された方式によるカラー画像形成に使用さ
れるものであれば、特に制限がな（・０着色顔料として
、例えば、青色粒子を得ろためには、ε型銅フタロシア
ニンブルー、ビクトリアブルーレーキ等か、緑色粒子用
には、ポリフロロポリブロモツクロンアニングリーン、
ポリクロロフタロシアニンクリーン等が、赤色粒子用に
は、ツーフト−ル系、ピラゾロン系、ビスアゾ系橙色顔
料等力・挙げられる。Colored particles for color image formation using the composition of the present invention are:
The polymer latex described above is used as a particle-forming substance, and usually,
They are mixed with organic coloring pigments, fillers, dyes, etc., and subjected to a granulation process such as spray drying to form colored particles of a predetermined particle size. In the present invention, the coloring pigments, fillers, dyes, etc. used are those specified in Japanese Patent Publication No. 55-27340. Showa 55-27
There is no particular restriction as long as it can be used for color image formation by the method shown in No. 341 etc. etc. For green particles, polyfluoropolybromotucuronine green,
Examples of pigments for red particles include polychlorophthalocyanine clean, and orange pigments such as twoftol-based, pyrazolone-based, and bisazo-based pigments.
昇華性染料として通常、青色粒子にはイエローに顕色す
る無色の昇華性ロイコ染料を、赤色粒子にはシアンに顕
色する無色の昇華性ロイコ染料を、また、緑色粒子には
マゼンタに顕色する無色の昇ともに混合して使用しても
良いし、また、出来−ヒつた着色粒子表面に塗布しても
良い。充てん剤としてコロイダルシリカ、酸化亜鉛、酸
化チタン、硫酸バリウム等が挙げられ、この様な充てん
剤は、着色粒子の耐ブロッキング性を向上させる目的で
、所望により、使用される。As sublimable dyes, blue particles usually use a colorless sublimable leuco dye that develops yellow, red particles use a colorless sublimable leuco dye that develops cyan, and green particles use a colorless sublimable leuco dye that develops magenta. It may be used by mixing it with a colorless powder, or it may be applied to the surface of the finished colored particles. Examples of fillers include colloidal silica, zinc oxide, titanium oxide, barium sulfate, and the like, and such fillers are used, if desired, for the purpose of improving the blocking resistance of colored particles.
本発明の重合体ラテックスと顔料等との混合の方法は特
に制限されないが、重合体ラテックスと顔料等を同時に
ホモジナイザー、あるいはボールミル等で混合する方法
、またはあらかじめ顔料等を適当な分散剤を用いて水分
散液となし、これと該ラテックスとをホモジナイザーや
ボールミル等で混合する方法°が例示される。この様に
調整された着色粒子製造用配合物は通常噴霧乾燥により
、造粒される。The method of mixing the polymer latex of the present invention with pigments, etc. is not particularly limited, but may include a method of mixing the polymer latex and pigments, etc. simultaneously with a homogenizer or a ball mill, or a method of mixing the pigments, etc. in advance with a suitable dispersant. An example is a method in which an aqueous dispersion is prepared and the latex is mixed with a homogenizer, a ball mill, or the like. The composition for producing colored particles prepared in this way is usually granulated by spray drying.
粒子形成用物質として、本発明の重合体ラテックスを用
いたカラー画像形成用着色粒子は、真球に近い、光透過
率の高い、耐ブロッキング性にすぐれた性能を有するも
のである。また製造の過程において、有機溶剤を使用し
ないので環境汚染、有機溶剤の回収等の問題が１啄（、
経済的利点も太きい。Colored particles for forming color images using the polymer latex of the present invention as a particle-forming substance have properties close to true spheres, high light transmittance, and excellent blocking resistance. In addition, since no organic solvents are used in the manufacturing process, there are problems such as environmental pollution and recovery of organic solvents.
The economic benefits are also significant.
