JPH0569135B2 - - Google Patents
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- Publication number
- JPH0569135B2 JPH0569135B2 JP60175150A JP17515085A JPH0569135B2 JP H0569135 B2 JPH0569135 B2 JP H0569135B2 JP 60175150 A JP60175150 A JP 60175150A JP 17515085 A JP17515085 A JP 17515085A JP H0569135 B2 JPH0569135 B2 JP H0569135B2
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- JP
- Japan
- Prior art keywords
- water
- group
- emulsion
- formula
- salt
- 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.)
- Expired - Lifetime
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- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
〔産業上の利用分野〕
本発明は水性樹脂エマルシヨンからなる接着剤
もしくはコーテイング剤用水分散型樹脂組成物に
関する。
〔従来の技術〕
乳化重合物即ち水性樹脂エマルシヨンからなる
接着剤もしくはコーテイング剤用水分散型樹脂組
成物の乾燥塗膜の耐水性、接着性等の性能向上を
目的としてエチレン性不飽和単量体の乳化重合時
に重合性乳化剤たとえば（メタ）アリル基（アリ
ル基および／またはメタリル基を略記。以下同様
の表現を用いる）含有スルホン酸塩（特開昭58−
7468号公報）、スルホン酸塩基含有芳香族（メタ）
アクリレート（特開昭57−198716号）などを用い
る技術がある。
〔発明が解決しようとする問題点〕
しかしながら（メタ）アリル基含有スルホン酸
塩、スルホン酸塩基含有芳香族（メタ）アクリレ
ートなどを用いる場合には、重合体エマルシヨン
の乾燥塗膜の耐水性および接着性が十分ではない
という問題点がある。
〔問題点を解決するための手段〕
本発明者らは乾燥塗膜の耐水性、接着性が優れ
た水性樹脂エマルシヨンからなる接着剤もしくは
コーテイング剤用水分散型樹脂組成物を得るべく
鋭意検討の結果、本発明に到達した。即ち本発明
は、一般式
[Industrial Application Field] The present invention relates to a water-dispersed resin composition for adhesives or coating agents comprising an aqueous resin emulsion. [Prior Art] Ethylenically unsaturated monomers have been developed for the purpose of improving the performance, such as water resistance and adhesion, of dry coatings of water-dispersed resin compositions for adhesives or coating agents made of emulsion polymers, that is, aqueous resin emulsions. During emulsion polymerization, a polymerizable emulsifier such as a (meth)allyl group (allyl group and/or methallyl group is abbreviated. The same expression will be used hereinafter)-containing sulfonate (JP-A-58-
7468), sulfonic acid group-containing aromatic (meth)
There is a technique using acrylate (Japanese Unexamined Patent Publication No. 57-198716). [Problems to be Solved by the Invention] However, when using (meth)allyl group-containing sulfonate salts, sulfonic acid group-containing aromatic (meth)acrylates, etc., the water resistance and adhesion of the dried coating film of the polymer emulsion may be affected. The problem is that there is not enough sex. [Means for Solving the Problems] The present inventors have conducted intensive studies to obtain a water-dispersed resin composition for adhesives or coating agents that is made of an aqueous resin emulsion and has excellent water resistance and adhesive properties for dry coatings. , arrived at the present invention. That is, the present invention is based on the general formula
【化】
（式中、Ｒは水素またはメチル基である。Ａはア
ルキレン基である。ｎは２以上の整数である。Ｍ
は１価または２価の陽イオンである。ｍは１〜２
の整数であり、陽イオンＭの原子価をあらわす。）
