JPS6214653A - Electrophotographic recording material - Google Patents
Electrophotographic recording materialInfo
- Publication number
- JPS6214653A JPS6214653A JP15388285A JP15388285A JPS6214653A JP S6214653 A JPS6214653 A JP S6214653A JP 15388285 A JP15388285 A JP 15388285A JP 15388285 A JP15388285 A JP 15388285A JP S6214653 A JPS6214653 A JP S6214653A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- recording material
- parts
- electrostatic recording
- organic powder
- 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.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/0202—Dielectric layers for electrography
- G03G5/0217—Inorganic components
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/0202—Dielectric layers for electrography
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/0202—Dielectric layers for electrography
- G03G5/0214—Organic non-macromolecular components
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Photoreceptors In Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
〔座業の利用分野〕
本発明は、ファクシミリ、高速静電印刷、静電転写等に
使用さｎる静電記録体に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of application for sedentary work] The present invention relates to an electrostatic recording medium used for facsimile, high-speed electrostatic printing, electrostatic transfer, etc.
静電記録法は、周知の如く、低抵抗処理を施し迄基体に
塗布等の方法により、高誘電体絶縁性樹脂の記録層を設
は几静電記録体に、電圧を印加した後静電潜像を形成せ
しめ、こｎ２着色トナーで顕像化する方法である。As is well known, in the electrostatic recording method, a recording layer of a high dielectric insulating resin is coated on a substrate by applying a low resistance treatment, and then a voltage is applied to the electrostatic recording medium. This is a method of forming a latent image and making it visible using N2 colored toner.
一般に静電記録体は支持体、導電層および誘電層の王者
を二層ま几は三層として結合することにより構成さｎる
。In general, electrostatic recording materials are constructed by combining a support, a conductive layer, and a dielectric layer into two or three layers.
たとえば、三層構造においては、紙ま九はプラスチック
フィルムの表面に低抵抗層を設け、その上に高誘電体絶
縁性の高分子物質を主体とする誘電層を設けて、この誘
電層上に静電記録を行うものである。For example, in a three-layer structure, a paper pillow has a low-resistance layer on the surface of a plastic film, and on top of that is a dielectric layer mainly made of a high-dielectric-insulating polymer material. It performs electrostatic recording.
このような誘電層を形成する高分子物質としては、アク
リル酸エステル、メタクリル酸エステル、酢酸ビニル、
塩化ビニル等の単一重合体または共重合体、ポリエチレ
ン、ポリスチレン、ポリビニルアセタール、シリコーン
、ポリウレタンなどが用いらｎている。Polymer materials that form such dielectric layers include acrylic esters, methacrylic esters, vinyl acetate,
Single polymers or copolymers such as vinyl chloride, polyethylene, polystyrene, polyvinyl acetal, silicone, polyurethane, etc. are used.
静電記録体に要求さｎる性能としては、（２）耐候性特
に耐湿性にすぐｎていること、（３） 一般紙のよう
な筆記性、捺印性？有すること＼
（４） 臭気や毒性のないこと、
等が挙げられる。The performance required for electrostatic recording media is (2) weather resistance, especially moisture resistance, and (3) writing and stamping properties similar to ordinary paper. (4) No odor or toxicity, etc.
静電記録体の誘電層に用いらｎている前記高分子物質は
通常適当な溶剤中に溶解した溶液か或は、水中に乳化懸
濁せしめ友乳化液の状態で塗液とし、こ−ａｔ叉持持基
体表面塗布して誘電層を形成せしめる。The polymeric substance used in the dielectric layer of the electrostatic recording medium is usually dissolved in a suitable solvent or emulsified and suspended in water to form a coating liquid. A dielectric layer is formed by coating the surface of a supporting substrate.
しかるに上記のような誘電層は、そのままでは表面が不
自然な光沢を有する平滑な非吸収性の連続皮膜を形成す
る九め、鉛筆、インキあるいはスタンプに対する受容性
、保持性か悪い。However, such a dielectric layer as described above forms a smooth, non-absorbing continuous film with an unnatural gloss on the surface, and has poor receptivity and retention for pencils, inks, and stamps.
−万誘電層は、記録時に印加電極とｆ象保持層面との間
の気中放電或いは直接的な電荷注入の現象を伴う過程を
経るが、その際の誘電層の表面は、微細な記録画像の白
ぬけを生じ九り、鮮明度を損ねたりしない程度に粗面で
ある万が放電開始電圧は低く、且つ画像も鮮明に記録し
得るので望ましい。- During recording, the dielectric layer undergoes a process that involves the phenomenon of air discharge or direct charge injection between the application electrode and the surface of the f-image holding layer; It is desirable that the surface be rough to the extent that it does not cause white spots or impair sharpness, but the discharge starting voltage is low and images can be recorded clearly.
そこでこうし几欠点を改善する友めに記録層中にシリカ
、鉛白、炭酸カルシウム、酸化チタン、クレーのような
無機顔料の微粉末を分散させる方法が採られてき九が、
こうし次無機顔料は多かれ少なかｎ吸湿性があるので、
こｆｔｔ−多量に用いると帯電特性が劣化し、画像濃度
があがらないという好ましくない現象が生じる。また無
機顔料が硬いｔめ電極の摩耗が激しいという欠点も付随
する。Therefore, methods have been adopted in which fine powders of inorganic pigments such as silica, white lead, calcium carbonate, titanium oxide, and clay are dispersed in the recording layer to improve these defects.
Since inorganic pigments are more or less hygroscopic,
If a large amount of this material is used, the charging characteristics will deteriorate, resulting in an undesirable phenomenon that the image density will not increase. Another drawback is that the electrodes, which are made of hard inorganic pigments, are subject to severe wear.
一万、粒径１０μｍ以下の有機微粉宋音無機顔料の代り
に記録層に分散させて上記欠点を改善する方法が検討さ
れている。該有機粉末は通常高誘電体絶縁性樹脂を溶剤
に溶解させた樹脂溶液中に１．−分散させる為に、該溶
剤に不溶であることが必須要件であり、従来使用されて
いる代表的な有機微粉末としてポリアクリロニトリル等
の熱可塑性樹脂が挙げらｎるが、粒径１０μｍ以下の微
粉末を得るのが難しく、生産性、コスト面で好ましくな
い。又、ポリメチルメタクリレート、ポリスチレン等の
非架橋タイプの熱可塑性樹脂の場合には、微粉末は得ら
ｎ易いものの該樹脂を溶解しない溶剤が限定さｎ、従っ
て高誘電体絶縁性樹脂の選択が困難であるのが現状であ
る。A method of improving the above-mentioned drawbacks by dispersing inorganic pigments in the recording layer instead of organic finely powdered Songyin inorganic pigments having a particle size of 10 μm or less has been studied. The organic powder is usually prepared by adding 1. - In order to disperse, it is an essential requirement to be insoluble in the solvent, and thermoplastic resins such as polyacrylonitrile are listed as typical organic fine powders conventionally used. It is difficult to obtain fine powder, which is unfavorable in terms of productivity and cost. In addition, in the case of non-crosslinked thermoplastic resins such as polymethyl methacrylate and polystyrene, although it is easy to obtain fine powder, the solvents that do not dissolve the resin are limited, and therefore the selection of high dielectric insulating resins is difficult. The current situation is that it is difficult.
本発明の目的とするところは、粉砕性に優ｎｔ有機微粉
末を用いて、高湿雰囲気下においても画像特性に優ｎ１
かつ筆記性、捺印性の優ｎｔ誘電体層を有する静電記録
体を提供することにある。The object of the present invention is to use an organic fine powder with excellent pulverizability to provide excellent image characteristics even in a high humidity atmosphere.
Another object of the present invention is to provide an electrostatic recording material having a dielectric layer with excellent writing and marking properties.
