KR100477343B1 - Water-based colored resin and their use - Google Patents
Water-based colored resin and their use Download PDFInfo
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- KR100477343B1 KR100477343B1 KR10-2002-0018007A KR20020018007A KR100477343B1 KR 100477343 B1 KR100477343 B1 KR 100477343B1 KR 20020018007 A KR20020018007 A KR 20020018007A KR 100477343 B1 KR100477343 B1 KR 100477343B1
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Abstract
본 발명은 착색 수지용 수성 분산체와 이를 이용한 수분산 착색 수지에 관한 것으로, 더욱 상세하게는 수성 분산체로 내수성, 내광성 등이 우수한 말레산 모노(메타)아크릴에스테르와 상기와 공중합 가능한 에틸렌성 불포화 단량체를 유화중합시켜 얻은 유화 중합체를 사용하고, 여기에 염료를 착색시켜 수분산 착색 수지를 제조함으로써, 내수성, 내약품성, 내용제성 및 내광성이 매우 우수하고 장기 저장안정성이 뛰어난 착색 수지용 수성 분산체와 이를 이용한 수분산 착색 수지에 관한 것이다.The present invention relates to an aqueous dispersion for a colored resin and a water-dispersible colored resin using the same, and more particularly, to an aqueous dispersion, a maleic acid mono (meth) acrylic ester having excellent water resistance and light resistance and an ethylenically unsaturated monomer copolymerizable with the above. By using the emulsion polymer obtained by the emulsion polymerization, and dyeing the dye therein to prepare a water-dispersible colored resin, the aqueous dispersion for colored resin having excellent water resistance, chemical resistance, solvent resistance and light resistance and excellent long-term storage stability and It relates to a water-dispersible colored resin using the same.
Description
본 발명은 착색 수지용 수성 분산체와 이를 이용한 수분산 착색 수지에 관한 것으로, 더욱 상세하게는 수성 분산체로 내수성, 내광성 등이 우수한 말레산 모노(메타)아크릴에스테르와 상기와 공중합 가능한 에틸렌성 불포화 단량체를 유화중합시켜 얻은 유화 중합체를 사용하고, 여기에 염료를 착색시켜 수분산 착색 수지를 제조함으로써, 내수성, 내약품성, 내용제성 및 내광성이 매우 우수하고 장기 저장안정성이 뛰어난 착색 수지용 수성 분산체와 이를 이용한 수분산 착색 수지에 관한 것이다.The present invention relates to an aqueous dispersion for a colored resin and a water-dispersible colored resin using the same, and more particularly, to an aqueous dispersion, a maleic acid mono (meth) acrylic ester having excellent water resistance and light resistance and an ethylenically unsaturated monomer copolymerizable with the above. By using the emulsion polymer obtained by the emulsion polymerization, and dyeing the dye therein to prepare a water-dispersible colored resin, the aqueous dispersion for colored resin having excellent water resistance, chemical resistance, solvent resistance and light resistance and excellent long-term storage stability and It relates to a water-dispersible colored resin using the same.
종래의 인쇄용 잉크 및 필기구용 수성 잉크는 무기계의 수분산 안료나 유기계의 수용성 염료 등으로 수성 폴리머 수지를 착색하거나 수용성 폴리머에 분산시켜 사용하여 왔다. 그러나, 무기계의 수분산 안료는 볼밀(Ball mill)이나 샌드밀(Sand mill)로 수분산 안료를 미세하게 분산하는 복잡한 공정이 필요하고, 경시적으로 분산 안료가 응집 또는 침전하는 현상이 있으므로 사용에 문제점이 있어 왔다. 또한, 수용성 유기 염료는 수분산 안료와 비교하여 색상이 진하고, 색상의 선명도가 우수하지만, 염료 자체가 수용성이기 때문에 내수성이 약한 단점이 있고, 더구나 내광성이 약하여 기록지의 장기 보관시 색상이 소색 또는 변색하는 단점이 있다.Conventional printing inks and water-based inks for writing instruments have been used by coloring an aqueous polymer resin or dispersing it in a water-soluble polymer with an inorganic water-based pigment or an organic water-soluble dye. However, the inorganic water-based pigments require a complicated process of finely dispersing the water-disperse pigments in a ball mill or sand mill, and the pigments disperse or precipitate over time. There has been a problem. In addition, water-soluble organic dyes have a darker color and superior color clarity than water-disperse pigments, but have a disadvantage in that water resistance is weak because the dyes themselves are water-soluble, and furthermore, due to their poor light resistance, the color may be discolored or discolored during long-term storage of recording paper. There is a disadvantage.
이러한 수용성 염료의 단점을 극복하기 위하여 공중합체 라텍스에 염료를 흡착시키는 방법들이 제안되어 왔다. 예를 들면, 일본 특허공고 평 5-62629호에서는 스티렌, 아크릴로니트릴, 메타크릴산 공중합체 라텍스에 형광 염료를 착색시키는 방법이 개시되어 있다. 상기 방법에 따른 잉크 조성물은 문구류의 감압 감열 기록지에 유용한 잉크로 되어 있으나, 공중합체의 가교성의 결여로 내수성, 내약품성, 내용제성이 열악하다. 또한, 공중합체 라텍스에 염료를 흡착시키는 방법으로 일본 특허공개 평 4-7367호에서는 메타크릴산 메틸, 메타크릴로니트릴, 메타크릴산 글리시딜, 메타크릴산을 함유한 착색 수지의 수성 분산체의 잉크 조성물이 개시되어 있다. 상기 잉크 조성물은 내알칼리성, 내용제성이 매우 열악할 뿐만 아니라 독극물로 지정된 메타크릴로니트릴을 착색 성분으로 사용하며, 또한 경제성에도 문제가 있다. 그리고, 반응성 단량체인 메타크릴산 글리시딜을 가교제로 사용하였으나 경제성 및 저장 안정성에 문제가 있다. 일본 특허공개 평 5-255567호에는 공액디엔계 단량체를 유화 중합하여 된 종입자에 시아노기, 카복실기, 글리시딜기를 갖는 에틸렌성 불포화 단량체를 유화중합하여 착색한 착색 수지의 잉크가 개시되어 있다. 상기 잉크의 경우에는 공액디엔계 단량체를 사용하여 입자 비중을 줄이고 저장안정성을 향상시켰으나, 2 단계의 중합의 공정이 번잡하여 경제성이 결여된 단점이 있다. In order to overcome the disadvantages of such water-soluble dyes, methods of adsorbing dyes on copolymer latexes have been proposed. For example, Japanese Patent Laid-Open No. 5-62629 discloses a method of coloring a fluorescent dye on styrene, acrylonitrile, and methacrylic acid copolymer latex. The ink composition according to the above method is an ink useful for pressure-sensitive heat-sensitive recording paper of stationery, but poor water resistance, chemical resistance, and solvent resistance due to the lack of crosslinkability of the copolymer. In addition, in Japanese Patent Application Laid-open No. Hei 4-7367, a method of adsorbing a dye to a copolymer latex, an aqueous dispersion of colored resin containing methyl methacrylate, methacrylonitrile, glycidyl methacrylate, and methacrylic acid An ink composition of is disclosed. The ink composition is not only very poor in alkali resistance and solvent resistance but also uses methacrylonitrile designated as a poison as a coloring component, and also has problems in economic efficiency. In addition, although glycidyl methacrylate, which is a reactive monomer, was used as a crosslinking agent, there is a problem in economy and storage stability. Japanese Patent Application Laid-Open No. 5-255567 discloses an ink of a colored resin obtained by emulsion-polymerizing and coloring an ethylenically unsaturated monomer having a cyano group, a carboxyl group, and a glycidyl group in a seed particle obtained by emulsion polymerization of a conjugated diene monomer. . In the case of the ink, the conjugated diene-based monomer is used to reduce the specific gravity of particles and improve storage stability. However, the two-stage polymerization process is complicated, and thus, there is a disadvantage in lack of economic efficiency.
