JPH0753635A - Emulsion composition and its production - Google Patents
Emulsion composition and its productionInfo
- Publication number
- JPH0753635A JPH0753635A JP12108894A JP12108894A JPH0753635A JP H0753635 A JPH0753635 A JP H0753635A JP 12108894 A JP12108894 A JP 12108894A JP 12108894 A JP12108894 A JP 12108894A JP H0753635 A JPH0753635 A JP H0753635A
- Authority
- JP
- Japan
- Prior art keywords
- emulsion composition
- emulsion
- vinyl
- epoxy group
- alicyclic epoxy
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は新規にして有用なるエマ
ルジョン組成物とその製造方法に関する。FIELD OF THE INVENTION The present invention relates to a novel and useful emulsion composition and a method for producing the same.
【０００２】さらに詳細には、特定の脂環式エポキシ基
を有するビニル系単量体類と共重合可能なビニル系単量
体類を、水性媒体中で乳化重合させることにより得られ
る、極めて有用性の高いエマルジョン組成物とその製造
方法に関する。More specifically, it is very useful, which is obtained by emulsion-polymerizing vinyl monomers copolymerizable with vinyl monomers having a specific alicyclic epoxy group in an aqueous medium. To an emulsion composition having high properties and a method for producing the same.
【０００３】本発明は脂環式エポキシ基を架橋成分とし
て用いるエマルジョン組成物であり、エマルジョン型塗
料、接着剤、シーリング剤、および特に繊維処理剤など
の各種用途に有用である新規なエマルジョン組成物に関
するものである。The present invention is an emulsion composition using an alicyclic epoxy group as a cross-linking component, and is a novel emulsion composition useful for various applications such as emulsion type paints, adhesives, sealing agents, and especially fiber treatment agents. It is about.
【０００４】[0004]
【従来の技術】これまでにも、塗料や接着剤、シーリン
グ剤、繊維処理剤などの各種用途に用いられるエマルジ
ョン組成物としては、グリシジルメタクリレートやＮ−
メチロールアクリルアミドなどを架橋成分として含有す
るエマルジョン組成物が、実用に供されてきた。2. Description of the Related Art Emulsion compositions used for various applications such as paints, adhesives, sealing agents, and fiber treatment agents have hitherto been used.
Emulsion compositions containing methylol acrylamide as a cross-linking component have been put to practical use.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、グリシ
ジルメタクリレートを架橋成分として含有するエマルジ
ョン組成物では、グリシジルメタクリレートは反応性が
高く乳化重合中に反応し、エマルジョン組成物の重合安
定性が悪くなるため、架橋成分としてのグリシジルメタ
クリレートの使用量に制限があり、架橋成分の含有量の
多いエマルジョン組成物の開発は望まれるところであ
る。However, in an emulsion composition containing glycidyl methacrylate as a cross-linking component, glycidyl methacrylate is highly reactive and reacts during emulsion polymerization, and the polymerization stability of the emulsion composition deteriorates. There is a limit to the amount of glycidyl methacrylate used as a crosslinking component, and development of an emulsion composition containing a large amount of crosslinking component is desired.
【０００６】また、Ｎ−メチロールアクリルアミドを架
橋成分として含有するエマルジョン組成物では、エマル
ジョン組成物塗布後の架橋生成（硬化反応）において、
Ｎ−メチロールアクリルアミドからホルムアルデヒドが
遊離するため、使用環境においてホルマリン臭が激しい
という欠点があり、Ｎ−メチロールアクリルアミドを架
橋成分として含有するエマルジョン組成物が用いられて
いる分野においては、ホルマリン臭の発生しない硬化系
のエマルジョン組成物の開発が望まれている。Further, in an emulsion composition containing N-methylol acrylamide as a cross-linking component, in the cross-link formation (curing reaction) after coating the emulsion composition,
Formaldehyde is released from N-methylol acrylamide, which has a drawback that the formalin odor is intense in the use environment. In the field where an emulsion composition containing N-methylol acrylamide as a crosslinking component is used, no formalin odor is generated. Development of a curable emulsion composition is desired.