本発明は、粒径１０μ以下の有機粉末樹脂が分散して配
合されている高誘電体絶縁性樹脂からなる誘電体層を、
低抵抗処理が施さｆＵｔ基体上に積層してなる静電記録
体にある。該記録体表面は粗面で光沢の消された記録層
であり、その結果、水性あるいは油性インキに対する受
容性が著しく改善さｎ、印刷、スタンプ等が可能となり
、鉛筆による書込み性にも優れ、さらにはシリカ等の無
機充填剤を用い几従来法と比べ、絶縁抵抗の低下がほと
んどなく、且つ高湿度条件下における記録に際しても鮮
明で高い記録濃度が得らｎ、又、記録端子の摩耗等も非
常に少ないという利点を有している。The present invention provides a dielectric layer made of a high dielectric insulating resin in which organic powder resin with a particle size of 10 μm or less is dispersed.
This electrostatic recording material is laminated on an fUt substrate that has been subjected to low resistance treatment. The surface of the recording material is a recording layer with a rough surface and no gloss, and as a result, the receptivity to water-based or oil-based inks is significantly improved, making it possible to print, stamp, etc., and also has excellent writing properties with a pencil. Furthermore, by using an inorganic filler such as silica, there is almost no drop in insulation resistance compared to conventional methods, and clear and high recording density can be obtained even when recording under high humidity conditions. It also has the advantage of being very small in number.
本発明で用いらする有機粉末の粒径は１０μｍ以下、好
ましくは６μｍ以下であることが必要である。粒径が１
０μｍｔｌ−越えると得らｎる記録層面か粗過ぎる几め
、筆記性、捺印性１画像特性の点で好ましくない。The particle size of the organic powder used in the present invention needs to be 10 μm or less, preferably 6 μm or less. Particle size is 1
If it exceeds 0 .mu.mtl, the surface of the recording layer obtained is too rough, which is unfavorable in terms of writing properties, printing properties, and image characteristics.
又、有機微粉末を構成する樹脂としては架橋さＡＦｊ熱
可塑性樹脂が用いらｎる。該樹脂は粉砕性に優ｎており
、粒径１０μｍ以下の微粉末を容易に得ることができる
。さらに高誘電体絶縁性樹脂全溶解するいずｎの浴剤に
も難溶又は不溶である。Further, as the resin constituting the organic fine powder, a crosslinked AFj thermoplastic resin is used. This resin has excellent crushability, and fine powder with a particle size of 10 μm or less can be easily obtained. Furthermore, it is poorly soluble or insoluble in any bath agent that completely dissolves the high dielectric insulating resin.
好ましい樹脂としては、［１０１重ｉｉチ以上、好まし
くはｌ１１重量％以上の架橋剤を含む単量体混合物全ラ
ジカル共重合することにより得らｎる熱可塑性樹脂や２
０モルチ以上、好ましくは３０モルチ以上の３官能以上
の多官能性単量体を含む単量体混合物を縮合重合させ几
ポリエステル樹脂が挙げらｎる。Preferred resins include thermoplastic resins obtained by total radical copolymerization of a monomer mixture containing at least 101% by weight, preferably at least 11% by weight of a crosslinking agent;
Examples include polyester resins produced by condensation polymerization of a monomer mixture containing a trifunctional or higher polyfunctional monomer having an amount of 0 mol or more, preferably 30 mol or more.
ラジカル共重合により得らｎる熱可塑性樹脂を構成する
単量体としては、モノオレフィン系単量体、ジオレフィ
ン系単量体及び架橋剤を用いることができる。As monomers constituting the thermoplastic resin obtained by radical copolymerization, monoolefin monomers, diolefin monomers, and crosslinking agents can be used.
モノオレフィン系単量体としては、例えばスチレン、Ｏ
−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルス
チレン、α−メチルスチレン、ｐ−エチルスチレン、２
・４−ジメチルスチレン、ｐ−ｎ−ブチルスチレン、
ｐ −ｔｅｒｔ−ブチルスチレン、ｐ−ｎ−へキシル
スチレン。Examples of monoolefin monomers include styrene, O
-Methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2
・4-dimethylstyrene, p-n-butylstyrene,
p-tert-butylstyrene, p-n-hexylstyrene.
ｐ−ｎ−オクチルスチレン＋ ｐ−ｎ−ノニルスチレ
ン、ｐ−ｎ−ｆシルスチレン、ｐ−ｎ−ドデシルスチレ
ン、ｐ−メトキシスチレン、ｐ−フェニルスチレン、ｐ
−クロルスチレン、３・４−ジクロルスチレン等のスチ
レン類：エチレン、プロピレン、ブチレン、インブチレ
ン等のエチレン系不飽和モノオレフィン類、塩化ビニル
、塩化ビニリデン、臭化ビニル、弗化ビニル等のハロゲ
ン化ビニル類：酢酸ビニル、プロピオン酸ビニル、ベン
ジェ駿ビニル、酪酸ビニル等のビニルエステル類ニアク
リル酸メチル、アクリル酸エチル、アクリル酸プロピル
、アクリル酸ｎ−ブチル、アクリル酸イソブチル、アク
リル酸ｎ−オクチル、アクリル酸ドデシル、アクリル酸
ラウリル、アクリル酸２−エチルヘキシル、アクリル酸
ステアリル、アクリル酸２−クロルエチル、アクリル酸
フェニル、α−クロルアクリル酸メチル、メタアクリル
酸メチル。p-n-octylstyrene + p-n-nonylstyrene, p-n-f silstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p
- Styrenes such as chlorostyrene and 3,4-dichlorostyrene; ethylenically unsaturated monoolefins such as ethylene, propylene, butylene, and imbutylene; halogens such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; Vinyl esters: vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzene, vinyl butyrate, methyl diacrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, Dodecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate.
メタクリル酸エチル、メタアクリル酸グロビル。Ethyl methacrylate, globil methacrylate.
メタアクリル酸ｎ−ブチル、メタアクリル酸イソブチル
、メタアクリル酸ｎ−オクチル、メタアクリル酸ドデシ
ル、メタアクリル酸ラウリル。n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate.
メタアクリル酸２−エチルヘキシル、メタアクリル酸ス
テアリル、メタアクリル酸フェニル。2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate.
メタアクリル醗ジメチルアミンエチル、メタアクリル酸
ジエチルアミノエチル等のα−メチル脂肪族モノカルボ
ン酸エステル類：アクリロニトリル、メタアクリロニト
リル、アクリルアミド、メタアクリルアミド等のアクリ
ル酸若しくはメタアクリル酸誘導体；ビニルメチルエー
テル、ビニルエチルエーテル、ビニルイソフチルエーテ
ル等のビニルエーテル類：ビニルメチルケトン、ビニル
へキシルケトン、メチルイソプロペニルケトン等のビニ
ルケトン類：Ｎ−ビニルピロール、Ｎ−ビニルカルバゾ
ール、Ｎ−ビニルインドール、Ｎ−ビニルピロリドン等
ノＮ−ビニル化合物類：ビニルナフタリン類、その他を
挙げることができる。又、ジオレフィン系単量体として
は、例えばプロパジエン、ブタジェン、 イソ’レン、
クロロブレン、ペンタジェン、ヘキサジエン等を挙げる
ことができる。こｎらの単量体は、単独又は、複数で用
いることができる。α-Methyl aliphatic monocarboxylic acid esters such as methacrylic dimethylamine ethyl and diethylaminoethyl methacrylate; Acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide; Vinyl methyl ether, vinyl ethyl Vinyl ethers such as ether and vinyl isophthyl ether: Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone: N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone, etc. - Vinyl compounds: vinylnaphthalenes and others. In addition, examples of diolefin monomers include propadiene, butadiene, iso'lene,
Chlorobrene, pentadiene, hexadiene, etc. can be mentioned. These monomers can be used alone or in combination.