以下、実施例により、本発明を具体的に説明するっ
実施例１
通常の乳化重合により、第１表に記した組成、ガラス転
移温度、ゲル含有量を有する６種類の重合体ラテ了りス
を調製したつ
第 １ 表
注）＊ガラス転移温度の測定法
ラテックスより成膜したフィルムを用い、粘弾１生の測
定より損失弾性率（Ｅ”）が最大となる温度をガラス転
移温度とした（測定周波数＋ ００ Ｈ７、昇温速度２
°Ｃ／分）。Hereinafter, the present invention will be explained in detail with reference to Examples. Table 1 Note) *Measurement method of glass transition temperature Using a film formed from latex, the glass transition temperature was defined as the temperature at which the loss modulus (E”) was maximum from the measurement of viscoelasticity. (Measurement frequency + 00 H7, heating rate 2
°C/min).
＊＊ゲル含有量の測定法
ラテックスを乾燥時の厚さが０．２ ｍｍとなるように
わく伺きのガラス板上に流し、２０°Ｃ１６５％ＲＨの
恒温恒湿下に２４時間放置し、乾燥フィルムを調整する
。次いで、このフィルムを約２本角に細分し、そのうち
の約ｏ、ｚｇ＋ を積ぞ１″−し、あらかじめ精秤した
１００メツシユのステンレス金網の円筒に入れ、テトラ
ヒドロフラン１００ｍ１中に室温で２４時間浸漬する。**Measurement method for gel content Pour the latex onto a glass plate so that the dry thickness is 0.2 mm, and leave it at constant temperature and humidity at 20°C and 165% RH for 24 hours. Condition the dry film. Next, this film was divided into about 2 square pieces, about 0, zg+ of which were stacked into 1"- squares, placed in a 100-mesh stainless steel wire mesh cylinder that had been accurately weighed in advance, and immersed in 100 ml of tetrahydrofuran at room temperature for 24 hours. do.
その後、金網ごと取り出し、真空乾燥機中で２４時間乾
燥したのち、精秤して不溶尊公の重量を測定し、もとの
共重合体フィルムに対する重量係をもってゲル量とする
。Thereafter, the wire mesh was taken out, dried in a vacuum dryer for 24 hours, and then accurately weighed to measure the weight of the insoluble filth, and the weight ratio to the original copolymer film was determined as the gel amount.
これらの６種類のラテックスをそれぞれ着色粒子形成用
物質として第２表に示す顔料等の分散液とボールミル中
で混合し、均一な水性分散液を調製した。These six types of latex were mixed in a ball mill with dispersions of pigments shown in Table 2 as substances for forming colored particles to prepare uniform aqueous dispersions.
第 ２ 表
注）（１）東洋インキ製造社製 ナフト−アゾ系顔料ｆ
２１ Ｃ，１，Ｐｉｇｍｅｎｔ Ｏｒａｎｇｅ ２１１
１５（３）東亜合成社製 アロンＴ−４０
（４）日量化学社製 スノーテックスＮこの分散液（固
形分６５チ）を並流型噴霧乾燥（入口温度８５℃、出口
温度４５℃）により、粒度分布のピークが１５〜３０μ
にある赤色画像形成用粒子を得た。Table 2 Note) (1) Naphtho-azo pigment f manufactured by Toyo Ink Manufacturing Co., Ltd.
21 C, 1, Pigment Orange 211
15 (3) Aron T-40 manufactured by Toagosei Co., Ltd. (4) Snowtex N manufactured by Nichiryo Kagaku Co., Ltd. This dispersion liquid (solid content 65 cm) was subjected to co-current spray drying (inlet temperature 85 °C, outlet temperature 45 °C). , the peak of particle size distribution is 15-30μ
Red image forming particles were obtained.
これらの粒子の性能を測定し、結果を第３表に示した。The performance of these particles was measured and the results are shown in Table 3.
試験法は以下の通りである。The test method is as follows.
＋１１形 状：走査型電子顕微鏡により、表面の平滑性
および粒子形状そのものを観察し、次の５点法で評価し
た。+11 Shape: Surface smoothness and particle shape itself were observed using a scanning electron microscope, and evaluated using the following 5-point method.
５点 みとんどか真球である。5 points: It is a perfect ball.
４点 表面に若干凹凸があるものもあ るが全体はほとんど真球に近い。4 points: Some have slight irregularities on the surface. However, the whole is almost a perfect sphere.