【０００７】[0007]
【課題を解決するための手段】そこで、本発明者らは、
特定の脂環式エポキシ基を有するビニル系単量体類を用
いることにより、架橋成分の含有量の多いエマルジョン
組成物を製造する場合においても乳化重合時のエマルジ
ョン組成物の重合安定性が良く、使用環境においてホル
マリン臭の発生しない硬化系のエマルジョン組成物を見
いだし、本発明を完成するに至った。Therefore, the present inventors have
By using vinyl monomers having a specific alicyclic epoxy group, the polymerization stability of the emulsion composition during emulsion polymerization is good even when an emulsion composition having a large content of a crosslinking component is produced, The present invention has been completed by finding out a curable emulsion composition that does not generate a formalin odor in a use environment.
【０００８】すなわち、本発明によれば、下記一般式
(I)That is, according to the present invention, the following general formula
(I)
【化２】 で表される脂環式エポキシ基を有するビニル系単量体類
を含有することを特徴とするエマルジョン組成物が提供
される。[Chemical 2] There is provided an emulsion composition comprising a vinyl-based monomer having an alicyclic epoxy group represented by:
【０００９】本発明のエマルジョン組成物は、上記一般
式(I)で表される脂環式エポキシ基を有するビニル系単
量体類、および、このビニル系単量体類と共重合可能な
ビニル系単量体類を、水性媒体中で乳化重合させること
により得られ、エマルジョン型塗料、接着剤、シーリン
グ剤、および、繊維処理剤などの各種用途において、上
記欠点を解決した新規なエマルジョン組成物を提供する
ものである。The emulsion composition of the present invention comprises a vinyl monomer having an alicyclic epoxy group represented by the general formula (I), and a vinyl copolymerizable with the vinyl monomer. A novel emulsion composition, which is obtained by emulsion-polymerizing a system monomer in an aqueous medium, and has solved the above-mentioned drawbacks in various applications such as emulsion-type paints, adhesives, sealing agents, and fiber treatment agents. Is provided.
【００１０】また、本発明のエマルジョン組成物は、水
性媒体中で乳化重合する以外に、前記一般式(I)で表さ
れる脂環式エポキシ基を有するビニル系単量体類、およ
び、このビニル系単量体類と共重合可能なビニル系単量
体類を重合または共重合して得られた重合体を水性媒体
中に分散させることによっても調整することができる。
本発明のエマルジョン組成物中の主要な成分である前
記一般式(I)で表される 脂環式エポキシ基を有するビニ
ル系単量体類のみをラジカル重合してもよいが、一般的
には、本発明のエマルジョン組成物中の主要な成分であ
る前記一般式(I) で表される脂環式エポキシ基を有する
ビニル系単量類と共重合可能なビニル系単量体類を共重
合してエマルジョン組成物を合成する。Further, the emulsion composition of the present invention comprises, in addition to emulsion polymerization in an aqueous medium, vinyl monomers having an alicyclic epoxy group represented by the general formula (I), and It can also be adjusted by polymerizing or copolymerizing vinyl monomers copolymerizable with vinyl monomers, and dispersing the polymer obtained in an aqueous medium.
Although only vinyl monomers having an alicyclic epoxy group represented by the general formula (I), which is the main component in the emulsion composition of the present invention, may be radically polymerized, , Copolymerizing vinyl monomers having alicyclic epoxy group represented by the general formula (I), which is a main component in the emulsion composition of the present invention, and copolymerizable vinyl monomers To synthesize an emulsion composition.
【００１１】本発明のエマルジョン組成物中の主要な成
分である前記一般式(I)で表される脂環式エポキシ基を
有するビニル系単量類と共重合可能なビニル系単量体類
としては、アクリル酸、メタクリル酸、マレイン酸、イ
タコン酸などの不飽和カルボン酸類、アクリル酸エステ
ル、メタクリル酸エステルなどの不飽和カルボン酸エス
テル類、ビニルエーテル類、および、スチレン誘導体な
どがある。As vinyl-based monomers copolymerizable with the vinyl-based monomers having an alicyclic epoxy group represented by the general formula (I), which is a main component in the emulsion composition of the present invention, Examples include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid, unsaturated carboxylic acid esters such as acrylic acid ester and methacrylic acid ester, vinyl ethers, and styrene derivatives.