架橋剤としては、ラジカル重合で通常用いらｎている重
合性二重結合を少なくとも２個有する化合物が用いられ
る。具体例としては、ジビニルベンゼン、ジビニルナフ
タレン及びそｎらの誘導体等の芳香族ジビニル化合物ニ
ジエチレングリコールジメタクリレート、ジエチレング
リコールジアクリレート、トリエチレングリコールジメ
タアクリレート、テトラエチレングリコールジメタクリ
レート、１，３−ブタンジオールジメタクリレート等の
ジエチレン性カルボン酸エステル：Ｎ、Ｎ−ジビニルア
ニリン、ジビニルエーテル、ジビニルスルフィド、ジビ
ニルスルホン等のジビニル化合物、及びトリメチロール
プロパントリメタクリレート等のビニル基金５個以上有
する化合物を挙げることかでき、こ扛らは単独で又は２
種以上を組み合せて用いることかできる。As the crosslinking agent, a compound having at least two polymerizable double bonds, which is commonly used in radical polymerization, is used. Specific examples include aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, and their derivatives, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and 1,3-butanediol. Diethylenic carboxylic acid esters such as dimethacrylate: divinyl compounds such as N,N-divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone, and compounds having five or more vinyl groups such as trimethylolpropane trimethacrylate can be mentioned. , these guys alone or two
More than one species can be used in combination.
架橋剤の添加量はα０１重ｔチ以上が必要であり、好ま
しくは［１１重量％以上である。架橋剤の添加量が少な
すぎると、得らｎる有機粉宋が溶剤に溶けてしまうので
好ましくない。The amount of the crosslinking agent added must be at least α01% by weight, preferably at least 11% by weight. If the amount of crosslinking agent added is too small, the resulting organic powder will dissolve in the solvent, which is not preferable.
縮合重合により得らｎるポリエステル樹脂は２価以上の
アルコールと２価以上のカルボン酸あるいはこｎらの酸
無水物との縮合重合によって得ら扛る。The polyester resin obtained by condensation polymerization is obtained by condensation polymerization of a dihydric or higher alcohol and a divalent or higher carboxylic acid or an acid anhydride thereof.
２価以上のアルコールの具体例としては、エチレングリ
コール、ジエチレングリコール、トリエチレングリコー
ル、ｔ２−７’ロピレンクリコール、１．３−グロピレ
ングリコール、１．４−ブタンジオール、ネオペンチル
グリコール、１゜４−ブタンジオール等のジオール類：
１．４−ビス（ヒドロキシメチル）シクロヘキサン、ビ
スフェノールＡ、水素添加ビスフェノールＡ、ポリオキ
シエチレン化ビスフェノールＡ、ポリオキシプロピレン
化ビスフェノールＡ等のエーテル化ビスフェノール類二
ンルビトール、１．２．！１゜６−ヘキサンテトロール
、１．４−ソルビタン。Specific examples of dihydric or higher alcohols include ethylene glycol, diethylene glycol, triethylene glycol, t2-7'ropylene glycol, 1,3-glopylene glycol, 1,4-butanediol, neopentyl glycol, 1゜4 - Diols such as butanediol:
1. Etherified bisphenols such as 4-bis(hydroxymethyl)cyclohexane, bisphenol A, hydrogenated bisphenol A, polyoxyethylated bisphenol A, polyoxypropylenated bisphenol A, etc. Dynrubitol, 1.2. ! 1°6-hexanetetrol, 1,4-sorbitan.
ペンタエリスリトール、ジペンタエリスリトール、トリ
ペンタエリスリトール、ショｌＬ１．２゜４−ブタント
リオール、１，２．５−ペンタントリオール、グリセロ
ール、２−メチルプロパントリオール、２−メチル−１
，２，４−ブタントリオール、ｉＪメチロールエタン、
トリメチロールプロパン、１，３．５−）リヒドロユシ
メチルベンゼン等の３価以上のアルコールが挙げられる
。Pentaerythritol, dipentaerythritol, tripentaerythritol, 1.2゜4-butanetriol, 1,2.5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1
, 2,4-butanetriol, iJ methylolethane,
Trimethyl or higher alcohols such as trimethylolpropane and 1,3.5-)lihydroyusimethylbenzene can be mentioned.
又、２価以上のカルボン酸の具体例としては、マレイン
酸、フマール酸、メサコニン酸、シトラコン識、イタコ
ン醗、グルタコン駿、フタル酸、イソフタル酸、テレフ
タル酸、シクロヘキサンジカルボン酸、コハク酸、アジ
ピン酸、セパチン酸、マロン酸、リルイン酸と低級アル
キルエステルの２量体等の２価の有機カルボン！１：１
．２．４−ベンゼントリカルボン酸、１，２．５−ベン
ゼントリカルボン酸、１．２．４−シクロヘキサントリ
カルボン酸、 ２．５．７−ナフタレントリカルボン
酸、１，２．４−す７タレントリカルボン散、１，２．
４−ブタントリカルボン酸、１，２．５−ヘキサントリ
カルボン酸、１，３−ジカルボキシル−２−メチル−２
−メチレンカルボキシプロパン、テトラ（メチレンカル
ボキシル）メタン、１，２，７．８−オクタンテトラカ
ルボン酸、エンボール３量体酸等の５価以上のカルボン
酸及びこｎらの酸無水物が挙げらｎる。Further, specific examples of divalent or higher carboxylic acids include maleic acid, fumaric acid, mesaconic acid, citraconic acid, itacone, glutacone, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, and adipic acid. , divalent organic carboxylic acid such as cepatic acid, malonic acid, dimer of liluic acid and lower alkyl ester! 1:1
．． 2.4-benzenetricarboxylic acid, 1,2.5-benzenetricarboxylic acid, 1.2.4-cyclohexanetricarboxylic acid, 2.5.7-naphthalenetricarboxylic acid, 1,2.4-su7talentricarboxylic acid, 1, 2.
4-butanetricarboxylic acid, 1,2.5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2
- Carboxylic acids with a valence of 5 or higher, such as methylenecarboxypropane, tetra(methylenecarboxyl)methane, 1,2,7.8-octanetetracarboxylic acid, and embol trimer acid, and their acid anhydrides. Ru.
３官能以上の多官能性単量体としては上記したよりな３
価以上のカルボン酸又はアルコールが用いらｎ１得られ
るポリエステル樹脂中にこｎら単量体単位の合計が２０
モルチ以上、好ましくは３０モルチ含まれていることが
必要である。２０モルチ未満では得られる有機粉末が溶
剤に溶けてしまうので好ましくない。As the polyfunctional monomer having three or more functionalities, the above-mentioned three
When a carboxylic acid or alcohol having a higher valence is used, a total of these monomer units is 20 in the polyester resin obtained.
It is necessary that the amount is molti or more, preferably 30 molti. If it is less than 20 molar, the resulting organic powder will dissolve in the solvent, which is not preferable.
溶媒で溶解して高誘電体絶縁性樹脂溶液中に有機粉末を
分散させる方法としては、特に限定されるものではなく
、ボールミル、アトライダー、バンバＩＪ−ミキサー等
の通常の分散混合機を用いることができる。このように
して得らｎた分散液を、予め低抵抗処理を施し九基体上
に破覆することにより帯電性ひいては画像性を損うこと
のない筆記特性の改善さｆ１７？−静電記録体が得らｎ
る。The method of dissolving the organic powder in a solvent and dispersing it in the high dielectric insulating resin solution is not particularly limited, and a normal dispersion mixer such as a ball mill, atrider, or Bamba IJ-mixer can be used. I can do it. By subjecting the dispersion thus obtained to a low-resistance treatment in advance and dispersing it on a substrate, it is possible to improve the writing characteristics without impairing the chargeability and image quality. - Electrostatic recording material obtained
Ru.