で示される硫酸エステル（塩）(A)と、これと共重
合し得る疎水性エチレン性不飽和単量体(B)および
必要により親水性エチレン性不飽和単量体(C)との
乳化重合により得られる水性樹脂エマルシヨンか
らなることを特徴とする接着剤もしくはコーテイ
ング剤用水分散型樹脂組成物である。
本発明に使用される一般式(1)で示される硫酸エ
ステル（塩）(A)において、Ａのアルキレン基とし
ては炭素数２〜４のアルキレン基、例えばエチレ
ン基、プロピレン基およびブチレン基があげられ
る。これらのアルキレン基は酸素と共にオキシア
ルキレン基を形成し、ｎ個の該オキシアルキレン
基は同種のものでもよくまた異種のもの（ブロク
またはランダム）でもよい。好ましいものはオキ
シプロピレン基およびオキシエチレン基とオキシ
プロピレン基との併用基（ブロツク、ランダム）
であり、とくに好ましいものは、ｎ個のオキシア
ルキレン（―OA）―基中にオキシプロピレン基が２
個以上存在する基である。
ｎは２以上、好ましくは２〜30、とくに好まし
くは３〜15の整数である。
Ｍの１価または２価の陽イオンとしては、水
素、アルカリ金属（ナトリウム、カリウムなど）、
アルカリ土類金属（カルシウム、マグネシウムな
ど）、アンモニウム、有機アミンカチオン（アル
カノールアミンカチオン、低級アルキルアミンカ
チオンなど）があげられる。これらのうち好まし
いものは、アルカリ金属（とくにナトリウムおよ
びカリウム）およびアンモニウムである。
本発明に使用される硫酸エステル（塩）の具体
例としては下式で示される化合物があげられる。
下式中EOはC2H4Oを、POはC3H6Oを示す。
(イ) 硫酸エステル塩基含有アクリル酸ポリアルキ
レングリコールエステル
CH2＝CH−COO（―EO）―8SO3Na (2)
CH2＝CH−COO（―PO）―10（EO）―2SO3K (3)
（ブロツク）
CH2＝CH−COO（―EO）―5（PO）―10SO3Na (4)
（ランダム）
CH2＝CH−COO（―PO）―15SO3NH4 (5)
(ロ) 硫酸エステル塩基含有メタクリル酸ポリアル
キレングリコールエステル[Formula, R is hydrogen or a methyl group. A is an alkylene group. n is an integer of 2 or more. M
is a monovalent or divalent cation. m is 1~2
is an integer representing the valence of the cation M. )
Emulsion polymerization of the sulfuric acid ester (salt) (A) represented by the formula, a hydrophobic ethylenically unsaturated monomer (B) that can be copolymerized with the sulfuric ester (salt), and optionally a hydrophilic ethylenically unsaturated monomer (C). This is a water-dispersed resin composition for adhesives or coating agents, which is characterized by comprising an aqueous resin emulsion obtained by. In the sulfuric acid ester (salt) (A) represented by the general formula (1) used in the present invention, the alkylene group of A includes an alkylene group having 2 to 4 carbon atoms, such as an ethylene group, a propylene group, and a butylene group. It will be done. These alkylene groups form an oxyalkylene group together with oxygen, and the n oxyalkylene groups may be of the same type or different types (block or random). Preferred are oxypropylene groups and combination groups of oxyethylene and oxypropylene groups (block, random)
and a particularly preferred one is one in which there are 2 oxypropylene groups in the n oxyalkylene (-OA) groups.
It is a group that exists in more than one group. n is an integer of 2 or more, preferably 2 to 30, particularly preferably 3 to 15. Monovalent or divalent cations of M include hydrogen, alkali metals (sodium, potassium, etc.),
Examples include alkaline earth metals (calcium, magnesium, etc.), ammonium, and organic amine cations (alkanolamine cations, lower alkylamine cations, etc.). Preferred among these are alkali metals (especially sodium and potassium) and ammonium. Specific examples of the sulfuric ester (salt) used in the present invention include compounds represented by the following formula.