【００１２】これらの少なくとも１種類以上の化合物を
本発明のエマルジョン組成物中の主要な成分である前記
一般式で表される脂環式エポキシ基を有するビニル系単
量類と共重合することができる。It is possible to copolymerize at least one of these compounds with a vinyl-based monomer having an alicyclic epoxy group represented by the above general formula, which is a main component in the emulsion composition of the present invention. it can.
【００１３】重合安定性および架橋成分の含有率から考
えると、一般式(I)で表される脂環式エポキシ基を有す
るビニル系単量体類は０．１〜５０重量部の範囲、さら
に０．２〜30重量部の範囲で用いるのが好ましい。０．
１重量部より含有量が少ないと、架橋度が充分でなく架
橋成分を含有することによる特徴がでず、また、５０重
量部より含有量が多くなると、重合安定性が悪くなるこ
とが多いので、好ましくない。Considering the polymerization stability and the content of the crosslinking component, the vinyl type monomers having an alicyclic epoxy group represented by the general formula (I) are in the range of 0.1 to 50 parts by weight, and further, It is preferably used in the range of 0.2 to 30 parts by weight. 0.
When the content is less than 1 part by weight, the degree of crosslinking is not sufficient and the characteristics due to the inclusion of the crosslinking component are not exhibited, and when the content is more than 50 parts by weight, the polymerization stability often deteriorates. , Not preferable.
【００１４】次に、本発明のエマルジョン組成物を得る
ための製造方法を詳しく説明する。本発明における乳化
重合方法としては、特に難しい技術は必要とせず、従来
から公知の合成技術を適用すれば充分であり、極めて容
易に行うことができる。Next, the production method for obtaining the emulsion composition of the present invention will be described in detail. The emulsion polymerization method of the present invention does not require a particularly difficult technique, and it is sufficient to apply a conventionally known synthesis technique, and it can be carried out very easily.
【００１５】代表的な方法を以下に記載する。A representative method is described below.
【００１６】まず、反応容器中に水および乳化剤を重合
性単量体の総量に対して０〜２％程度の濃度になるよう
に仕込む。First, water and an emulsifier are charged into a reaction vessel so that the concentration thereof is about 0 to 2% with respect to the total amount of polymerizable monomers.
【００１７】水の仕込み量は最終的なエマルジョン組成
物の固形分濃度によって変わるが、反応容器中に仕込む
水の量はエマルジョンに含まれる水の１０重量％を仕込
むと良い。また、最終的なエマルジョン組成物の固形分
濃度は７５重量％以下にするのが好ましい。The amount of water charged varies depending on the solid content concentration of the final emulsion composition, but the amount of water charged into the reaction vessel is preferably 10% by weight of water contained in the emulsion. The solid content concentration of the final emulsion composition is preferably 75% by weight or less.
【００１８】固形分濃度が７５％以上では重合中に粗大
粒子を形成しやすく、安定した重合が行いにくいので、
共に好ましくない。When the solid content concentration is 75% or more, coarse particles are easily formed during the polymerization, and stable polymerization is difficult to carry out.
Both are not preferable.
【００１９】引き続いて４０〜９５℃に昇温し、かつ、
攪拌しながら一般式(I)で表される脂環式エポキシ基を
有するビニル系単量類および共重合可能なビニル系単量
体類と乳化剤および水を用いてプレエマルション化した
ものを滴下する。Subsequently, the temperature is raised to 40 to 95 ° C., and
While stirring, a vinyl emulsion having an alicyclic epoxy group represented by the general formula (I) and a copolymerizable vinyl monomer, a pre-emulsion using an emulsifier and water are added dropwise. .