本発明に用いらｎる基体としては、通常の静電記録体に
用いらｎる紙、プラスチックフィルム等が挙げらｎ、特
に制限されるものではない。Examples of the substrate used in the present invention include paper, plastic film, etc. used in ordinary electrostatic recording materials, but are not particularly limited.
基体に低抵抗処理する方法としては、焦機塩類、金属粉
、界面活性剤、高分子電解質等を基体に含浸させるかあ
るいは基体表面に塗布する方法やアルミニウム等の導電
物質を蒸着させる方法等の通常の方法が挙げらｎる。Methods for low-resistance treatment on the substrate include impregnating or coating the substrate with pyrotechnic salts, metal powder, surfactants, polymer electrolytes, etc., or coating the substrate surface with evaporation of conductive substances such as aluminum. Common methods include:
本発明に用いらｎる高誘電体絶縁性樹脂としては、通常
静電記碌体に使用さｎるものを適用することができ、特
に制限さ牡るものではない。As the high dielectric insulating resin used in the present invention, those commonly used in electrostatic recording materials can be used, and there are no particular limitations.
具体例としては、メチルメタクリレート／ ｎ −ブチ
ルメタクリレート共重合体に代表さｎるアクリル系樹脂
や、塩化ビニル／酢酸ビニル共重合体に代表される塩化
ビニル系樹脂等が挙げらｎる。Specific examples include acrylic resins typified by methyl methacrylate/n-butyl methacrylate copolymer, vinyl chloride resins typified by vinyl chloride/vinyl acetate copolymer, and the like.
高誘電体絶縁性樹脂を溶解させるために用いらｎる溶剤
は該樹脂の組成にエフ適時選択され、特に限定さｎるも
のではない。The solvent used to dissolve the high dielectric insulating resin is selected appropriately depending on the composition of the resin, and is not particularly limited.
具体例としては、トルエン、キシレン等の炭化水Ｘ 系
化合物：イソグロビルアルコール、ｎ−ブチルアルコー
ル等のアルコール化合物；メチルエチルケトン、メチル
イソブチルケトン等のケトン化合物：酢酸エチル、酢酸
ブチル等のエステル化合物：イソグロビルエーテル、ｎ
−ブチルエーテル等のエーテル化合物等が挙げらｎる。Specific examples include hydrocarbon X-based compounds such as toluene and xylene; alcohol compounds such as isoglobil alcohol and n-butyl alcohol; ketone compounds such as methyl ethyl ketone and methyl isobutyl ketone; ester compounds such as ethyl acetate and butyl acetate; isoglobyl ether, n
Examples include ether compounds such as -butyl ether.
以下、本発明を実施例で詳細に説明する。Hereinafter, the present invention will be explained in detail with reference to Examples.
〔実施例１〕
攪拌機付きオートクレーブに水５ｏｏｘｔ部を入ｎ、次
に主懸濁安定剤としてリン酸三カルシウム（太平化学社
製）を１．５重量部と懸濁安定助剤としてドデシルベン
ゼンスルフオン酸ソーダ１（１０１重量部添加し、攪拌
により均一に分散させ、こｎにメタアクリル酸メチル２
０重量部、ジエチレングリコールジメタアクリレート８
０重量部に重合開始剤としてベンゾイルパーオキサイド
α０３重量部、ｔ−ブチルパーオキシベンゾエートｎ０
２重量部を溶解させた溶液を導入し、窒素置換し、９０
℃で７時間、続いて１０５℃で３時間重合を行つ友後、
常温まで冷却を行つ几。得らｎた重合体を多量の水で洗
浄し、８０℃で４８時間乾燥した。得らｔＬ九粗粒状樹
脂粉砕器（アイカ万能粉砕器Ｍ−２０型）にて２分間粉
砕した後、ジグザグ分ＲＷＭアルビネ社製： Ｉ Ｑ
ＯＭＺＲ）にて粒径１〜１０μｍの有機粉末（Ａ） を
得た。得ら：ｎ、友粉末の溶剤への溶解性を表１に示し
皮。[Example 1] Put 50xt parts of water into an autoclave equipped with a stirrer, then add 1.5 parts by weight of tricalcium phosphate (manufactured by Taihei Kagaku Co., Ltd.) as a main suspension stabilizer and dodecylbenzenesulfate as a suspension stabilizing agent. Add 1 (101 parts by weight) of sodium fluoride, disperse uniformly by stirring, and add 2 parts of methyl methacrylate.
0 parts by weight, diethylene glycol dimethacrylate 8
0 parts by weight, 3 parts by weight of benzoyl peroxide α0 and t-butyl peroxybenzoate n0 as polymerization initiators.
A solution containing 2 parts by weight was introduced, the atmosphere was replaced with nitrogen, and the temperature was 90
After polymerization at 105°C for 7 hours, followed by 3 hours at 105°C,
A container that cools down to room temperature. The obtained polymer was washed with a large amount of water and dried at 80° C. for 48 hours. After pulverizing the obtained resin for 2 minutes with a coarse granular resin pulverizer (Aica universal pulverizer M-20 type), zigzag portion RWM manufactured by Albine Co., Ltd.: IQ
An organic powder (A) having a particle size of 1 to 10 μm was obtained using OMZR). Table 1 shows the solubility of the obtained powder in solvents.
次に該有機粉末（〜３０重量部、メチルメタアクリレ−
）／ｎ−ブチルメタアクリレート共重合体（共重合重量
比４０対６０）の２０％、トルエン溶液４００重量部を
ボールミルに入ｎ５３時間分散させ几。Next, the organic powder (~30 parts by weight, methyl methacrylate)
)/n-butyl methacrylate copolymer (copolymerization weight ratio 40:60) and 400 parts by weight of a toluene solution were placed in a ball mill and dispersed for 53 hours.
この分散液を、表面固有抵抗値ｔ１０７０になるように
、導電剤の１ｎＯＲ３４（ダウケミカル社製）で処理し
友。重さ５０１７ｍ”の上質紙の一表面Ｋ、塗布乾燥後
の重さが６９７ｍ”になるように塗布して静電気記録体
を作成し皮。This dispersion was treated with a conductive agent, 1nOR34 (manufactured by Dow Chemical Company), to give a surface resistivity value of t1070. An electrostatic recording medium was prepared by coating one surface of a high-quality paper weighing 5017 m'' so that the weight after coating and drying was 697 m''.
かくして得ら２１１静電記録体に対し、２０℃。20° C. for the thus obtained 211 electrostatic recording material.
６５１％ＲＨの条件でベルト式単針電極を有する静電式
ファクシミリ受信装置を用い、印加電圧５００ｖで画像
を複製し九ところ、画像濃度か高くコントラストの鮮明
な画像が得らｆ”Ｌ７ｔ、まｔ光沢がペーパーライクで
あり、水溶性インクに対する筆記性が優れてい几。更に
３０℃、９０％ＲＨの高温高湿下に於いても画像濃度が
高く画質の変化は殆んど認めら社なかつ比。Using an electrostatic facsimile receiving device with a belt-type single-needle electrode under the condition of 651% RH, an image was reproduced with an applied voltage of 500 V, and an image with high image density and clear contrast was obtained. It has a paper-like gloss and excellent writing performance with water-soluble inks.Furthermore, the image density is high even under high temperature and high humidity conditions of 30°C and 90% RH, and there is almost no change in image quality. ratio.