３点 表面に若干凹凸かあるものの数 が多くなる。3 points: Number of items with slight unevenness on the surface will increase.
２点 表面に凹凸が多数あり陥没球も かなりある。2 points: There are many irregularities on the surface and the ball is sunken. There are quite a few.
１点 表面に凹凸が多数あり陥没球が 非常に多い。1 point: There are many unevenness on the surface and the ball is depressed. Very many.
（２）光透過性二光学顕微鏡により視野中の５０個の着
色粒子の各々について光の透過性の
良し悪しを粒子の明暗により５点法で
評価し、５０個の粒子の平均１直で示した。(2) Light transmittance The quality of light transmittance for each of the 50 colored particles in the field of view was evaluated using a 5-point method based on the brightness and darkness of the particles using a two-optical microscope, and the average of the 50 particles was calculated by one point. Ta.
５点 非常に明るい
４点 かなり明るい
３点 やや明る（・
２点 やや暗い
１点暗い
（３）耐ブロッキング性：１００ＣＣのガラス瓶の中に
。5 points Very bright 4 points Quite bright 3 points Slightly bright (2 points Slightly dark 1 point Dark (3) Blocking resistance: In a 100CC glass bottle.
約Ｂ□ｃｃの着色粒子を入れ、５０℃のオープン中に２
４時間放置した後、着
色粒子を取り出し、どの程度、ブロッ
キングして（・るか観察したつ
第 ３ 表
これらの結果より、自己架橋性官能基を有した単量体を
重合体の一成分として使用することにより、着色粒子の
耐ブロッキング性が大幅に改良されることか判る。これ
は着色粒子の造粒工程中かあるいは貯蔵中に重合体が自
己架橋したことにより、耐ブロッキング性が改良された
ものと考えられる。また、青色粒子、緑色粒子について
も同様な結果が得られた。Add approximately B□cc of colored particles and heat for 2 hours while opening at 50℃.
After leaving it for 4 hours, the colored particles were taken out and observed to see how much they were blocked. It can be seen that the blocking resistance of the colored particles is significantly improved by using the colored particles.This is due to self-crosslinking of the polymer during the granulation process of the colored particles or during storage, which improves the blocking resistance. Similar results were also obtained for blue particles and green particles.
実施例２
第４表に記した７種のラテックスを用い、実施例１と同
様にして赤色着色粒子を得た。これらの赤色粒子の試験
結果を第５表に示した。Example 2 Red colored particles were obtained in the same manner as in Example 1 using the seven latexes listed in Table 4. The test results for these red particles are shown in Table 5.
第 ４ 表
、第 ５ 表
この結果から、重合体のゲル含有量あるいは自己架橋性
単量体の含有量が本発明範囲外になると着色粒子の耐ブ
ロッキング性が極端に低下することが分かる。Tables 4 and 5 The results show that when the gel content of the polymer or the content of the self-crosslinking monomer is outside the range of the present invention, the blocking resistance of the colored particles is extremely reduced.
実施例３
通常の乳化重合により、第６表に記した組成およびゲル
量金有する７種類の重合体ラテックスを得た。Example 3 Seven types of polymer latices having the compositions and gel amounts shown in Table 6 were obtained by conventional emulsion polymerization.
第 ６ 表
これら７種類の重合体ラテックスを用い、実施例１と同
様にして赤色着色粒子を得た。これらの赤色粒子の性状
を第７表に示した。Table 6 Red colored particles were obtained in the same manner as in Example 1 using these seven types of polymer latex. The properties of these red particles are shown in Table 7.
この結果より、自己架橋性単量体が０．３重量％未満で
あるか、もしくはゲル含有量が４０重量％未満であると
、青色粒子の耐ブロッキング性が極端に低下することが
分かる。また自己架橋性単量体としてヒドロキシエチル
アクリレート、アクリルアミド、ジビニルベンゼンを夫
々使用した場合についても実験を行ったが同様な結果が
得られた。This result shows that when the self-crosslinking monomer content is less than 0.3% by weight or the gel content is less than 40% by weight, the blocking resistance of the blue particles is extremely reduced. Experiments were also conducted using hydroxyethyl acrylate, acrylamide, and divinylbenzene as self-crosslinking monomers, and similar results were obtained.