【００２０】重合開始剤は単量体類と同時に滴下しても
良いし、事前にプレエマルションに混合しておいても良
い。重合温度は使用される開始剤によっても異なるが、
一般には１００℃以下、特に５０〜９０℃の温度範囲が
好ましい。重合温度が１００℃以上では水が沸騰し、粗
大粒子を形成し易い。The polymerization initiator may be added dropwise at the same time as the monomers, or may be mixed in the pre-emulsion in advance. The polymerization temperature varies depending on the initiator used,
Generally, a temperature range of 100 ° C. or lower, particularly 50 to 90 ° C. is preferable. When the polymerization temperature is 100 ° C. or higher, water boils and coarse particles are easily formed.
【００２１】逆に５０℃未満では重合反応速度が遅くな
り、重合に長時間を要するので、共に好ましくない。On the other hand, if the temperature is lower than 50 ° C., the polymerization reaction rate becomes slow and the polymerization takes a long time.
【００２２】プレエマルションおよび重合開始剤の滴下
終了後、さらに少量の重合開始剤を添加して重合時と同
じ温度で２〜５時間反応させ、重合を停止させる。After the completion of dropping of the pre-emulsion and the polymerization initiator, a small amount of the polymerization initiator is further added and the reaction is carried out at the same temperature as the polymerization for 2 to 5 hours to terminate the polymerization.
【００２３】プレエマルション化に使用する乳化剤の量
は重合性単量体の総量に対して２〜８％程度の濃度にな
るように仕込む。使用する水は脱イオン水が好ましい。The amount of the emulsifier used for pre-emulsification is adjusted so as to have a concentration of about 2 to 8% with respect to the total amount of the polymerizable monomers. The water used is preferably deionized water.
【００２４】重合開始剤としては、過硫酸ソーダ、過硫
酸アンモニウムなどの過硫酸塩、過酸化水素のごとき過
酸化物、クメンハイドロパーオキサイドのごとき有機過
酸化物、またそれらの過酸化物と還元剤との組み合せに
よるレドックス系開始剤、などの周知の開始剤を用いる
ことができる。Examples of the polymerization initiator include persulfates such as sodium persulfate and ammonium persulfate, peroxides such as hydrogen peroxide, organic peroxides such as cumene hydroperoxide, and peroxides and reducing agents thereof. Well-known initiators such as redox-based initiators in combination with can be used.
【００２５】重合開始剤の使用量はモノマ−に対して通
常０．１〜２％、好ましくは、０．２〜１％である。The amount of the polymerization initiator used is usually 0.1 to 2%, preferably 0.2 to 1% with respect to the monomer.
【００２６】重合開始剤の使用量が０．１％より、少な
いと重合反応が進行しにくくなり、エマルジョン中の残
存モノマ−が多くなる。逆に２％より多いと重合度が上
がらず強度が出ないので好ましくない。When the amount of the polymerization initiator used is less than 0.1%, the polymerization reaction is difficult to proceed, and the amount of residual monomers in the emulsion increases. On the contrary, if it is more than 2%, the degree of polymerization does not increase and the strength does not appear, which is not preferable.
【００２７】乳化剤としては、従来この分野において公
知の各種ノニオン性界面活性剤単独あるいはアニオン性
界面活性剤との併用で充分である。As the emulsifier, it is sufficient to use various nonionic surfactants conventionally known in this field alone or in combination with the anionic surfactant.
【００２８】また、単量体類を重合または共重合して得
られた重合体を水性媒体中に分散させることによって調
整する場合は、まず、反応容器中に溶剤を仕込む。When the polymer obtained by polymerizing or copolymerizing the monomers is prepared by dispersing it in an aqueous medium, first, a solvent is charged into the reaction vessel.
【００２９】次いで、４０〜９０℃の温度範囲に加温、
かつ、攪拌しながら重合性単量体および重合開始剤を滴
下する。通常、重合の終点は残存する単量体の濃度を測
定しながら追跡し、通常は単量体類の濃度が１％未満に
なったところとする。Then, heating to a temperature range of 40 to 90 ° C.,
At the same time, the polymerizable monomer and the polymerization initiator are added dropwise with stirring. Usually, the end point of the polymerization is traced while measuring the concentration of the remaining monomer, and usually, it is taken as the point where the concentration of the monomers is less than 1%.