In the formula below, EO represents C 2 H 4 O and PO represents C 3 H 6 O. (a) Acrylic acid polyalkylene glycol ester containing sulfate ester base CH 2 = CH−COO(—EO)— 8 SO 3 Na (2) CH 2 = CH−COO(—PO)— 10 (EO)— 2 SO 3 K (3) (Block) CH 2 = CH−COO(―EO)― 5 (PO)― 10 SO 3 Na (4) (Random) CH 2 = CH−COO(―PO)― 15 SO 3 NH 4 ( 5) (b) Polyalkylene glycol methacrylate ester containing sulfate ester base
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
以下実施例および比較例により本発明をさらに
説明するが本発明はこれらの実施例および比較例
に限定されるものではない。
実施例 １
撹拌機、滴下ロート、窒素導入口、温度計、お
よび還流冷却器を備えた反応容器にイオン交換水
117.5ｇ、炭酸水素ナトリウム0.08ｇ、過硫酸ア
ンモニウム0.16ｇ、スチレン22ｇ、ブチルアクリ
レート18ｇおよび式(9)の硫酸エステル塩1.6ｇを
仕込み撹拌乳化し、窒素置換後撹拌下75℃で30分
間重合した。ひきつづきイオン交換水134.5ｇ、
式(9)の硫酸エステル塩5.6ｇ、炭酸水素ナトリウ
ム0.28ｇ、過硫酸アンモニウム0.56ｇ、スチレン
77ｇおよびブチルアクリレート63ｇからなる乳化
液を滴下ロートより２時間にわたり滴下し、撹拌
下80℃で重合を行ないさらに過硫酸アンモニウム
１％水溶液18ｇを追加後85℃に昇温し２時間重合
を行ない、濃度41重量％、粘度15cpsの重合体エ
マルシヨン（本発明の組成物）を得た。
実施例 ２
撹拌機、滴下ロート、窒素導入口、温度計およ
び還流冷却器を備えた反応容器にイオン交換水
117.5ｇ、過硫酸カリウム0.16ｇ、メチルメタク
リレート20ｇ、ブチルアクリレート20ｇおよび式
(5)の硫酸エステル塩1.6ｇを仕込み撹拌乳化し、
窒素置換後75℃で30分間重合した。ひきつづきイ
オン交換水134.5ｇ、式(5)の硫酸エステル塩5.6
ｇ、過硫酸カリウム0.56ｇ、メチルメタクリレー
ト69ｇ、ブチルアクリレート69ｇおよびアクリル
酸２ｇからなる乳化液を滴下ロートより２時間に
わたり滴下し、撹拌下80℃で重合を行ないさらに
過硫酸カリウム１％水溶液18ｇを追加後85℃に昇
温し２時間重合を行ない、濃度41重量％粘度
10cpsの重合体エマルシヨン（本発明の組成物）
を得た。
実施例 ３
撹拌機、滴下ロート、窒素導入口、温度計およ
び還流冷却器を備えた反応容器にイオン交換水
117.5ｇ、過硫酸カリウム0.16ｇ、酢酸ビニル20
ｇ、ブチルメタクリレート20ｇおよび式(10)の硫酸
エステル塩1.6ｇを仕込み撹拌乳化し、窒素置換
後75℃で30分間重合した。ひきつづきイオン交換
水134.5ｇ、式(10)の硫酸エステル塩5.6ｇ、過硫酸
カリウム0.56ｇ、酢酸ビニル68ｇ、ブチルメタア
クリレート68ｇおよびメタアクリル酸４ｇからな
る乳化液を滴下ロートより２時間にわたり滴下
し、撹拌下75℃で重合を行ない、濃度41重量％粘
度15cpsの重合体エマルシヨン（本発明の組成物）
を得た。
比較例 １
実施例１において乳化剤として用いた硫酸エス
テル塩のかわりに同重量のドデシルアリルスルホ
コハク酸ナトリウムを使用し、実施例１の方法に
従つて乳化重合を行ない、濃度41重量％粘度
35cpsの重合体エマルシヨンを得た。
比較例 ２
実施例１において乳化剤として用いた硫酸エス
テル塩のかわりに同重量のアクリロイルオキシノ
ニルベンゼンスルホン酸ナトリウムを使用し、実
施例１の方法に従つて乳化重合を行ない、濃度40
重量％粘度15cpsの重合体エマルシヨンを得た。
比較例 ３
実施例２において乳化剤として用いた硫酸エス
テル塩のかわりに同重量のドデシルメタリルスル
ホコハク酸アンモニウムを使用し、実施例２の方
法に従つて乳化重合を行ない、濃度40％粘度
35cpsの重合体エマルシヨンを得た。
比較例 ４
実施例２において乳化剤として用いた硫酸エス
テル塩のかわりに同重量のメタアクリロイルオキ
シノニルベンゼンスルホン酸ナトリウムを使用し
実施例２の方法に従つて乳化重合を行ない、濃度
40％粘度15cpsの重合体エマルシヨンを得た。
試験例 １
実施例１〜３の本発明の組成物および比較例１
〜４の重合体エマルシヨンをガラス板上に乾燥フ
イルム厚さが0.2mmになるように塗布し25℃で24
時間次いで60℃で５時間乾燥して、ガラス板上に
樹脂フイルムを形成した。
この樹脂フイルムを形成したガラス板およびガ
ラス板から剥離した樹脂フイルムを用いて下記の
方法により耐水性試験、接着性試験、耐屈曲性試
験、耐水強度および耐水接着性試験を行なつた。
試験結果を表−１に示す。
耐水性試験：樹脂フイルムを形成したガラス板を
水中に120時間浸漬し樹脂フイルムを観察した。
○…樹脂フイルムは透明のままで白濁しない。
△…樹脂フイルムはやや白濁しているが８ポイ
ントのひらがな活字が透視できる。
×…樹脂フイルムは白濁しており８ポイントの
ひらがな活字が透視できない。
接着性試験：ガラス板とフイルム間の接着力を引
張り強度試験機を用いた180°剥離強度測定値で
示した。
耐屈曲性試験：フイルムの180°屈曲による破壊ま
でに要する屈曲回数を測定した。
耐水強度試験：水中に48時間浸漬後のフイルムの
引張破断強度を浸漬前のフイルムの引張破断強
度と比較した。
○…フイルムの水中浸漬による強度低下が５％
未満のもの
△…フイルムの水中浸漬による強度低下が５％
以上50％未満のもの
×…フイルムの水中浸漬による強度低下が50％
以上のもの
耐水接着性試験：樹脂フイルムを形成したガラス
板を240時間水中に浸漬しうき、はがれの有無
を観察した
○…うき、はがれなし
△…一部うき、はがれあり
×…全面はがれあり
The present invention will be further explained below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples. Example 1 Ion-exchanged water was added to a reaction vessel equipped with a stirrer, dropping funnel, nitrogen inlet, thermometer, and reflux condenser.