미국특허 제5,942,560호, 미국특허 제5,721,313호, 미국특허 제5,294,664호, 미국특허 제4,623,689호 등에는 중합성 계면활성제를 사용하여 입자 표면에 음이온성기를 갖는 폴리머 에멀젼에 양이온 염료를 이용하여 착색한 방법이 개시되어 있다. 이 잉크 조성물은 양이온 염료의 결합과 폴리머 자체의 분산 안정성을 주기 위하여 충분한 양의 중합성 계면활성제를 사용하여야 하지만 가격면에서 유리하지 않다. 또한, 음이온성 염료의 경우는 착색이 어려우므로 사용할 수 있는 염료의 종류와 색수가 제한되어 있다. U.S. Patent No. 5,942,560, U.S. Patent 5,721,313, U.S. Patent 5,294,664, U.S. Patent 4,623,689, etc., use a polymerizable surfactant to color a polymer emulsion having an anionic group on the surface of the particle using a cationic dye. Is disclosed. This ink composition must use a sufficient amount of polymerizable surfactant to give the bond of the cationic dye and the dispersion stability of the polymer itself, but is not cost effective. In addition, in the case of anionic dyes, since coloring is difficult, the kind and color number of dyes which can be used are limited.
그리고, 일본 특허공개 평 6-228487호에서는 반 에스테르화 된 스티렌-말레산 수지를 잉크 조성물로 사용한 것이 개시되어 있고, 미국특허 제5,880,238호에는 폴리에틸렌 글리콜 모노에테르의 반 에스테르화된 무수 말레산과 스티렌과 아크릴산의 공중합 수지를 잉크로 사용한 예가 개시되어 있으며, 일본 특허공개 평 8-314137호에서는 시판되는 스티렌-말레산 수지를 히드록시기를 갖는 (메타)아크릴로일기를 갖는 단량체와 반응시켜 얻는 반 에스테르화 된 스틸렌-말레산 수지를 다른 비닐 단량체들과 공중합하여 잉크 조성물로 사용한 것이 개시되어 있다. 상기와 같이 공중합체 라텍스에 염료를 흡착시키는 방법들 또한 내용제성, 내알칼리성에 문제가 있고, 감열지나 감압지에서 소색이나 변색이 발생하는 문제가 있었다.Japanese Patent Application Laid-Open No. 6-228487 discloses the use of a semi-esterified styrene-maleic acid resin as an ink composition, and US Patent No. 5,880,238 discloses a semi-esterified maleic anhydride and styrene of polyethylene glycol monoether. Examples of using an acrylic copolymer resin as an ink are disclosed, and Japanese Patent Application Laid-open No. Hei 8-314137 discloses a semi-esterified product obtained by reacting a commercially available styrene-maleic acid resin with a monomer having a (meth) acryloyl group having a hydroxyl group. Copolymerization of styrene-maleic resin with other vinyl monomers is disclosed as an ink composition. As described above, the method of adsorbing the dye on the copolymer latex also has a problem in solvent resistance and alkali resistance, and there is a problem that discoloration or discoloration occurs in thermal paper or pressure-sensitive paper.
이에, 본 발명자들은 상기와 같은 문제점을 해결하기 위하여 수성 분산체로 내수성, 내광성 등이 우수한 물성을 가진 말레산 모노(메타)아크릴에스테르와 상기 말레산 모노(메타)아크릴에스테르와 공중합 가능한 에틸렌성 불포화 단량체를 유화중합시켜 얻은 유화 중합체를 사용하고, 여기에 염료를 착색시켜 수분산 착색 수지를 제조함으로써, 본 발명을 완성하였다.Accordingly, the inventors of the present invention are ethylenically unsaturated monomers copolymerizable with maleic mono (meth) acrylic ester and maleic acid mono (meth) acrylic ester having an excellent water resistance and light resistance as an aqueous dispersion in order to solve the above problems. The present invention was completed by coloring an dye thereto using an emulsion polymer obtained by emulsion polymerization to produce an aqueous dispersion colored resin.
따라서, 본 발명은 가교제 및 산성관능기로 물성이 우수한 말레산의 모노(메타)아크릴에스테를 사용함으로써 내수성, 내광성, 내약품성, 내용제성 및 저장 안정성 등의 물성이 우수하고, 색조가 선명하고, 장기 저장안정성이 뛰어나 열경화성을 갖고 있는 염료 등의 분야에 유용하게 사용할 수 있는 착색 수지의 수성 분산체 및 이를 이용한 착색 수지를 제공하는데 그 목적이 있다. Therefore, the present invention is excellent in physical properties such as water resistance, light resistance, chemical resistance, solvent resistance and storage stability by using a mono (meth) acrylic ester of maleic acid having excellent physical properties as a crosslinking agent and an acidic functional group, clear color tone, long term It is an object of the present invention to provide an aqueous dispersion of colored resin that can be usefully used in fields such as dyes having excellent storage stability and thermosetting properties, and colored resins using the same.