【００３０】次いで、５０〜９０℃の温度範囲を保持さ
れた別途調整した乳化剤水溶液を攪拌しながら重合体溶
液に添加する。Next, a separately adjusted aqueous emulsifier solution maintained in the temperature range of 50 to 90 ° C. is added to the polymer solution while stirring.
【００３１】重合体溶液の添加はエマルジョン組成物の
安定化保持の観点から滴下方式が好ましい。重合開始剤
や乳化剤の種類および使用濃度はエマルジョン重合する
際に使用する場合と同じでよい。The addition of the polymer solution is preferably a dropping method from the viewpoint of keeping the emulsion composition stable. The type and concentration of the polymerization initiator and the emulsifier may be the same as those used in emulsion polymerization.
【００３２】さらに、減圧下で脱溶剤して溶剤の含有量
を低下させても良い。Further, the solvent content may be reduced by removing the solvent under reduced pressure.
【００３３】次に実施例をあげて本発明を説明する。Next, the present invention will be described with reference to examples.
【００３４】［実施例１］コンデンサ−、攪拌機、還流
冷却器、窒素導入管を備えた反応器に、水８０重量部、
および、乳化剤（ワロラートｕ：東振化学社製品；エマ
ルゲン−１２０：花王社製品）１重量部を仕込み撹拌
し、７０℃まで昇温した。次に、一般式（化１）で表さ
れる脂環式エポキシ基を有するビニル系単量体（Ｒがメ
チル基、ｎが０）（以下、モノマーＡ１と示す）１０重
量部、ブチルアクリレート１８０重量部、メタクリル酸
１０重量部、水１２５重量部、乳化剤（ワロラートｕ：
東振化学社製品；エマルゲン−１２０：花王社製品）８
重量部、および、分子量調節剤（ｔ−ドデシルメルカプ
タン）０．０５重量部を乳化状態にしたものと、１０％
過硫酸アンモニウム水溶液５重量部を、２時間で滴下し
た。Example 1 A reactor equipped with a condenser, a stirrer, a reflux condenser, and a nitrogen inlet tube was charged with 80 parts by weight of water.
Then, 1 part by weight of an emulsifier (Walolato u: product of Toshin Chemical Co., Ltd .; Emulgen-120: product of Kao Corporation) was charged and stirred, and the temperature was raised to 70 ° C. Next, 10 parts by weight of a vinyl monomer having an alicyclic epoxy group represented by the general formula (Formula 1) (R is a methyl group, n is 0) (hereinafter referred to as a monomer A1), and butyl acrylate 180 Parts by weight, methacrylic acid 10 parts by weight, water 125 parts by weight, emulsifier (warolato u:
Toshin Chemical Co., Ltd. product; Emulgen-120: Kao Co. product) 8
10 parts by weight, and 0.05% by weight of a molecular weight regulator (t-dodecyl mercaptan) in an emulsified state.
5 parts by weight of an ammonium persulfate aqueous solution was added dropwise over 2 hours.
【００３５】この時の反応系内の温度は７０〜８０℃に
保った。滴下終了後、さらに、１０％過硫酸アンモニウ
ム水溶液２重量部を添加し、４時間反応系の温度を７０
〜８０℃に保ち固形分４９．５％のエマルジョン組成物
を得た。The temperature in the reaction system at this time was maintained at 70 to 80 ° C. After the completion of dropping, 2 parts by weight of 10% ammonium persulfate aqueous solution was further added, and the temperature of the reaction system was adjusted to 70% for 4 hours.
An emulsion composition having a solid content of 49.5% was obtained by keeping at -80 ° C.
【００３６】得られたエマルジョン組成物の性状を表
２．に示す。The properties of the resulting emulsion composition are shown in Table 2. Shown in.
【００３７】［実施例２〜４］表１．に示した条件で、
実施例１と同様に、各エマルジョンを合成し、性状を測
定した。[Examples 2 to 4] Table 1. Under the conditions shown in
Each emulsion was synthesized and the properties were measured in the same manner as in Example 1.