〔実施例２〕
攪拌機付きオートクレーブに水３００重量部を入１、矢
に部分鹸化ポリビニルアルコール（日本合成化学工業製
ゴーセノールＧＨ−２０）α５重量部添加し、攪拌によ
り均一に分散させ、これに重合開始剤としてベンゾイル
パーオキサイド２重量部ｔ−ブチルパーオキシベンゾエ
ート１重量部をスチレン６０重量部、ジビニルナフタレ
ン４０重量部に溶解させた溶液を導入し、窒素置換し９
０℃で４時間、続いて１００℃で３時間重合を行った後
、常温まで冷却を行つ九。[Example 2] Put 300 parts by weight of water into an autoclave equipped with a stirrer, add 5 parts by weight of partially saponified polyvinyl alcohol (Gohsenol GH-20 manufactured by Nippon Gosei Kagaku Kogyo) to the arrow, disperse uniformly by stirring, and add polymerization to this. A solution of 2 parts by weight of benzoyl peroxide and 1 part by weight of t-butyl peroxybenzoate as an initiator dissolved in 60 parts by weight of styrene and 40 parts by weight of divinylnaphthalene was introduced, and the mixture was replaced with nitrogen.
9. Polymerization was carried out at 0°C for 4 hours, then at 100°C for 3 hours, and then cooled to room temperature.
得られた重合体を実施例１と同様に粉砕し、分級し、粒
径１〜１０μｍの有機粉末（Ｂ）を得九〇得らＡ几粉末
の溶剤への溶解性を表１に示した。The obtained polymer was crushed and classified in the same manner as in Example 1 to obtain an organic powder (B) with a particle size of 1 to 10 μm.The solubility of the obtained powder A in a solvent is shown in Table 1. .
次に実施例１と同様の操作を行い静電記録体を得た。こ
の静電記録体は、実施例１と同様に光沢が低くペーパー
ライクであり、筆記性が良好であつ７ｔ６ま九多針電極
を有する静電式ファクシミリ受信装置を用い、２０’Ｃ
，６０％Ｒ４の条件で印加電圧６ａｏｖ、Ｈ密度８本／
ｎで画像を複製したところ、濃度が高くよごｎがない、
鮮明でコントラストの良い画像が得らｆ′Ｌ７２１．。Next, the same operation as in Example 1 was performed to obtain an electrostatic recording material. Similar to Example 1, this electrostatic recording material has low gloss and paper-like properties, has good writability, and uses an electrostatic facsimile receiving device having 7t6 or 90 multi-needle electrodes.
, 60% R4 condition, applied voltage 6aov, H density 8 lines/
When I duplicated the image with n, the density was high and there was no dirt.
Clear images with good contrast can be obtained with f'L721. .
また解像力が良く、画線のかすｎは全く無かつ几。更に
、３０℃、９０チＲＨの高温高湿度条件下に於いても殆
んど画質は低下せず、鮮明な画像が得ら：ｎ、ｚ。尚、
この記録体は光沢が低くベーパーライ°りであり、水性
インクに対しても筆記性良好であつｔｏ
〔実施例３〕
攪拌機付きオートクレーブに水３００重量部を入ｎ、次
に部分鹸化ポリビニルアルコール田水合成化学工業製ゴ
ーセノールＧＨ−２０）１５重量部添加し、攪拌により
均一に分散させ、これに重合開始剤としてベンゾイルパ
ーオキサイド１５重量部、ｔ−プチルバーオキシベンゾ
エ−トロ５重量部をスチレン３０重量部、メタアクリル
酸エチル６５′ＭｔＬ部、ジビニルベンゼン５重量部に
溶解させ几溶液を導入し、窒素置換し、９０℃で６時間
、続いて１００℃で３時間重合を行った後、常温まで冷
却を行つ几。得らｎた重合体は、実施例１と同様に粉砕
し、分級し、粒径１〜１０μｍの有機粉末（Ｃ）を得た
。得らｎた粉末の溶剤への溶解性を表１に示し友。Also, the resolution is good, and there are no scratches on the lines. Furthermore, even under high temperature and high humidity conditions of 30° C. and 90° RH, the image quality hardly deteriorates and clear images can be obtained: n, z. still,
This recording medium has low gloss and is vapor-like, and has good writing properties even with water-based ink. [Example 3] 300 parts by weight of water was placed in an autoclave equipped with a stirrer, and then partially saponified polyvinyl alcohol water was added. 15 parts by weight of Gohsenol GH-20) manufactured by Synthetic Kagaku Kogyo Co., Ltd. were added and dispersed uniformly by stirring, and 15 parts by weight of benzoyl peroxide and 5 parts by weight of t-butylbaroxybenzoetro as polymerization initiators were added to this and 30 parts by weight of styrene. Parts by weight, 65'MtL parts of ethyl methacrylate, and 5 parts by weight of divinylbenzene were introduced into a solution, the atmosphere was replaced with nitrogen, and polymerization was carried out at 90°C for 6 hours, then at 100°C for 3 hours, and then at room temperature. Cool down to a temperature of 0. The obtained polymer was pulverized and classified in the same manner as in Example 1 to obtain an organic powder (C) with a particle size of 1 to 10 μm. Table 1 shows the solubility of the obtained powder in solvents.
次いで有機粉末（０） ２５部、塩化ビニル−酢酸ビニ
ル共重合体（共重合モル比６０対４０）の２０％トルエ
ン−メチルエチルケトン溶液２ｏ。Next, 25 parts of organic powder (0) and 20% of a 20% toluene-methyl ethyl ketone solution of vinyl chloride-vinyl acetate copolymer (copolymerization molar ratio 60:40) were added.
重量部をアトライタ′−ヲ用いて３０分間分散し、実施
例１と同様に導電処理を施した上質紙に、乾燥後の重量
が６９７ｍ”となるように塗布して静電記録体を作成し
た。得らｎた静電記録体は、光沢が低くペーパーライク
であり、賠記性か良好であった。The weight part was dispersed for 30 minutes using an attritor, and applied to high-quality paper that had been subjected to conductive treatment in the same manner as in Example 1 so that the weight after drying was 697 m'' to prepare an electrostatic recording medium. The obtained electrostatic recording material had low gloss and paper-like appearance, and had good recording properties.
更に実施例１と同様にして画像を出したところ帯電性が
良く画像濃度が高く、また汚ｎがなく、かつ解像力が優
ｎており非常に鮮明な画像が得らｎ次・
〔比較例１〕
攪拌機付きオートクレーブに水ｓｏｎ重量部を入れ、次
に主懸濁安定剤としてリン酸カルシウム（太平化学社製
）を１．５重量部と懸濁安定助剤トしテトテシルベンゼ
ンスルフォン酸ンーダ’１（１０１重量部添加し、攪拌
により均一に分散させ、こｎに重合開始剤としてベンゾ
イルパーオキサイド０．０５重量部、ｔ−ブチルパーオ
キシベンゾエートα０２重量部？メタアクリル醗メチル
１００重量部に溶解させ九溶液を導入し、窒素置換し、
９０℃で７時間、続いて１０５℃で３時間重合を行った
後、常温まで冷ｆ５を行つｔ０得らｎＬ重合体を多量の
水で洗浄し、８０℃で４８時間莞燥し友。得らｎた粒状
樹脂を粉砕器（アイカ万能粉砕器Ｍ−２０型）にて２分
間粉砕し几後、ジグザグ分級機（アルビネ社製１ｏ Ｏ
ＭＺＲ）にて粒径１〜１０μの有機粉末（Ｄ）を得た。Furthermore, when an image was produced in the same manner as in Example 1, it had good chargeability, high image density, no stains, and excellent resolution, resulting in a very clear image.[Comparative Example 1] ] Put parts by weight of water into an autoclave equipped with a stirrer, then add 1.5 parts by weight of calcium phosphate (manufactured by Taihei Kagaku Co., Ltd.) as a main suspension stabilizer and a suspension stabilizing aid to prepare tetotecylbenzenesulfonate '1 ( 101 parts by weight were added and uniformly dispersed by stirring, and dissolved in 0.05 parts by weight of benzoyl peroxide and 100 parts by weight of methyl methacrylate as polymerization initiators. Introduce the solution, replace with nitrogen,
Polymerization was carried out at 90°C for 7 hours, followed by 3 hours at 105°C, and then cooled to room temperature. The resulting nL polymer was washed with a large amount of water and dried at 80°C for 48 hours. The obtained granular resin was pulverized for 2 minutes using a pulverizer (Aica all-purpose pulverizer model M-20), and then crushed using a zigzag classifier (manufactured by Albine Co., Ltd., 1000 mm).