実施例４
通常の乳化重合により、第８表に記した組成、ゲル含有
量、ガラス転移温度を有する５種類の重合体ラテックス
を調製した。Example 4 Five types of polymer latices having the compositions, gel contents, and glass transition temperatures shown in Table 8 were prepared by conventional emulsion polymerization.
第 ８ 表
これら５種類の重合体ラテックスを用い、実施例】と同
様にして赤色着色粒子を得た（但し噴霧乾燥機の入口温
度を６０〜１２０℃、出口温度を３０〜５０℃に調節し
た）。これらの赤色粒子の性状を第９表に示した。Table 8 Using these five types of polymer latex, red colored particles were obtained in the same manner as in Example (however, the inlet temperature of the spray dryer was adjusted to 60 to 120°C and the outlet temperature to 30 to 50°C. ). The properties of these red particles are shown in Table 9.
第 ９ 表
この結果より、重合体のガラス転移温度が一１０℃以下
になると１着色粒子の形状および耐ブロッキング性が悪
くなることが分かる。Table 9 The results show that when the glass transition temperature of the polymer is below 110°C, the shape and blocking resistance of the colored particles deteriorate.
実施例５
ブタジェン３０重量％、スチレン６６重ｉ％、アクリル
酸２重ｉ％、グリシジルメタクリレート２重量係（ラテ
ックスＡ）；ブタジェン３０重量％、スチレン４６重量
％、メチルメタアクリレ−）２０重量％、アクリル酸２
重量係、グリシジルメタクリレート２重量％（ラテック
スＢ）；ブタジェン３０重量％、メチレフ３６重景係、
アクリル酸２ｉ１ｆ−ｆｆｉ％、グリシジルメタクリレ
ート２重量％（ラテックスＣ）の組成を有し、ゲル含有
量が７２〜７５チの重合体ラテックスも製造し、実施例
１と同様にして赤色着色粒子を得た。これらの赤色粒子
の性状を第１０表に示した。Example 5 30% by weight of butadiene, 66% by weight of styrene, 2% by weight of acrylic acid, 2% by weight of glycidyl methacrylate (latex A); 30% by weight of butadiene, 46% by weight of styrene, 20% by weight of methyl methacrylate. , acrylic acid 2
Weight section, glycidyl methacrylate 2% by weight (latex B); butadiene 30% by weight, Metilef 36 weight section,
A polymer latex having a composition of acrylic acid 2i1f-ffi% and glycidyl methacrylate 2% by weight (Latex C) and a gel content of 72 to 75% was also produced, and red colored particles were obtained in the same manner as in Example 1. Ta. The properties of these red particles are shown in Table 10.
第１０表
第１０表の結果は、ブタジェン以外の組成が変化しても
、得られた着色粒子の性能には影響がないことが分かる
。Table 10 The results in Table 10 show that even if the composition other than butadiene changes, the performance of the obtained colored particles is not affected.
特許出願人 日本ゼオン株式会社Patent applicant: Zeon Corporation
Claims (1)
色粒子製造用組成物において、重合体鎖中にｉｌｌ ０
．５〜１０重量％の少なくとも一種のエチレン性不飽和
酸、（２１０，３〜１５重量％の少なくとも１種の共重
合可能な自己架橋性単量体ならびに（３） ８０〜９９
．２重量係の、少なくとも共役ジエンを含む前記の各単
量体と共重合可能な単量体を含有するガラス転移温度が
一１０℃以上で、かつゲル含有量が４０重量％以上であ
る自己架橋性重合体のラテックスを粒子形成用物質とし
て使用することを特徴とするカラー画像形成用着色粒子
製造用組成物。In a composition for producing colored particles for color image formation consisting of a colored pigment and a particle-forming substance, ill 0 is present in the polymer chain.