다음 화학식 1로 표시되는 말레산 모노(메타)아크릴에스테르와 에틸렌성 불포화 단량체를 유화중합시켜 얻은 유화중합체인 것임을 특징으로 하는 착색 수지용 수성 분산체.The aqueous dispersion for colored resins characterized in that it is an emulsion polymer obtained by emulsion-polymerizing maleic acid mono (meth) acrylic ester represented by following General formula (1) and ethylenically unsaturated monomer.
상기 화학식 1에서, R은 수소원자 또는 C1 ∼ C6의 알킬기이고, n은 1 ∼ 3의 정수이다.In Formula 1, R is a hydrogen atom or an alkyl group of C 1 to C 6 , n is an integer of 1 to 3.
이와같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
본 발명은 말레산 모노(메타)아크릴에스테르를 가교제 및 산성 관능기로 사용하여 에틸렌성 불포화 단량체와 유화중합시켜 얻은 유화 중합체를 착색 수지용 수성 분산체로 사용하고, 여기에 염료를 착색시켜 착색 수지를 제조함으로써 내수성, 내약품성, 내용제성 및 내광성이 매우 우수하고 장기 저장안정성이 뛰어나 인쇄잉크, 필기구용 잉크, 마킹펜용 잉크, 날염 및 수성 도료에 유용한 착색 수지용 수성 분산체와 이를 이용한 수분산 착색 수지에 관한 것이다.The present invention uses an emulsion polymer obtained by emulsion polymerization of an ethylenically unsaturated monomer using a maleic acid mono (meth) acrylic ester as a crosslinking agent and an acidic functional group as an aqueous dispersion for coloring resin, and coloring the dye therein to produce a coloring resin. It is excellent in water resistance, chemical resistance, solvent resistance and light resistance, and excellent in long-term storage stability.It is suitable for printing dispersions, ink for writing instruments, marking pen inks, printing dispersions and aqueous dispersions for coloring resins which are useful for water-based paints and water-dispersible coloring resins using the same. It is about.
본 발명의 수성 분산체에서 가교제 및 산성관능기로 사용되는 상기 화학식 1로 표시되는 말레산 모노(메타)아크릴에스테르는 무수 말레산 또는 말레산과 분자중에 적어도 1개의 히드록시기 및 (메타)아크릴로일기를 갖는 에틸렌성 불포화 단량체를 반응시켜 얻는다. 이때, 상기 분자중에 적어도 1개의 히드록시기 및 (메타)아크릴로일기를 갖는 에틸렌성 불포화 단량체로는 예컨대 2-히드록시에틸 (메타)아크릴레이트, 3-히드록시프로필 (메타)아크릴레이트, 4-히드록시부틸 (메타)아크릴레이트, 폴리에틸렌글리콜 (메타)아크릴레이트, 폴리프로필렌글리콜 (메타)아크릴레이트, 폴리카프로락톤 (메타)아크릴레이트, 펜타에리트리톨 (메타)아크릴레이트, 트리메틸올프로판 (메타)아크릴레이트, 네오펜틸 글리콜 (메타)아크릴레이트, 1,6-헥산디올 (메타)아크릴레이트, 글리세롤 (메타)아크릴레이트, 2-히드록시 디에틸 (메타)아크릴레이트, 폴리부틸렌글리콜 (메타)아크릴레이트, 디펜타에리트리톨 (메타)아크릴레이트, 글리시딜 메타크릴레이트, 글리시딜 아크릴레이트 등을 사용할 수 있다. 즉, 상기 말레산 모노(메타)아크릴에스테르는 말레산 또는 무수말레산과 히드록시기를 갖는 상기 단량체와의 개환 부가 반응 또는 통상의 에스테르화 반응에 의해 제조할 수 있으며, 바람직하게는 개환 부가 반응에 의해 제조하는 것이 좋다. 이때, 상기 말레산 또는 무수 말레산과 분자중에 적어도 1개의 히드록시기 및 (메타)아크릴로일기를 갖는 에틸렌성 불포화 단량체의 몰비는 1:1 ∼ 1:2가 바람직하나, 더욱 바람직하게는 1: 1.1 ∼ 1: 1.5 몰비의 범위가 좋다. 만일, 상기 반응비가 1:1 몰비 미만이면 미반응 말레산 또는 무수 말레산이 많아서 산가가 너무 높아지는 문제가 있고, 1:2 몰비를 초과하면 친수성의 에틸렌성 불포화 단량체가 많아서 유화에 문제가 있다. 상기 말레산 모노(메타)아크릴에스테르를 얻기 위한 개환 부가 반응은 통상 40 ℃ 내지 200 ℃에서 행하는 것이 가능하지만, 디에스테르의 생성 및 겔화를 방지하기 위하여 무수 말레산의 녹는점인 50 ℃ 내지 70 ℃ 에서 30분 내지 18 시간 반응시키는 것으로 충분하다. 또한, 당량 반응의 경우에는 무용제 상태에서 반응시키는 것이 바람직하나 과량의 히드록시기를 갖는 에틸렌성 불포화 단량체를 사용하여 용제를 대신 할 수도 있다. 반응의 진행은 적외선 스펙트럼에 의해 산무수물의 감소를 추적할 수도 있고, 프로톤 핵자기공명 스펙트럼에 의한 확인도 가능하다. 이때, 반응 촉진제로서 트리에틸 아민, 모포린, 펜타메틸 디메틸아민 등의 3급 아민류, 4급 암모늄염을 촉매로 사용하는 것도 가능하다. 또한 공지인 중합 금지제를 사용하여 반응중에 중합물이 생성됨을 방지하는 것도 가능하다.The maleic acid mono (meth) acrylic ester represented by Formula 1 used as a crosslinking agent and an acidic functional group in the aqueous dispersion of the present invention has maleic anhydride or maleic anhydride and at least one hydroxy group and (meth) acryloyl group in the molecule. Obtained by reacting ethylenically unsaturated monomer. At this time, as the ethylenically unsaturated monomer having at least one hydroxy group and (meth) acryloyl group in the molecule, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy Roxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polycaprolactone (meth) acrylate, pentaerythritol (meth) acrylate, trimethylolpropane (meth) acrylic Latex, neopentyl glycol (meth) acrylate, 1,6-hexanediol (meth) acrylate, glycerol (meth) acrylate, 2-hydroxy diethyl (meth) acrylate, polybutylene glycol (meth) acrylic Latent, dipentaerythritol (meth) acrylate, glycidyl methacrylate, glycidyl acrylate and the like can be used. That is, the maleic acid mono (meth) acrylic ester may be prepared by ring-opening addition reaction or normal esterification reaction of maleic acid or maleic anhydride with the monomer having a hydroxy group, preferably by ring-opening addition reaction. Good to do. At this time, the molar ratio of the maleic acid or maleic anhydride and the ethylenically unsaturated monomer having at least one hydroxy group and (meth) acryloyl group in the molecule is preferably 1: 1 to 1: 2, more preferably 1: 1.1 to The range of 1: 1.5 molar ratio is good. If the reaction ratio is less than 1: 1 molar ratio, the amount of unreacted maleic acid or maleic anhydride is too high, and the acid value is too high. If the ratio is more than 1: 2 molar ratio, there are many hydrophilic ethylenically unsaturated monomers. The ring-opening addition reaction for obtaining the maleic acid mono (meth) acrylic ester