An organic powder (D) with a particle size of 1 to 10 μm was obtained using MZR).
得らｎた粉末の溶剤への溶解性を表１に示した。Table 1 shows the solubility of the obtained powder in a solvent.
次に有機粉末（均３０重量部、メチルメタアクリレート
／ｎ−ブチルメタアクリレート共重合体（共重合重量比
４０対６０）の２０チトル工ン溶液４００重量部をボー
ルミルに入ｎ１３時間分散させｔｏ
この分散液を表面固有抵抗値を１０７０になるように、
導電剤のｆｆ１ＯＲ３４（ダウケミカル社製）で処理し
九重さ５０９７ｍ”の上質紙の一表面に、塗布乾燥後の
重さか６９７ｍ”になるように塗布して静電記録体を作
成し友。Next, 400 parts by weight of a 20% solution of organic powder (30 parts by weight, methyl methacrylate/n-butyl methacrylate copolymer (copolymerization weight ratio 40:60)) was placed in a ball mill and dispersed for 13 hours. Adjust the surface resistivity of the dispersion to 1070.
An electrostatic recording medium was prepared by treating with a conductive agent ff1OR34 (manufactured by Dow Chemical Company) and coating it on one surface of high-quality paper with a weight of 5097 m'' so that the weight after drying was 697 m''.
かくして得らｆｔ７を静電記録体の表面は、光沢を持ち
、かつ滑らかであるため、電圧を印加し友後静電潜像を
形成せしめ、こｎを着色トナーで顕像化したとき、鮮明
度が低かった。ま友、筆記性、捺印性についてもかなり
劣っ九。The surface of the electrostatic recording medium is glossy and smooth, so when a voltage is applied to form an electrostatic latent image, and this image is visualized with colored toner, it becomes clear. The degree was low. It is also quite poor in terms of writing and stamping properties.
〔比較例２〕
攪拌機付きオートクレーブに水３００重量部を入ｎ、次
に主懸濁安定剤としてリン酸三カルシウム（太平化学社
製） ’ｋ ｔ ５重量部と懸濁安定助剤として、ドデ
シルベンゼンスルフオン酸ソーダをｃＬ０１重量部添加
し、攪拌により均一に分散させ、こｎに重合開始剤とし
てベンゾイルパーオキサイドα０３重量部、ｔ −７’
チルパ一オキシベンゾエートα０２重量部をメタアクＩ
）ｋＲ１チル２０重量部、ジエチレンクＩ７ ：７一ル
ジメタアクリレート８０重量部に溶解させた溶液を導入
し、窒素置換し、９０℃で７時間、続いて１０５℃で５
時間重合を行つｔ後、常温まで冷却を行つ几。得ら；ｆ
ｔ７を重合体を多量の水で洗浄し、８（Ｉｃで４８時間
莞燥し比。得らｎ粗粒状樹脂を粉砕器（アイカ万能粉砕
器Ｍ−２０型）にて粉末にし、ジグザグ分級機（アルピ
ネ社製−１００ＭＺＲ）にて粒径１１〜２ｏｐ？Ｆ！の
有機粉末を得た。[Comparative Example 2] Add 300 parts by weight of water to an autoclave equipped with a stirrer, then add 5 parts by weight of tricalcium phosphate (manufactured by Taihei Kagaku Co., Ltd.) as a main suspension stabilizer and dodecyl as a suspension stabilizing agent. 1 part by weight of sodium benzenesulfonate was added and dispersed uniformly by stirring, and to this was added 3 parts by weight of benzoyl peroxide α0 as a polymerization initiator, t -7'
2 parts by weight of tilpa-oxybenzoate α0 was added to Metaac I.
) A solution prepared by dissolving 20 parts by weight of kR1 chill and 80 parts by weight of diethylene chloride I7:7-1 dimethacrylate was introduced, the atmosphere was replaced with nitrogen, and the mixture was heated at 90°C for 7 hours, then at 105°C for 5 hours.
After performing polymerization for a period of time, the container is cooled to room temperature. Obtain; f
The polymer of t7 was washed with a large amount of water, and dried for 48 hours using Ic. (Alpine Co., Ltd. -100MZR) to obtain an organic powder with a particle size of 11 to 2 op?F!.
次に該有機粉末３０重量部、メチルメタアクリレート／
ｎ−ブチルメタアクリレート共重合体（共重合重量比４
０対６０）の２０％トルエン溶液４００重量部をボール
ミルに入ｆ’Ｌ、３時間分散させた。Next, 30 parts by weight of the organic powder, methyl methacrylate/
n-butyl methacrylate copolymer (copolymerization weight ratio 4
400 parts by weight of a 20% toluene solution (0:60) was placed in a ball mill and dispersed for 3 hours.
この分散液を表面固有抵抗値’ｊｊ１０７Ωになるよう
に、導電剤のＩｎｃ！Ｒ３４（ダウケミカル社製）で処
理し友、重さ５０９７ｍ”の上質紙の一表面に塗布乾燥
後の重さが６９７ｍ”になるように塗布して静電記録体
を作成し友。The conductive agent, Inc. An electrostatic recording material was prepared by treating with R34 (manufactured by Dow Chemical Company) and coating it on one surface of a high-quality paper weighing 5097 m'' so that the weight after drying was 697 m''.
得ら−ｎ几静電記録体の表面は、粗過ぎるため電圧番印
加し友後、静電潜＠全形成させ着色トナーで顕像化させ
たとき、鮮明度が低く、白ぬけも生じてい念。ま粗衣面
強度についても粒径１〜１０μｍの有機粉末使用時と比
較して弱かつ九〇
表 １
有機粉末の溶剤への溶解性
〇二可溶 ×：不溶
〔比較例３〕
脱イオン水７００重量部に、亜硝酸す） ＩＪウムα６
重量部、メタ重亜酸ナトリウム６部を加えて溶液とし、
硫酸でｐＨ２，、５に調節し友。こｎにアクリロニトリ
ル１００部を、５５℃、空気存在下で攪拌しながら８０
分間で均等に加えて４時間重合した。重合終了後、得ら
ｆ１７’ｊ重合体を大量の水で洗浄し、乾燥した。次い
で実施例と同一条件で粉砕１分級したところ、１０μｍ
以下の微粉末は非常に少量しか得らｎなかつｔｏ〔実施
例４〕
テレフタル酸３３２ｔと、２，２−ビス（４−ヒドロキ
シフェニル）プロパン１５２ｔと、ペンタエリスリトー
ル９１ｆとｔ、温度計、ステンレススチール製攪拌器、
ガラス製窒素ガス導入管及び流下式コンデンサ紫備えた
丸底フラスコ内に入ｎ、このフラスコをマントルヒータ
ーにセットし、窒素ガス導入管よＶ窒素ガスを導入して
フラスコ内を不活性雰囲気に保つ友状態で昇温せしめ友
。次いで０．０５９のジブチル錫オキシドを加え、軟下
点において反応を追跡しながら、温度２００℃で反応せ
しめ、ポリエステル樹脂を得文。The surface of the electrostatic recording material was too rough, so when a voltage was applied and the electrostatic latent was fully formed and visualized with colored toner, the clarity was low and some white spots appeared. Just in case. The coating surface strength is also weaker than when organic powder with a particle size of 1 to 10 μm is used. 700 parts by weight, nitrous acid) IJum α6
parts by weight and 6 parts of sodium metabiite to form a solution,
Adjust the pH to 2.5 with sulfuric acid. To this, 100 parts of acrylonitrile was added to 80 parts of acrylonitrile while stirring at 55°C in the presence of air.