【００３８】［比較例１〜２］表１．に示した条件で、
実施例１と同様に、各エマルジョンを合成し、性状を測
定した。[Comparative Examples 1 and 2] Table 1. Under the conditions shown in
Each emulsion was synthesized and the properties were measured in the same manner as in Example 1.
【００３９】 表１/エマルジョンの合成 実施例 比較例 １ ２ ３ ４ １ ２ （反応器初期仕込） 水 ８０ ８０ ８０ ８０ ８０ ８０ 乳化剤 １ １ １ １ １ １ （モノマー乳化物） 水 １２５ １２５ １２５ １２５ １２５ １２５ 乳化剤 ８ ８ ８ ８ ８ ８ モノマーＡ１ １０ ５０ １０ − − − モノマーＡ２ − − − １０ − − ＧＭＡ − − − − １０ − Ｎ−ＭＡＮ − − − − − １０ ブチルアクリレート １００ １４０ １００ １８０ １８０ １００ スチレン ８０ − ８０ − − ８０ メタクリル酸 １０ １０ − １０ １０ １０ アクリル酸 − − １０ − − − 分子量調節剤 0.05 0.05 0.05 0.05 0.05 0.05 （重合開始剤） 10％過硫酸アンモニウム ５ ５ ５ ５ ５ ５ （反応条件） 反応温度 ７０℃ ７０℃ ８０℃ ７０℃ ７０℃ ７０℃ 滴下時間 ２時間 ２時間 ２時間 ２時間 ２時間 ２時間 熟成時間 ４時間 ４時間 ４時間 ４時間 ４時間 ４時間 （注１）モノマーＡ１：一般式(I)で表される脂環式エ
ポキシ基を有するビニル系単量体（Ｒがメチル基、ｎが
０） （注１）モノマーＡ２：一般式(I)で表される脂環式エ
ポキシ基を有するビニル系単量体（Ｒが水素原子、ｎが
０） また、表１中の略号は以下の通りである。Table 1 / Emulsion Synthesis Examples Comparative Example 1 2 3 4 1 2 (Initial Charge of Reactor) Water 80 80 80 80 80 80 80 Emulsifier 1 1 1 1 1 1 1 (Monomer Emulsion) Water 125 125 125 125 125 125 125 Emulsifier 8 8 8 8 8 8 Monomer A1 10 50 10 --- Monomer A2 --- --10 --- GMA --- --10 -N-MAN --- --- 10 Butyl acrylate 100 140 140 100 180 180 100 Styrene 80 -80--80 Methacrylic acid 1010-10101010 Acrylic acid--10 --- Molecular weight regulator 0.05 0.05 0.05 0.05 0.05 0.05 (Polymerization initiator) 10% Ammonium persulfate 5 5 5 5 5 5 (reaction conditions) Reaction Temperature 70 ° C 70 ° C 80 ° C 70 ° C 70 ° C 70 ° C Dropping time 2 hours 2 hours 2 hours Time 2 hours 2 hours 2 hours Aging time 4 hours 4 hours 4 hours 4 hours 4 hours 4 hours 4 hours (Note 1) Monomer A1: Vinyl monomer having alicyclic epoxy group represented by general formula (I) ( R is a methyl group, n is 0) (Note 1) Monomer A2: a vinyl monomer having an alicyclic epoxy group represented by the general formula (I) (R is a hydrogen atom, n is 0) The abbreviations in 1 are as follows.
【００４０】ＧＭＡ：グリシジルメタクリレート Ｎ−ＭＡＮ：Ｎ−メチロールアクリルアミド 表２/エマルジョンの性状 実施例 比較例 １ ２ ３ ４ １ ２ 固形分（％） 49.5 49.2 49.6 49.8 49.8 48.2 重合安定性（mg／１kg） 3.5 10.3 3.0 1.8 18.5 12.1機械安定性（mg／１kg） 410 859 357 405 3574 2350 （注） 重合安定性；重合終了時のグリッツ量［１ｋｇ
のエマルジョン中の２００メッシュろ過残さの重量（ｍ
ｇ）］で表示した。GMA: Glycidyl Methacrylate N-MAN: N-Methylolacrylamide Table 2 / Emulsion Properties Example Comparative Example 1 2 3 4 12 Solid content (%) 49.5 49.2 49.6 49.8 49.8 48.2 Polymerization stability (mg / 1 kg) 3.5 10.3 3.0 1.8 18.5 12.1 Mechanical stability (mg / 1kg) 410 859 357 405 3574 2350 (Note) Polymerization stability; Glitz amount at the end of polymerization [1kg
Weight of 200 mesh filtration residue in the emulsion of (m
g)].