can usually be carried out at 40 ° C to 200 ° C, but in order to prevent the formation and gelation of diesters, the melting point of maleic anhydride is 50 ° C to 70 ° C. It is sufficient to react for 30 minutes to 18 hours at. In addition, in the case of an equivalent reaction, it is preferable to make it react in a solventless state, but it can also replace a solvent using the ethylenically unsaturated monomer which has an excess hydroxyl group. The progress of the reaction can be traced to the reduction of acid anhydride by the infrared spectrum, or can be confirmed by the proton nuclear magnetic resonance spectrum. At this time, it is also possible to use tertiary amines, such as triethyl amine, morpholine, pentamethyl dimethylamine, and quaternary ammonium salts as a catalyst for the reaction. It is also possible to use known polymerization inhibitors to prevent the formation of polymers during the reaction.
본 발명은 상기와 같은 말레산 모노(메타)아크릴에스테르를 가교제 및 산성관능기로 사용하여 착색수지를 가교 시킴으로써 내용제성, 내약품성을 강화시키는 외에도 염료의 착색, 잉크의 선명도 및 지류와의 접착력을 갖게 하는 성분으로 사용하는데 그 특징이 있다. 종래 착색 수지에서는 카복실기 함유 단량체로서 메타크릴산이나 아크릴산 등의 모노 카복실산을 염료의 발색성 및 선명성을 향상시키는 성분으로서 많이 사용하고 있지만, 친수성으로 라텍스의 안정성이나 물성의 저하를 주는 요인으로 사용량에 한계가 있다. 그러나, 본 발명에서 사용하는 말레산 모노(메타)아크릴에스테르는 가교제로서 물성을 강인하게 하고, 소수성이므로 라텍스의 에멀젼이 보다 안정한 특징을 가지고 있다. 이러한 특징을 가지는 말레산의 모노(메타)아크릴에스테르는 전체 수성 분산체 중에 1 ∼ 20 중량% 함유하는 것이 바람직하며, 더욱 바람직하게는 5 ∼ 15 중량% 함유하는 것이 좋다. 만일, 그 함유량이 1 중량% 미만이면 가교 효과가 적어 내용제성, 내약품성이 나빠지고, 색상의 선명도가 나빠지게 되며, 20 중량%를 초과하면 과도한 가교결합으로 입자가 너무 커지거나, 안정된 유화 중합체를 얻는 것이 곤란하다.The present invention crosslinks the colored resin using the maleic acid mono (meth) acrylic ester as a crosslinking agent and an acidic functional group to enhance solvent resistance and chemical resistance, and to have coloring of dyes, clarity of ink, and adhesion to tributaries. It is used as an ingredient to have its characteristics. Conventionally, in colored resins, monocarboxylic acids such as methacrylic acid and acrylic acid are frequently used as carboxyl group-containing monomers as components for improving color development and clarity of dyes. There is. However, the maleic acid mono (meth) acrylic ester used in the present invention has strong physical properties as a crosslinking agent and is hydrophobic, so that the emulsion of latex has more stable characteristics. It is preferable to contain 1-20 weight% of mono (meth) acrylic ester of maleic acid which has such a characteristic in the whole aqueous dispersion, More preferably, it is preferable to contain 5-15 weight%. If the content is less than 1% by weight, the crosslinking effect is low, so that the solvent resistance and chemical resistance are poor, and the vividness of the color is deteriorated. When the content is more than 20% by weight, the particles become too large due to excessive crosslinking, or a stable emulsion polymer. Is difficult to get.
그리고, 본 발명에 따른 수성 분산체를 얻기위해 상기 화학식 1로 표시되는 말레산 모노(메타)아크릴에스테르와 공중합 가능한 에틸렌성 불포화 단량체로는 시아노기 함유 에틸렌성 불포화 단량체, 히드록시기를 갖는 에틸렌성 불포화 단량체 및 상기와 공중합 가능한 스티렌계 또는 (메타)아크릴레이트계 에틸렌성 불포화 단량체를 사용할 수 있다. In addition, the ethylenically unsaturated monomer copolymerizable with the maleic acid mono (meth) acrylic ester represented by Formula 1 to obtain an aqueous dispersion according to the present invention is a cyano group-containing ethylenically unsaturated monomer, an ethylenically unsaturated monomer having a hydroxy group. And styrene-based or (meth) acrylate-based ethylenically unsaturated monomers copolymerizable with the above.
상기 시아노기 함유 에틸렌성 불포화 단량체는 폴리머의 주위 환경에 극성을 주고 염료의 흡착을 도와 착색 수지의 색을 선명하게 하고 내광성을 향상시키는 성분으로 사용되며, 예컨대 아크릴로니트릴 또는 메타크릴로니트릴을 사용할 수 있으며, 바람직하게는 아크릴로니트릴을 사용하는 것이 좋다. 상기 시아노기 함유 에틸렌성 불포화 단량체는 전체 수성 분산체 중에 10 ∼ 35 중량% 함유하는 것이 바람직하며, 만일 그 함유량이 10 중량% 미만이면 착색 수지의 내광성이 나쁘고 선명하지 않고, 35 중량%를 초과하면 유화 중합체 제조시 중합 반응이 나빠지게 되고, 입자내의 공중합성도 열악하기 때문에 품질적인 관리가 어려우며, 친수성이 커서 오리고무가 발생하기 쉽다.The cyano group-containing ethylenically unsaturated monomer is used as a component that gives polarity to the surrounding environment of the polymer and helps the adsorption of dyes to brighten the color of the colored resin and improve the light resistance. For example, acrylonitrile or methacrylonitrile may be used. It is preferable to use acrylonitrile. The cyano group-containing ethylenically unsaturated monomer is preferably contained in 10 to 35% by weight in the total aqueous dispersion, if the content is less than 10% by weight if the light resistance of the colored resin is bad and not clear, if it exceeds 35% by weight In the production of emulsion polymers, the polymerization reaction becomes poor, and the copolymerization in the particles is also poor, so that quality control is difficult and hydrophilicity is large, and thus, rubber is likely to occur.