The mixture was added evenly in minutes and polymerized for 4 hours. After the polymerization was completed, the obtained f17'j polymer was washed with a large amount of water and dried. Then, when it was crushed and classified under the same conditions as in the example, it was found to have a particle size of 10 μm.
The following fine powders were obtained only in very small quantities [Example 4] 332 tons of terephthalic acid, 152 tons of 2,2-bis(4-hydroxyphenyl)propane, 91 tons of pentaerythritol, thermometer, stainless steel made stirrer,
Place it in a round-bottomed flask equipped with a glass nitrogen gas inlet tube and a flow-down condenser, set this flask on a mantle heater, and introduce nitrogen gas through the nitrogen gas inlet tube to maintain an inert atmosphere inside the flask. A friend who raises the temperature in a friend state. Next, 0.059 dibutyltin oxide was added and the reaction was allowed to proceed at a temperature of 200° C. while monitoring the reaction at the softening point to obtain a polyester resin.
得られた樹脂を冷却後、粉砕器（アイカ万能粉砕器Ｍ−
２０型）にて粉末にし、ジグザグ分級機（アルピネ社製
１００ ＭＺＲ）にて粒径１〜１０μｍの有機粉末を得
几。得らｎ７を有機粉末は表１に示すいずｎの溶剤も不
溶であつ友。After cooling the obtained resin, a pulverizer (Aica universal pulverizer M-
20 type) to obtain an organic powder with a particle size of 1 to 10 μm using a zigzag classifier (Alpine 100 MZR). The organic powder obtained was insoluble in all the solvents shown in Table 1.
次に核有機粉末３０重量部、メチルメタアクリレ−）／
ｎ−ブチルメタアクリレート共重合体（共重合重合比４
０対６０）の２０チメチルイソプチルケトン溶液４００
重量部をボールミルに入ｎ１３時間分散させた。Next, 30 parts by weight of nuclear organic powder, methyl methacrylate)/
n-butyl methacrylate copolymer (copolymerization polymerization ratio 4
0:60) solution of 20 dimethyl isobutyl ketone 400
Parts by weight were placed in a ball mill and dispersed for 13 hours.
この分散液を表面固有抵抗値ｆｔ１０７Ωになるように
、導電剤のＫＯＲ３４（ダウケミカル社製）で処理し次
重さ５０９７ｍ”の上質紙の一表面に、塗布乾燥後の重
さが６９７ｍ”になるように塗布して静電記録体を作成
し友。This dispersion was treated with a conductive agent KOR34 (manufactured by Dow Chemical Co.) to give a surface resistivity value of 107Ω, and then coated on one surface of a high-quality paper weighing 5097 m" and weighing 697 m" after drying. Create an electrostatic recording material by applying it as desired.
得らｆｌ、几靜電記録体に対し、２０℃、６５％ＲＨの
条件でベルト式単針電極を有する静電式フ、アクシミリ
受信装置を用い、印加電圧５００Ｖで画像を複製した結
果、画像濃度が高くコントラストの鮮明な画像が得らｎ
几。を几光沢がなくペーパーライクであり、水溶性イン
クに対する筆記性が優ｎてい几。更に３０℃、９０チＲ
Ｈの高温高湿下に於いても画像濃度が高く画質の変化は
殆んど認められなかった。As a result of duplicating the image on the obtained fl, 几睜甜 recorder under the conditions of 20°C and 65% RH using an electrostatic type facsimile receiving device with a belt-type single needle electrode and an applied voltage of 500 V, the image density was It is possible to obtain clear images with high contrast.
几. It is paper-like with no gloss, and has excellent writing properties with water-soluble inks. Furthermore, 30°C, 90°C
Even under high temperature and high humidity conditions, the image density was high and almost no change in image quality was observed.
〔実施例５〕
イソフタル酸１２５ｔとベンゼン−１，２，４−トリカ
ルボン酸３１５ｆと、１．４−ブタンジオ−１ｋ２０５
ｆと、グリセロール４５ｆとを実施例４と同様に、反応
、粉砕１分級を行い、粒径１〜１０μｍの有機粉末樹脂
を得た。得らｎ九粉末は実施例４同様表１の溶剤に不溶
であつ几。[Example 5] 125t of isophthalic acid, 315f of benzene-1,2,4-tricarboxylic acid, and 205t of 1,4-butanedio-1k
f and glycerol 45f were reacted, pulverized and classified in the same manner as in Example 4 to obtain an organic powder resin with a particle size of 1 to 10 μm. As in Example 4, the obtained N9 powder was insoluble in the solvents listed in Table 1.
さらに実施例４と同様な操作を行い静電記録体を得九。Further, the same operation as in Example 4 was carried out to obtain an electrostatic recording material.
この静電記録体は、実施例４と同様に光沢が低くペーパ
ーライクであり、筆記性、捺印性が良好であつ次。ｔＸ
多針電極を有する静電式ファクシミリ受信装置を用い、
２０℃、６０４ＲＨの条件で印加電圧−６００Ｖ、線密
度８本／Ｗで画像を複製し九ところ、高濃度でかっ汚れ
がないコントラストのはつきりした画像が ′得
られ、かすｎは生じなかつ几。更に３０ｔｌ：。Similar to Example 4, this electrostatic recording material had low gloss and paper-like properties, and had good writing and printing properties. tX
Using an electrostatic facsimile receiving device with multi-needle electrodes,
When an image was reproduced under the conditions of 20°C and 604 RH, an applied voltage of -600 V, and a linear density of 8 lines/W, a high-density, sharp-contrast image with no scratches was obtained, and no smudges were generated.几. Another 30 tl:.
９０％ＲＨＣ）高温高湿度条件下に於いても殆んど画質
の低下は見らｎなかつ友。(90% RHC) Even under high temperature and high humidity conditions, there is almost no deterioration in image quality.
〔実施例６〕
フタル酸５３２ｆとベンゼン−１，２，５−トリカルボ
ン酸４２０ｔと、トリエチレングリコール１５０ｔと、
グリセロールＩ ＢＯｆとを、実施例４と同様に、反応
、粉砕１分級を行い、粒径１．〜１０μｍの有機粉末を
得友。得らｎた粉末は実施例４同様表１に示す溶剤に不
溶であっ九。[Example 6] 532f of phthalic acid, 420t of benzene-1,2,5-tricarboxylic acid, 150t of triethylene glycol,
Glycerol I BOf was reacted, crushed and classified in the same manner as in Example 4, and the particle size was 1. ~10 μm organic powder is available. As in Example 4, the obtained powder was insoluble in the solvents shown in Table 1.