【００４１】機械安定性；測定条件、試料５０ｇをマー
ロン測定機に入れ、１５ｋｇ/ｃｍ2圧下、１０００ｒｐ
ｍで１５分間試験した後、グリッツ量を測定した。Mechanical stability: Measuring conditions: 50 g of a sample was put in a Marlon measuring machine, and under a pressure of 15 kg / cm 2 , 1000 rp
After testing for 15 minutes at m, the amount of gritz was measured.
【００４２】《応用例》実施例１および比較例２で得ら
れたエマルジョンを用いて製造直後、室温６ケ月保存後
の各時点で繊維加工用バインダ−としての性能試験を行
なった。<Application Example> Using the emulsions obtained in Example 1 and Comparative Example 2, a performance test as a binder for fiber processing was conducted immediately after production and after storage for 6 months at room temperature.
【００４３】＜フロック加工用性能試験＞ （加工布の作製条件）バインダ−に28%アンモニア水を
添加して粘度25000cps調整し、これをドクタ−ナイフに
よりレ−ヨンスフ綾９Ａ上に塗布量200g/ｍ2になる用に
均一に塗布し、ただちに電気植毛を用いて電圧30KV、極
間距離10ｃｍで1.5デニ−ル、0.6ｍｍのレ−ヨンパイル
を植毛した。次いで、110℃で10分間加熱乾燥し、冷却
後余剰の パイルを除去した。<Performance test for flocking> (Conditions for manufacturing working cloth) 28% ammonia water was added to a binder to adjust the viscosity to 25000 cps, and this was coated on a rayon cloth 9A with a doctor knife to a coating amount of 200 g / It was evenly applied to obtain m 2 and immediately, using electric flocking, flocking of rayon pile of 0.6 mm with 1.5 denier at a voltage of 30 KV and a distance between electrodes of 10 cm. Then, it was dried by heating at 110 ° C. for 10 minutes, and after cooling, the excess pile was removed.
【００４４】（耐磨耗性試験）学振型染色磨耗堅牢度試
験機を用いてJIS-L-1084 45R法にしたがって試験した。
水湿潤時耐磨耗性は試験片を水中に15分間浸漬した
後、湿潤状態で、パ−クレン湿潤時耐磨耗性は試験片を
パ−クレン中に15分間浸漬した後、湿潤状態で夫々試験
した。耐磨耗性はパイルが脱落して基布表面が露出する
までの摩擦回数で判定し、以下の表３に記載した。(Abrasion resistance test) Tests were performed according to JIS-L-1084 45R method using a Gakushin type dyeing abrasion fastness tester.
Abrasion resistance when wet with water is in a wet state after the test piece is immersed in water for 15 minutes, and abrasion resistance when wet with percren is in a wet state after the test piece is immersed in percrene for 15 minutes. I tested each one. The abrasion resistance was judged by the number of times of friction until the pile fell off and the surface of the base cloth was exposed, and is shown in Table 3 below.