．． 5-10% by weight of at least one ethylenically unsaturated acid, (210, 3-15% by weight of at least one copolymerizable self-crosslinking monomer and (3) 80-99
．． Self-crosslinking containing a monomer copolymerizable with each of the above-mentioned monomers containing at least a conjugated diene, having a glass transition temperature of 110°C or higher and a gel content of 40% by weight or higher. 1. A composition for producing colored particles for forming a color image, characterized in that a latex of a synthetic polymer is used as a particle-forming substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58188422A JPS6080857A (en) | 1983-10-11 | 1983-10-11 | Composition for manufacturing colored particle for forming color image |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58188422A JPS6080857A (en) | 1983-10-11 | 1983-10-11 | Composition for manufacturing colored particle for forming color image |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6080857A true JPS6080857A (en) | 1985-05-08 |
| JPH0449940B2 JPH0449940B2 (en) | 1992-08-12 |
Family
ID=16223384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58188422A Granted JPS6080857A (en) | 1983-10-11 | 1983-10-11 | Composition for manufacturing colored particle for forming color image |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6080857A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62189476A (en) * | 1986-02-15 | 1987-08-19 | Mitsui Toatsu Chem Inc | Toner composition for electrophotography |
| US6140038A (en) * | 1998-07-09 | 2000-10-31 | Fuji Photo Film Co., Ltd | Heat-developable image-recording material |
| US6194480B1 (en) * | 1997-04-10 | 2001-02-27 | Fuji Photo Film Co., Ltd. | Pigment composition and colored photosensitive composition |
| EP1114849A1 (en) * | 2000-01-07 | 2001-07-11 | PolymerLatex GmbH & Co.KG | Aqueous styrene-diene-dispersions for the strengthening of bituminous fleece |
| EP1316597A2 (en) * | 2001-11-29 | 2003-06-04 | Basf Aktiengesellschaft | Glycidyl (meth)acrylate containing adhesive |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103025934B (en) | 2010-07-29 | 2014-09-10 | 株式会社可乐丽 | Amorphous heat fusion fiber, fiber structure body, and heat-resistant molded article |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5655414A (en) * | 1979-10-11 | 1981-05-16 | Japan Synthetic Rubber Co Ltd | Polymer particle |
| JPS57172348A (en) * | 1981-03-13 | 1982-10-23 | Konishiroku Photo Ind Co Ltd | Electrostatic image developing toner |
| JPS5817454A (en) * | 1981-07-24 | 1983-02-01 | Canon Inc | Toner |
-
1983
- 1983-10-11 JP JP58188422A patent/JPS6080857A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5655414A (en) * | 1979-10-11 | 1981-05-16 | Japan Synthetic Rubber Co Ltd | Polymer particle |
| JPS57172348A (en) * | 1981-03-13 | 1982-10-23 | Konishiroku Photo Ind Co Ltd | Electrostatic image developing toner |
| JPS5817454A (en) * | 1981-07-24 | 1983-02-01 | Canon Inc | Toner |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62189476A (en) * | 1986-02-15 | 1987-08-19 | Mitsui Toatsu Chem Inc | Toner composition for electrophotography |
| US6194480B1 (en) * | 1997-04-10 | 2001-02-27 | Fuji Photo Film Co., Ltd. | Pigment composition and colored photosensitive composition |
| US6140038A (en) * | 1998-07-09 | 2000-10-31 | Fuji Photo Film Co., Ltd | Heat-developable image-recording material |
| EP1114849A1 (en) * | 2000-01-07 | 2001-07-11 | PolymerLatex GmbH & Co.KG | Aqueous styrene-diene-dispersions for the strengthening of bituminous fleece |
| US6693146B2 (en) | 2000-01-07 | 2004-02-17 | Polymerlatex Gmbh & Co. Kg. | Self-crosslinking aqueous polystyrene-butadiene dispersions for consolidating bituminizable nonwovens and also consolidated nonwovens |
| EP1316597A2 (en) * | 2001-11-29 | 2003-06-04 | Basf Aktiengesellschaft | Glycidyl (meth)acrylate containing adhesive |
| EP1316597A3 (en) * | 2001-11-29 | 2004-02-04 | Basf Aktiengesellschaft | Glycidyl (meth)acrylate containing adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0449940B2 (en) | 1992-08-12 |
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