117.5 g, sodium bicarbonate 0.08 g, ammonium persulfate 0.16 g, styrene 22 g, butyl acrylate 18 g, and 1.6 g of the sulfuric ester salt of formula (9) were charged and emulsified with stirring, and after nitrogen substitution, polymerization was carried out at 75° C. for 30 minutes with stirring. Continued ion exchange water 134.5g,
5.6 g of sulfate ester salt of formula (9), 0.28 g of sodium bicarbonate, 0.56 g of ammonium persulfate, styrene
An emulsion consisting of 77 g and 63 g of butyl acrylate was added dropwise from the dropping funnel over 2 hours, and polymerization was carried out at 80°C while stirring. After adding 18 g of a 1% aqueous solution of ammonium persulfate, the temperature was raised to 85°C and polymerization was carried out for 2 hours. A polymer emulsion (composition of the invention) of 41% by weight and a viscosity of 15 cps was obtained. Example 2 Ion-exchanged water was added to a reaction vessel equipped with a stirrer, dropping funnel, nitrogen inlet, thermometer, and reflux condenser.
117.5g, potassium persulfate 0.16g, methyl methacrylate 20g, butyl acrylate 20g and formula
Add 1.6 g of the sulfate ester salt of (5), stir and emulsify.
After purging with nitrogen, polymerization was carried out at 75°C for 30 minutes. Continued: 134.5 g of ion-exchanged water, 5.6 g of sulfate ester salt of formula (5)
An emulsion containing 0.56 g of potassium persulfate, 69 g of methyl methacrylate, 69 g of butyl acrylate, and 2 g of acrylic acid was added dropwise from a dropping funnel over 2 hours, and polymerization was carried out at 80°C with stirring, followed by addition of 18 g of a 1% aqueous solution of potassium persulfate. After addition, the temperature was raised to 85℃ and polymerization was carried out for 2 hours, resulting in a concentration of 41% by weight and viscosity.
10 cps polymer emulsion (composition of the invention)
I got it. Example 3 Ion-exchanged water was added to a reaction vessel equipped with a stirrer, dropping funnel, nitrogen inlet, thermometer, and reflux condenser.
117.5g, potassium persulfate 0.16g, vinyl acetate 20
g, butyl methacrylate, 20 g, and 1.6 g of the sulfuric acid ester salt of formula (10) were charged, stirred and emulsified, and after purging with nitrogen, polymerization was carried out at 75° C. for 30 minutes. Subsequently, an emulsion consisting of 134.5 g of ion-exchanged water, 5.6 g of the sulfuric ester salt of formula (10), 0.56 g of potassium persulfate, 68 g of vinyl acetate, 68 g of butyl methacrylate, and 4 g of methacrylic acid was added dropwise from the dropping funnel over a period of 2 hours. , polymerization was carried out at 75° C. with stirring to form a polymer emulsion (composition of the present invention) having a concentration of 41% by weight and a viscosity of 15 cps.