상기 히드록시기를 갖는 에틸렌성 불포화 단량체는 본 발명의 수성 분산체에서 염료와 단량체의 혼합 매개체로, 시아노기 함유 에틸렌성 불포화단량체의 호모 폴리머의 생성을 방지하기 위하여, 또는 유화 중합시 빈번히 발생하는 오리 고무화를 막기 위하여 사용하며, 예컨대 2-히드록시에틸 (메타)아크릴레이트, 3-히드록시프로필 (메타)아크릴레이트, 4-히드록시부틸 (메타)아크릴레이트, 폴리에틸렌글리콜 (메타)아크릴레이트, 폴리프로필렌글리콜 (메타)아크릴레이트, 펜타에리트리톨 (메타)아크릴레이트, 트리메틸올프로판 (메타)아크릴레이트, 네오펜틸 글리콜 (메타)아크릴레이트, 1,6-헥산디올 (메타)아크릴레이트, 글리세롤 (메타)아크릴레이트, 2-히드록시 디에틸 (메타)아크릴레이트, 폴리부틸렌글리콜 (메타)아크릴레이트, 디펜타에리트리톨 (메타)아크릴레이트 등을 사용할 수 있다. 이러한 히드록시기를 갖는 친수성 에틸렌성 불포화 단량체는 전체 수성 분산체 중에 0 ∼ 10 중량% 함유하는 것이 바람직하며, 특히 상기 화학식 1로 표시되는 말레산 모노(메타)아크릴에스테르의 제조시 과량의 히드록시기를 갖는 에틸렌성 불포화 단량체를 사용시에는 첨가하지 않을 수도 있으나 통상 1 ∼ 8 중량% 함유한다. 만일 그 함유량이 10 중량%를 초과하면 라텍스의 제조시 유화가 어렵게 되는 문제가 있다.The ethylenically unsaturated monomer having the hydroxy group is a mixed medium of the dye and the monomer in the aqueous dispersion of the present invention, to prevent the production of homopolymers of cyano group-containing ethylenically unsaturated monomers, or duck rubber that occurs frequently during emulsion polymerization Used to prevent oxidation, such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, poly Propylene glycol (meth) acrylate, pentaerythritol (meth) acrylate, trimethylolpropane (meth) acrylate, neopentyl glycol (meth) acrylate, 1,6-hexanediol (meth) acrylate, glycerol (meth ) Acrylate, 2-hydroxy diethyl (meth) acrylate, polybutylene glycol (meth) acrylate, dipentaerythritol ( L) may be used, such as acrylate. The hydrophilic ethylenically unsaturated monomer having such a hydroxy group is preferably contained in 0 to 10% by weight in the total aqueous dispersion, in particular ethylene having an excess of hydroxy group in the preparation of the maleic acid mono (meth) acrylic ester represented by the formula (1) Although it may not be added when a unsaturated unsaturated monomer is used, it contains 1 to 8 weight% normally. If the content is more than 10% by weight there is a problem that the emulsification becomes difficult during the production of the latex.
상기 스티렌계 또는 (메타)아크릴레이트계 에틸렌성 불포화 단량체는 착색 수지에 경질성을 부여하고 동시에 내광성을 향상시키기 위하여 사용하며, 예컨대 스티렌, 알파 메틸 스티렌, 비닐 톨루엔, N-프로필 메타아크릴레이트, N-부틸 메타크릴레이트, t-부틸 메타크릴레이트, 메틸 메타크릴레이트, 에틸 메타크릴레이트, 이소부틸 메타크릴레이트, 2-에틸헥실 메타크릴레이트, 시클로헥실 메타크릴레이트, 벤질 메타크릴레이트 등을 사용할 수 있으며, 바람직하게는 스티렌 또는 메틸 메타크릴레이트 등의 굳은 중합체를 부여하는 단량체를 사용하는 것이 좋다. 그리고, 상기 단량체들은 본 발명에서 경질성 부여하는 성분으로 단일 성분을 사용할 수 있지만 2 종 이상 혼합하여 사용할 수 도 있다. 상기 경질성을 주는 에틸렌성 불포화 단량체는 전체 수성 분산체 중에 40 ∼ 85 중량% 함유하는 것이 바람직하며, 더욱 바람직하게는 50 ∼ 80 중량%가 좋다. 만일 그 함유량이 40 중량% 미만이면 유화 중합이 곤란하며 내광성이 나빠지고 은폐력이 적은 문제가 있고, 85 중량%를 초과하면 착색성분이 적게 되어 발색성이 나빠지게 된다. The styrene-based or (meth) acrylate-based ethylenically unsaturated monomer is used to impart hardness to the colored resin and at the same time improve light resistance, such as styrene, alpha methyl styrene, vinyl toluene, N-propyl methacrylate, N -Butyl methacrylate, t-butyl methacrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate and the like can be used. It is preferable to use a monomer imparting a hard polymer such as styrene or methyl methacrylate. In addition, the monomers may be used as a component for imparting rigidity in the present invention, but may be used by mixing two or more kinds. It is preferable to contain 40-85 weight% of the ethylenically unsaturated monomers which give the said rigidity in the whole aqueous dispersion, More preferably, 50-80 weight% is good. If the content is less than 40% by weight, the emulsion polymerization is difficult, there is a problem that the light resistance is poor and the hiding power is small, when the content exceeds 85% by weight, the coloring component is reduced and the color development is poor.