【００４５】 表３ フロック加工 耐磨耗性（回数） Ａ Ｂ Ｃ Ｄ 繊維加工用バインダ−（実施例１で得られたエマルジョン） 製造直後 なし >1000 >1000 >1000 室温６ケ月保存後 なし >1000 880 750繊維加工用バインダ−（比較例２で得られたエマルジョン） 製造直後 有り >1000 >1000 >1000 室温６ケ月保存後 有り >1000 850 730 表３において、Ａは加工時ホルマリン臭気の有無、Ｂは
常温、Ｃは水湿潤時、Ｄはそれぞれパ−クレン湿潤時の
摩擦回数である。[0045] Table 3 flocking abrasion resistance (number) A B C D Fibers machining binder - (emulsion obtained in Example 1) None Immediately after Manufacturing> 1000>1000> 1000 RT 6 months without after storage> 1000 880 750 Textile processing binder (emulsion obtained in Comparative Example 2) Immediately after production >1000>1000> 1000 After storage at room temperature for 6 months Yes> 1000 850 730 In Table 3, A indicates presence or absence of formalin odor during processing, B Is the normal temperature, C is the number of times of rubbing when wet with water, and D is the number of times of rubbing when wet with parklen.
【００４６】[0046]
【発明の効果】本発明のエマルジョン組成物を繊維加工
用バインダ−として使用すれば従来から使用されている
Ｎ−メチロールアクリルアミドと同程度ないしはそれ以
上の耐磨耗性を有し、かつ、ホルムアルデヒドが発生し
ないため、作業環境が改善される。（以下余白）When the emulsion composition of the present invention is used as a binder for fiber processing, it has abrasion resistance equal to or higher than that of N-methylol acrylamide conventionally used, and formaldehyde The work environment is improved because it does not occur. (Below margin)
Claims (3)
たは正の整数を示す。》で表される脂環式エポキシ基を
有するビニル系単量体類を重合または共重合して得られ
ることを特徴とするエマルジョン組成物。1. The following general formula (I): << R represents a methyl group or a hydrogen atom. n represents zero or a positive integer. ] An emulsion composition obtained by polymerizing or copolymerizing vinyl monomers having an alicyclic epoxy group represented by.
を有するビニル系単量体類０．１〜５０重量部、一般式
(I)で表される脂環式エポキシ基を有するビニル系単量
体類と共重合可能なビニル系単量体類５０〜９９．９重
量部を、共重合して得られることを特徴とするエマルジ
ョン組成物。2. 0.1 to 50 parts by weight of a vinyl-based monomer having an alicyclic epoxy group represented by the general formula (I),
50 to 99.9 parts by weight of vinyl-based monomers copolymerizable with the vinyl-based monomers having an alicyclic epoxy group represented by (I), obtained by copolymerization. Emulsion composition.
を有するビニル系単量体類、および、このビニル系単量
体類と共重合可能なビニル系単量体類を、水性媒体中で
乳化重合させることを特徴とする請求項１のエマルジョ
ン組成物の製造方法。3. A vinyl-based monomer having an alicyclic epoxy group represented by the general formula (I), and vinyl-based monomers copolymerizable with the vinyl-based monomer, The method for producing an emulsion composition according to claim 1, wherein the emulsion polymerization is carried out in an aqueous medium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12108894A JPH0753635A (en) | 1993-06-07 | 1994-06-02 | Emulsion composition and its production |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5-135742 | 1993-06-07 | ||
| JP13574293 | 1993-06-07 | ||
| JP12108894A JPH0753635A (en) | 1993-06-07 | 1994-06-02 | Emulsion composition and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0753635A true JPH0753635A (en) | 1995-02-28 |
Family
ID=26458539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12108894A Pending JPH0753635A (en) | 1993-06-07 | 1994-06-02 | Emulsion composition and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0753635A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998051718A1 (en) * | 1997-05-15 | 1998-11-19 | Nippon Steel Chemical Co., Ltd. | Alkali-soluble resins and image-forming material prepared by using the same |
| US7485239B2 (en) | 2002-08-06 | 2009-02-03 | Kobe Steel, Ltd | Component of glass-like carbon for CVD apparatus and process for production thereof |
-
1994
- 1994-06-02 JP JP12108894A patent/JPH0753635A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998051718A1 (en) * | 1997-05-15 | 1998-11-19 | Nippon Steel Chemical Co., Ltd. | Alkali-soluble resins and image-forming material prepared by using the same |
| US7485239B2 (en) | 2002-08-06 | 2009-02-03 | Kobe Steel, Ltd | Component of glass-like carbon for CVD apparatus and process for production thereof |
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