I got it. Comparative Example 1 Emulsion polymerization was carried out according to the method of Example 1 using the same weight of sodium dodecylallylsulfosuccinate instead of the sulfuric ester salt used as the emulsifier in Example 1, and the concentration was 41% by weight.
A polymer emulsion of 35 cps was obtained. Comparative Example 2 Emulsion polymerization was carried out according to the method of Example 1 using the same weight of sodium acryloyloxynonylbenzenesulfonate instead of the sulfuric ester salt used as the emulsifier in Example 1, and the concentration was 40.
A polymer emulsion with a weight percent viscosity of 15 cps was obtained. Comparative Example 3 Emulsion polymerization was carried out according to the method of Example 2 using the same weight of ammonium dodecylmethallyl sulfosuccinate instead of the sulfuric ester salt used as the emulsifier in Example 2, resulting in a concentration of 40% viscosity.
A polymer emulsion of 35 cps was obtained. Comparative Example 4 Emulsion polymerization was carried out according to the method of Example 2 using the same weight of sodium methacryloyloxynonylbenzenesulfonate instead of the sulfuric ester salt used as the emulsifier in Example 2, and the concentration was
A 40% polymer emulsion with a viscosity of 15 cps was obtained. Test Example 1 Compositions of the present invention of Examples 1 to 3 and Comparative Example 1
The polymer emulsion of ~4 was coated on a glass plate so that the dry film thickness was 0.2 mm, and it was heated at 25℃ for 24 hours.
The resin film was then dried at 60° C. for 5 hours to form a resin film on the glass plate. Using the glass plate on which this resin film was formed and the resin film peeled from the glass plate, a water resistance test, an adhesion test, a bending resistance test, a water resistance strength test, and a water resistance adhesion test were conducted according to the following methods.
The test results are shown in Table-1. Water resistance test: The glass plate on which the resin film was formed was immersed in water for 120 hours, and the resin film was observed. ○...The resin film remains transparent and does not become cloudy. △...The resin film is slightly cloudy, but the 8-point hiragana type can be seen through. ×...The resin film is cloudy and the 8-point hiragana type cannot be seen through. Adhesion test: The adhesion between the glass plate and the film was measured using a tensile strength tester at 180° peel strength. Bending resistance test: The number of times the film was bent by 180° until it broke was measured. Water resistance strength test: The tensile strength at break of the film after being immersed in water for 48 hours was compared with the tensile strength at break of the film before immersion. ○…The strength decreases by 5% when the film is immersed in water.
Less than △…The strength decreases by 5% when the film is immersed in water.
or more than 50% ×…The strength reduction due to film immersion in water is 50%
Water resistant adhesion test for the above: A glass plate with a resin film formed on it was immersed in water for 240 hours, and the presence or absence of peeling was observed.
本発明の組成物は従来の重合体エマルシヨンに
くらべて、重合体エマルシヨンの乾膜塗膜の耐水
性および接着性がきわめて向上したものである。
また、乾燥塗膜の耐屈曲性が高く、耐水強度が高
い。さらに本発明の組成物は泡立ちも少ない他乾
燥塗膜の帯電防止性が向上するという効果があ
る。
The composition of the present invention has significantly improved water resistance and adhesion of the dry film coating of the polymer emulsion compared to conventional polymer emulsions.
In addition, the dried coating film has high bending resistance and high water resistance. Furthermore, the composition of the present invention has the effect of less foaming and improved antistatic properties of the dried coating film.