본 발명에 따른 착색 수지용 수성 분산체는 상기와 같은 성분들을 이용하여 유화중합시켜 제조한 유화 중합체이다. 상기 유화중합은 계면활성제를 첨가하여 행한 통상의 유화중합 방법에 의해 제조한 것이고, 유화중합 방법은 계면활성제의 종류, 양을 목적에 맞게 적정 선택하여 취급하고 중합온도는 50 ∼ 90 ℃로 하는 것이 바람직하며, 중합 개시제로는 과유산암모늄, 과유산 칼륨 또는 필요에 따라 환원제를 병용하여 사용할 수도 있다. 상기 계면활성제로는 도데실설폰산 나트륨 염, 알킬벤젠설폰산염, 알킬페닐 설폰산염, 알킬알릴 설폰산의 포르마린 축합물, 알킬알릴설폰산의 케톤 화합물, 설포 호박산 에스테르 염, 폴리옥시에틸렌 알킬설페이드 염 등의 음이온 계면활성제, 폴리옥시 에틸렌 알킬 페닐 에테르류, 폴리옥시 에틸렌 알킬 에테르류, 폴리옥시 에틸렌 알킬 에스테르류, 폴리옥시 에틸렌 알킬 솔비탄 에스테르류, 글리세린 지방산 에스테르류, 펜타에리스리톨, 솔비탄 지방산 에스테르류, 마니탄 지방산 에스테르류, 폴리에틸렌 옥사이드, 고급 지방산, 고급 알코올 등의 비이온 계면활성제 등을 단독 또는 2 종 이상 혼합하여 사용할 수 있다. 계면활성제의 첨가량은 전체 수성 분산체 중에 2 ∼ 30 중량% 사용하는 것이 바람직하며, 더욱 바람직하게는 3 ∼ 10 중량% 사용하는 것이 좋다. 그리고, 상기 본 발명에 따른 수성 분산체에는 중화제로 모노 에탄올아민, N,N-디에틸에탄올아민, 암모니아수, 디에탄올 아민, 트리에탄올 아민 등의 염기를 첨가하여 사용할 수도 있다. 또한, 본 발명의 수성 분산체에서는 물성을 향상시키기 위한 용도로서 방부제, 소포제, 적외선 흡수제 등의 첨가제와 수용성 수지, 에멀젼 등의 바인더류를 첨가할 수 있다. The aqueous dispersion for colored resins according to the present invention is an emulsion polymer prepared by emulsion polymerization using the above components. The emulsion polymerization is prepared by the usual emulsion polymerization method performed by adding a surfactant, and the emulsion polymerization method is appropriately selected and handled the type and amount of the surfactant according to the purpose, and the polymerization temperature is 50 ~ 90 ℃. Preferably, the polymerization initiator may be used in combination with ammonium peroxide, potassium peroxide or, if necessary, a reducing agent. The surfactant includes sodium dodecyl sulfonic acid salt, alkylbenzene sulfonate, alkylphenyl sulfonate, formarin condensate of alkylallyl sulfonic acid, ketone compound of alkylallyl sulfonic acid, sulfo succinic acid ester salt, polyoxyethylene alkyl sulfide salt Anionic surfactants, polyoxy ethylene alkyl phenyl ethers, polyoxy ethylene alkyl ethers, polyoxy ethylene alkyl esters, polyoxy ethylene alkyl sorbitan esters, glycerin fatty acid esters, pentaerythritol, sorbitan fatty acid esters, etc. And nonionic surfactants such as mannitan fatty acid esters, polyethylene oxide, higher fatty acids, higher alcohols, and the like, may be used alone or in combination of two or more thereof. The amount of the surfactant added is preferably 2 to 30% by weight in the total aqueous dispersion, more preferably 3 to 10% by weight. The aqueous dispersion according to the present invention may also be used by adding a base such as mono ethanolamine, N, N-diethylethanolamine, aqueous ammonia, diethanol amine, triethanol amine, etc. as a neutralizing agent. Moreover, in the aqueous dispersion of this invention, additives, such as a preservative, an antifoamer, an infrared absorber, and binders, such as water-soluble resin and an emulsion, can be added as a use for improving physical properties.
상기와 같은 성분을 사용하여 유화 중합시킨 유화 중합체의 입자는 평균 입경이 0.01 ∼ 10 ㎛, 바람직하게는 0.01 ∼ 0.5 ㎛로 조절하는 등 그 자체 공지인 임의의 방법으로 제조할 수 있다. 본 발명에 사용하는 유화 중합체의 입경은 0.5 ㎛ 이하인 것이 바람직하며, 만일 유화 중합체의 입경이 0.5 ㎛를 초과하면 유화 중합체가 침강하기 쉽고, 잉크가 원활하게 유동하지 않는 문제가 있다.Particles of the emulsion polymer subjected to emulsion polymerization using the above components can be produced by any method known per se, such as adjusting the average particle size to 0.01 to 10 µm, preferably 0.01 to 0.5 µm. It is preferable that the particle diameter of the emulsion polymer used for this invention is 0.5 micrometer or less, and if the particle diameter of an emulsion polymer exceeds 0.5 micrometer, there exists a problem that an emulsion polymer tends to settle and ink does not flow smoothly.
또한, 본 발명은 상기와 같은 성분으로 제조한 유화 중합체를 염료로 착색된 수지를 얻기위한 수성 분산체로 사용하여 제조한 착색 수지를 포함한다. 이때, 본 발명에 따른 착색 수지는 상기 수성 분산체로 사용한 유화 중합체 성분 100 중량부에 대하여 염료 1 ∼ 10 중량부를 첨가하여 착색시킨다. 만일 염료의 첨가량이 1 중량부 미만이면 색도가 낮게 되어 착색수지로서의 사용에 문제가 있고, 10 중량부를 초과하면 비중이 너무 높아져서 유화중합체가 불안정하게 되는 문제가 있다.The present invention also includes a colored resin prepared by using the emulsion polymer prepared with the above components as an aqueous dispersion for obtaining a resin colored with a dye. At this time, the coloring resin which concerns on this invention is colored by adding 1-10 weight part of dye with respect to 100 weight part of emulsion polymer components used as the said aqueous dispersion. If the amount of dye added is less than 1 part by weight, the chromaticity is low, and there is a problem in use as a colored resin. If the amount is more than 10 parts by weight, the specific gravity is too high, resulting in an unstable emulsion polymer.