次いで該有機粉末２５部、塩化ビニル−酢酸ビニル共重
合体（共重合モル比６ｏ対４０）の２０％トルエン−メ
チルエチルケトン溶１ｔ ２０口重量部をアトライダー
を用いて４５分間分散し、実施例４と同様に導電処理を
施した上質紙に、乾燥後の重量が６１７ｍ”となるよう
に塗布して静電記録体を作成し九〇得ら′ｔ′Ｌ九静電
記録体は光沢が低く、ペーパーライフであり、筆記性が
良好であつ友。更に実施例４と同様にして画像を出し友
ところ、帯電性が艮〈画像濃度が高く、′！几汚ｎが無
く、そして解像力が優れ次画像が得らｎ交〇
〔比較例４〕
フタル酸４．５６９と、トリエチレングリコール２８１
ｆと、グリセロール４５ｆとを温度計、ステンレススチ
ール製攪拌器、ガラス製窒素ガス導入管及び流下式コン
デンサを備えた丸底フラスコ内に入ｎ１このフラスコを
マントルヒーターにセットし、窒素ガス導入管より窒素
ガスを導入してフラスコ内を不活性雰囲気に保った状態
で昇温せしめ九〇そしてα０５ｆのジプチル錫オキシド
を加え軟下点において反応を追跡しながら温度２００℃
で反応せしめ、ポリエステル樹脂を得几。Next, 25 parts of the organic powder and 20 parts by weight of 1 t of 20% toluene-methyl ethyl ketone solution of vinyl chloride-vinyl acetate copolymer (copolymerization molar ratio 6o:40) were dispersed for 45 minutes using an atrider. An electrostatic recording medium was prepared by coating high-quality paper that had been subjected to conductive treatment in the same manner as above so that the weight after drying would be 617 m''. , paper life, and good writing performance.Furthermore, when an image was produced in the same manner as in Example 4, the charging property was excellent (the image density was high, there was no smudge, and the resolution was excellent). The following image was obtained: n intersection [Comparative Example 4] Phthalic acid 4.569 and triethylene glycol 281
Put f and 45f of glycerol into a round bottom flask equipped with a thermometer, a stainless steel stirrer, a glass nitrogen gas inlet tube, and a flow-down condenser. While keeping the inside of the flask in an inert atmosphere by introducing nitrogen gas, the temperature was raised to 90°C, and diptyltin oxide of α05f was added, and the temperature was raised to 200°C while monitoring the reaction at the softening point.
to obtain polyester resin.
得らｎた樹脂を冷却後、粉砕器（アイカ万能粉砕器Ｍ−
２０型）にて粉末にし、ジグザグ分級機（アルピネ社製
１００ ＭＺＲ）にて粒径１〜１０μｍの粉末樹脂を得
九〇
次に粉末樹脂３０ｉ量部、メチルアクリレ−）／ｎ−ブ
チルメタアクリレート共重合体（共重合重合比４０対６
０）の２０％メチルイソブチルケトン溶液４００！ｊｉ
部？ボールミルに入ｊＬ、３時間分散させた。After cooling the obtained resin, use a pulverizer (Aika universal pulverizer M-
20 type) to obtain a powder resin with a particle size of 1 to 10 μm using a zigzag classifier (Alpine 100 MZR). Polymer (copolymerization ratio 40:6
0) 20% methyl isobutyl ketone solution 400! ji
Department? The mixture was placed in a ball mill and dispersed for 3 hours.
この分散液を表面固有抵抗値’ｉ１０’Ωになるように
、導電剤のｌ０Ｒ３４（ダウケミカル社製）で処理した
重さ５０ｔｌｍχの上質紙の一表面に、塗布乾燥後の重
さが６９７ｍ”になるように塗布して静電記録体を作成
し友。This dispersion was applied to one surface of a 50 tlmx high-quality paper treated with a conductive agent 10R34 (manufactured by Dow Chemical Co.) so that the surface resistivity value was 'i10' Ω, and the weight after drying was 697 m''. Create an electrostatic recording material by applying it so that it becomes a friend.
得らｎた静電記録体の表面は、光沢を持ち、かつ滑らか
である几め、静電潜像を着色トナーで顕像化したとき、
鮮明度が低かっ几。また、筆記性、捺印性についてもか
なり劣った。The surface of the electrostatic recording material obtained is glossy and smooth, and when the electrostatic latent image is visualized with colored toner,
The clarity is low. Furthermore, the writing and stamping properties were also quite poor.
〔比較例５〕
フタル酸３３２ｔと、ベンゼン−１，２，５−トリカル
ボン酸４２０ｔと、トリエチレングリコール１５０ｆと
、ペンタエリスリトール２００ｆとを比較例４と同様に
反応、粉砕２分級を行い粒径１５〜２５μｍの粉末樹脂
を得友。更に比較例４と同様の操作を行い、静電記録体
を得交Ｏ
得られ几靜電記録体の表面は粗過ぎる之め、静電潜像を
着色トナーで顕像化し友とき、白ぬけが生じ、鮮明度が
低い。また表面強度については実施例４の有機粉末使用
時と比較して弱かった。[Comparative Example 5] 332 t of phthalic acid, 420 t of benzene-1,2,5-tricarboxylic acid, 150 f of triethylene glycol, and 200 f of pentaerythritol were reacted in the same manner as in Comparative Example 4, and the mixture was crushed and classified into two particles with a particle size of 15. ~25 μm powder resin is available. Furthermore, the same operation as in Comparative Example 4 was carried out to obtain an electrostatic recording material.The surface of the obtained electrostatic recording material was too rough, so the electrostatic latent image was visualized with a colored toner, and the white spots were removed. occurs, and the clarity is low. Moreover, the surface strength was weaker than that in Example 4 when the organic powder was used.
以上詳述したように本発明で用いらｎる有機粉体は通常
の粉砕２分級手段により容易に効率的に得らｎ１通常の
高誘電体絶縁性樹脂を溶解させる溶剤に不溶であり、か
つ優れ比特性を有する静電記録体を提供することができ
る。As detailed above, the organic powder used in the present invention can be easily and efficiently obtained by ordinary pulverization and classification means, is insoluble in a solvent that dissolves ordinary high dielectric insulating resin, and An electrostatic recording medium having excellent ratio characteristics can be provided.
Claims (1)
合されている高誘電体絶縁性樹脂からなる誘電体層を、
低抵抗処理が施された基体上に積層してなる静電記録体
。 ２、有機粉末が、少なくとも０．０１重量％の架橋剤を
含む単量体混合物をラジカル共重合させたものである特
許請求の範囲第１項記載の静電記録体。 ３、有機粉末が、少なくとも２０モル％の３官能以上の
多官能性単量体を含む単量体混合物を縮合重合させたポ
リエステル樹脂である特許請求の範囲第１項記載の静電
記録体。[Claims] 1. A dielectric layer made of a high dielectric insulating resin in which crosslinked organic powder with a particle size of 10 μm or less is dispersed,
An electrostatic recording material that is laminated on a substrate that has been treated with low resistance. 2. The electrostatic recording material according to claim 1, wherein the organic powder is obtained by radical copolymerization of a monomer mixture containing at least 0.01% by weight of a crosslinking agent. 3. The electrostatic recording material according to claim 1, wherein the organic powder is a polyester resin obtained by condensation polymerization of a monomer mixture containing at least 20 mol % of a trifunctional or higher polyfunctional monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15388285A JPS6214653A (en) | 1985-07-12 | 1985-07-12 | Electrophotographic recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15388285A JPS6214653A (en) | 1985-07-12 | 1985-07-12 | Electrophotographic recording material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6214653A true JPS6214653A (en) | 1987-01-23 |
Family
ID=15572170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15388285A Pending JPS6214653A (en) | 1985-07-12 | 1985-07-12 | Electrophotographic recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6214653A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50127634A (en) * | 1974-03-27 | 1975-10-07 | ||
| JPS56132346A (en) * | 1980-03-19 | 1981-10-16 | Matsushita Electric Ind Co Ltd | Electrostatic recorder |
| JPS57100434A (en) * | 1980-12-16 | 1982-06-22 | Matsushita Electric Ind Co Ltd | Electrostatic recording body |
-
1985
- 1985-07-12 JP JP15388285A patent/JPS6214653A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50127634A (en) * | 1974-03-27 | 1975-10-07 | ||
| JPS56132346A (en) * | 1980-03-19 | 1981-10-16 | Matsushita Electric Ind Co Ltd | Electrostatic recorder |
| JPS57100434A (en) * | 1980-12-16 | 1982-06-22 | Matsushita Electric Ind Co Ltd | Electrostatic recording body |
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