Claims (1)
ルキレン基である。ｎは２以上の整数である。Ｍ
は１価または２価の陽イオンである。ｍは１〜２
の整数であり、陽イオンＭの原子価をあらわす。）
で示される硫酸エステル（塩）(A)と、これと共重
合し得る疎水性エチレン性不飽和単量体(B)および
必要により親水性エチレン性不飽和単量体(C)との
乳化重合により得られる水性樹脂エマルシヨンか
らなることを特徴とする接着剤もしくはコーテイ
ング剤用水分散型樹脂組成物。 ２ −（AO）o−基中にオキシプロピレン基が２個
以上存在する特許請求の範囲第１項記載の樹脂組
成物。 ３ (A)、(B)および(C)の量が全単量体の合計重量に
基づいて(A)が0.1〜20％、(B)が60〜99.9％、(C)が
０〜20％である特許請求の範囲第１項または第２
項記載の樹脂組成物。[Claims] 1 General formula: (wherein, R is hydrogen or a methyl group. A is an alkylene group. n is an integer of 2 or more. M
is a monovalent or divalent cation. m is 1~2
is an integer representing the valence of the cation M. )
Emulsion polymerization of the sulfuric acid ester (salt) (A) represented by the formula, a hydrophobic ethylenically unsaturated monomer (B) that can be copolymerized with the sulfuric ester (salt), and optionally a hydrophilic ethylenically unsaturated monomer (C). A water-dispersed resin composition for adhesives or coating agents, characterized by comprising an aqueous resin emulsion obtained by. 2. The resin composition according to claim 1, wherein two or more oxypropylene groups are present in the 2-(AO) o- group. 3 The amounts of (A), (B) and (C) are 0.1 to 20% of (A), 60 to 99.9% of (B), and 0 to 20% of (C) based on the total weight of all monomers. % of claim 1 or 2
The resin composition described in .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17515085A JPS6234947A (en) | 1985-08-08 | 1985-08-08 | Waer dispersion type resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17515085A JPS6234947A (en) | 1985-08-08 | 1985-08-08 | Waer dispersion type resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6234947A JPS6234947A (en) | 1987-02-14 |
| JPH0569135B2 true JPH0569135B2 (en) | 1993-09-30 |
Family
ID=15991144
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17515085A Granted JPS6234947A (en) | 1985-08-08 | 1985-08-08 | Waer dispersion type resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6234947A (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2744842B2 (en) * | 1990-11-02 | 1998-04-28 | 東洋インキ製造株式会社 | Aqueous resin dispersion |
| DE19514266A1 (en) * | 1995-04-15 | 1996-10-17 | Basf Ag | Process for the preservation of a mineral shaped body |
| JP3804791B2 (en) | 2000-06-07 | 2006-08-02 | セイコーエプソン株式会社 | Ink jet recording ink, recording method, recorded matter, and ink jet recording apparatus |
| JP3599677B2 (en) | 2001-03-19 | 2004-12-08 | クラリアントポリマー株式会社 | Coating composition for inkjet recording medium and inkjet recording medium |
| JP3640921B2 (en) | 2001-12-28 | 2005-04-20 | クラリアントポリマー株式会社 | Synthetic resin emulsion, easily water-swellable pressure-sensitive adhesive composition comprising the same, and method for producing synthetic resin emulsion |
| WO2006043571A1 (en) | 2004-10-18 | 2006-04-27 | Seiko Epson Corporation | Encapsulation product, process for producing the same, and ink composition |
| JP4682892B2 (en) | 2005-04-19 | 2011-05-11 | セイコーエプソン株式会社 | Microcapsule manufacturing method, microcapsule, electrophoretic display device, and electronic apparatus |
| JP5034298B2 (en) | 2005-04-19 | 2012-09-26 | セイコーエプソン株式会社 | Microcapsule, method for producing microcapsule, electrophoretic display device and electronic apparatus |
| JP4207161B2 (en) | 2005-04-20 | 2009-01-14 | セイコーエプソン株式会社 | Microencapsulated metal particles and method for producing the same, aqueous dispersion, and ink jet ink |
| JP4857799B2 (en) | 2006-02-10 | 2012-01-18 | セイコーエプソン株式会社 | Photoelectric conversion element, method for manufacturing photoelectric conversion element, and electronic device |
| CN101861367B (en) | 2007-11-15 | 2013-08-28 | 精工爱普生株式会社 | Ink composition |
| JP4940178B2 (en) * | 2008-03-31 | 2012-05-30 | 旭有機材工業株式会社 | Method and apparatus for mixing powder particles |
| JP6028373B2 (en) | 2012-04-05 | 2016-11-16 | セイコーエプソン株式会社 | Electrophoretic particles, method for producing electrophoretic particles, electrophoretic dispersion, electrophoretic sheet, electrophoretic device, and electronic apparatus |
| SG11201503925QA (en) | 2012-11-28 | 2015-06-29 | Mitsubishi Gas Chemical Co | Resin composition, prepreg, laminate, metallic foil clad laminate, and printed circuit board |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2832834B2 (en) * | 1988-08-23 | 1998-12-09 | 東芝機械株式会社 | Spray device for die casting machine |
-
1985
- 1985-08-08 JP JP17515085A patent/JPS6234947A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6234947A (en) | 1987-02-14 |
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