상기 염료로는 염기성 염료(카치온 염료), 산성 염료, 직접 염료, 분산염료, 유용성 염료, 형광증백 염료 등의 유기염료를 사용할 수 있으며, 상기 염료를 단독 또는 2종 이상 혼합하여 사용할 수 있으며, 선명한 색조를 원하는 경우 형광 염료를 사용한다. 상기 염료는 예를 들어, 칼라 인덱스 넘버로 표시하면, 베이직 엘로우(Basic Yellow) 1, 40, 41, 베이직 레드(Basic Red) 1, 13, 14, 27, 39, 베이직 바이올렛(Basic Violet) 7, 10, 11, 베이직 오렌지(Basic Orange) 22, 베이직 블루(Basic Blue) 3, 7, 베이직 그린(Basic Green) 4, 에시드 엘로우(Acid yellow) 3, 7, 에시드 레드(Acid Red) 77, 에시드 블루(Acid Blue) 9, 디스퍼스 엘로우(Disperse Yellow) 121, 다이렉트 오렌지(Direct Orange) 11, 솔벤트 블루(Solvent Blue) 5, 피그먼트 엘로우(Pigment Yellow) 1 등의 염료를 사용할 수 있다. 상기 중에서도, 베이직 엘로우 40, 51, 베이직 레드 1, 베이직 바이올렛 10, 11등의 염료가 좋다. As the dye, organic dyes such as basic dyes (cationic dyes), acid dyes, direct dyes, disperse dyes, oil-soluble dyes, and fluorescent whitening dyes may be used. The dyes may be used alone or in combination of two or more kinds thereof. If you want a hue, use a fluorescent dye. For example, the dye may be expressed as a color index number, Basic Yellow 1, 40, 41, Basic Red 1, 13, 14, 27, 39, Basic Violet 7, 10, 11, Basic Orange 22, Basic Blue 3, 7, Basic Green 4, Acid Yellow 3, 7, Acid Red 77, Acid Blue Dyes such as (Acid Blue) 9, Disperse Yellow 121, Direct Orange 11, Solvent Blue 5, Pigment Yellow 1 and the like can be used. Among these, dyes, such as basic yellow 40, 51, basic red 1, basic violet 10, 11, are preferable.
본 발명에 따른 착색 수지는 수성분산체에 염료를 착색시키는 일반적인 방법에 의하여 이루어진다. 예를 들면, 염료의 착색은 유화 중합시 또는 공중합 반응이 종료되고 난 후 실온에서 염료 수용액을 첨가하여 착색시키는 방법 또는 유리전이점 이하의 온도에서 가열하여 착색하는 방법이 가능하지만, 상기의 방법에 한정되는 것은 아니다. The colored resin according to the present invention is made by a general method of coloring a dye with an aqueous acid. For example, the coloring of the dye may be performed by adding an aqueous dye solution at room temperature at the time of emulsion polymerization or after completion of the copolymerization reaction or coloring by heating at a temperature below the glass transition point. It is not limited.
또한, 상기 착색 수지에는 염료의 점착을 돕기위해 점착 보조제와 수중에 유리된 양이온성 염료의 흡착 보조제로서 수용성 당류를 사용할 수 있다. 상기 수용성 당류로는 알긴산, 메틸 셀룰로스, 카르복실 메틸 셀룰로스, 히드록시 에틸 셀룰로스, 알파 시클로덱스트린, 글루코스, 크실로오스, 말토스, 아라비노스 등을 사용할 수 있으며, 바람직하게는 알긴산, 메틸 셀룰로스, 카르복실 메틸 셀룰로스, 히드록시 에틸 셀룰로스, 알파-시클로덱스트린 등을 사용하는 것이 좋다. 그리고, 상기 수용성 당류는 수중에 0.01 ∼ 2 중량% 용해시켜 사용할 수 있다.In addition, water-soluble sugars may be used for the colored resin as an adsorbent for adhering the cationic dye and the adjuvant in the water to assist the adhesion of the dye. Alginic acid, methyl cellulose, carboxyl methyl cellulose, hydroxy ethyl cellulose, alpha cyclodextrin, glucose, xylose, maltose, arabinose and the like can be used as the water-soluble sugars, and preferably alginic acid, methyl cellulose, carbohydrate and the like. Preference is given to using methyl methyl cellulose, hydroxy ethyl cellulose, alpha-cyclodextrin and the like. The water-soluble sugars can be used by dissolving 0.01 to 2% by weight in water.
상기와 같은 본 발명에 따른 착색 수지에는 보습성 및 분산 안정성, 저온 저장 안정성 등의 효과를 부여하기 위하여 친수성 고비등점 저휘발성 용매를 첨가하는 것이 가능하다. 상기 친수성 고비등점 저휘발성 용매로는 글리세린, 에틸렌 글리콜, 디에틸렌 글리콜, 트리에틸렌 글리콜, 프로필렌글리콜, 디프로필렌글리콜, 폴리프로필렌 글리콜 등의 다가 알코올류나에틸렌글리콜 모노 메틸 에테르, 에틸렌 글리콜 에틸 에테르, 에틸렌 글리콜 모노부틸 에테르, 디에틸렌 글리콜 모노 메틸 에테르, 디에틸렌글리콜 모노 부틸 에테르 등의 에테르화물, 디에테르화물, 에스테르화물 등을 사용할 수 있다.To the colored resin according to the present invention as described above, it is possible to add a hydrophilic high boiling point low-volatile solvent in order to give effects such as moisture retention and dispersion stability, low temperature storage stability. As the hydrophilic high boiling point low-volatile solvent, polyhydric alcohols such as glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, ethylene glycol mono methyl ether, ethylene glycol ethyl ether, ethylene glycol Etherates such as monobutyl ether, diethylene glycol mono methyl ether, diethylene glycol mono butyl ether, diethers, esterifieds and the like can be used.
상기와 같은 본 발명에 따른 착색 수지는 내용제성, 내알칼리성이 우수하고, 감열지나 감압지에서 소색이나 변색이 없다. 또한, 선명한 색조를 나타내고 내광성이 높으며 많은 색을 나타내는데 적합하므로, 본 발명의 착색 수지는 필기구나 인쇄잉크, 마킹펜용 잉크 등에 매우 유용하며, 그 외에도 날염 및 수성 도료에 유용하게 사용될 수 있다.The colored resin according to the present invention as described above is excellent in solvent resistance and alkali resistance, and does not discolor or discolor in thermal paper or pressure-sensitive paper. In addition, since it is a vivid color tone, high light resistance, and suitable for displaying many colors, the colored resin of the present invention is very useful for writing, printing ink, marking pen ink, and the like, and can be useful for printing and water-based paints.
이하, 본 발명을 실시예에 의거하여 더욱 상세하게 설명하겠는 바, 본 발명이 실시예에 의하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by Examples.
실시예 1. 말레산 모노(메타)아크릴에스테르의 제조Example 1 Preparation of Maleic Mono (meth) acrylic Ester
교반기, 환류 냉각기 및 질소 도입관을 구비한 플라스크에 무수 말레산 (30 g)과 2-히드록시에틸 메타크릴레이트(46 g)을 가하고 70 ℃의 오일조에서 3시간 교반하여 모노-2-(메타크릴로일)에틸 말레산 에스테르를 점성있는 투명 오일로 얻었다. 얻어진 화합물을 프로톤 핵자기공명 스펙트럼(300 MHz)으로 분석한 결과 목적물로의 전환율이 97% 이었다.Maleic anhydride (30 g) and 2-hydroxyethyl methacrylate (46 g) were added to a flask equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube, and stirred in an oil bath at 70 ° C. for 3 hours to give mono-2- ( Methacryloyl) ethyl maleic acid ester was obtained as a viscous transparent oil. The obtained compound was analyzed by Proton nuclear magnetic resonance spectrum (300 MHz). The conversion to the target product was 97%.
1H NMR (CDCl3): d 1.96 (s, 3H), 4.42-4.44 (m, 2H), 4.51-4.53 (m, 2H), 5.62 (s, 1H), 6.15 (s, 1h), 6.38-6.46 (m, 2H), 8.3 (br, 1h, COOH). 1 H NMR (CDCl 3 ): d 1.96 (s, 3H), 4.42-4.44 (m, 2H), 4.51-4.53 (m, 2H), 5.62 (s, 1H), 6.15 (s, 1h), 6.38- 6.46 (m, 2 H), 8.3 (br, 1 h, COOH).
실시예 2. 착색 수지 제조Example 2. Preparation of Colored Resin
온도계, 교반기, 환류 냉각기를 구비한 4구 플라스크에 이온교환수 35 중량부를 가하고 80 ℃로 승온하였다. 또 다른 삼각 플라스크에 이온교환수 40 중량부에 도데실설폰산나트륨 3 중량부와 폴리옥시에틸렌에테르황산나트륨 5 중량부를 가하여 교반하여 녹인 후, 여기에 상기 실시예 1에 의해 제조된 모노-2-(메타크릴로일)에틸 말레산 에스테르 5 중량부와 스티렌 30 중량부, 2-히드록시에틸 메타크릴레이트 1 중량부, 아크릴로니트릴 12 중량부, 염료로 베이직 엘로우 40(경인화학 제품) 3 중량부를 첨가하고 충분히 교반하여 유화시키고 개시제로서 암모늄 퍼설페이트 0.2 중량부를 가하여 유화액을 제조하였다. 유화액을 상기 80 ℃로 승온한 4구 플라스크에 2 시간 동안 적가한 후 5 시간 중합 반응을 시켰다. 반응이 끝난 후, 상온으로 냉각하여 40%의 고형분을 갖는 노란색의 착색 수지를 얻었다. 얻어진 착색 수지 입자의 크기를 입자 분포계로 측정한 바 0.25 ㎛이었고 점도는 3.5 cps (25 ℃)이었다. 35 weight part of ion-exchange water was added to the 4-neck flask provided with the thermometer, the stirrer, and the reflux condenser, and it heated up at 80 degreeC. In another Erlenmeyer flask, 3 parts by weight of sodium dodecyl sulfonate and 5 parts by weight of sodium polyoxyethylene ether sulfate were added to 40 parts by weight of ion-exchanged water, stirred, and dissolved therein, followed by mono-2- (meta) prepared in Example 1 above. 5 parts by weight of chryloyl) ethyl maleic acid ester, 30 parts by weight of styrene, 1 part by weight of 2-hydroxyethyl methacrylate, 12 parts by weight of acrylonitrile, and 3 parts by weight of Basic Yellow 40 (Kyungin Chemical) as a dye And sufficiently stirred to emulsify, and 0.2 part by weight of ammonium persulfate was added as an initiator to prepare an emulsion. The emulsion was added dropwise to the four neck flask heated to 80 ° C. for 2 hours and then subjected to a polymerization reaction for 5 hours. After the reaction was completed, it was cooled to room temperature to obtain a yellow colored resin having a solid content of 40%. It was 0.25 micrometer and the viscosity was 3.5 cps (25 degreeC) when the size of the obtained colored resin particle was measured with the particle distribution meter.
상기에 의해 제조된 착색 수지 150 중량부에 에틸렌글리콜 30 중량부 및 이온교환수 120 중량부를 혼합 교반시켜 노란색 형광의 마킹펜용 잉크를 얻었다.30 parts by weight of ethylene glycol and 120 parts by weight of ion-exchanged water were mixed and stirred to 150 parts by weight of the colored resin prepared as described above to obtain a yellow fluorescent marking pen ink.
실시예 3. 착색 수지 제조Example 3. Colored resin preparation
온도계, 교반기, 환류 냉각기를 구비한 4구 플라스크에 이온교환수 30 중량부를 가하고 80 ℃로 승온하였다. 또 다른 삼각 플라스크에 이온교환수 30 중량부에 도데실설폰산나트륨 2 중량부와 폴리옥시에틸렌에테르황산나트륨 5 중량부를 가하여 교반하여 녹인 후, 여기에 상기 실시예 1에 의해 제조된 모노-2-(메타크릴로일)에틸 말레산 에스테르 4 중량부와 스티렌 32 중량부, 메틸 메타크릴레이트 5 중량부, 2-히드록시에틸 메타크릴레이트 1 중량부, 아크릴로니트릴 8 중량부를 첨가하고 충분히 교반하여 유화시키고 개시제로서 암모늄 퍼설페이트 0.2 중량부를 가하여 유화액을 제조하였다. 유화액을 상기 80 ℃로 승온한 4구 플라스크에 2 시간 동안 적가한 후 5 시간 중합 반응을 시켰다. 얻어진 유화 중합체에 염료로 베이직 블루 3(경인화학 제품) 1 중량부, 알킬나프탈렌설폰산나트륨 1 중량부 및 이온교환수 20 중량부의 혼합물을 상온에서 첨가하여 1 시간에 걸쳐 서서히 90 ℃로 승온시켜 염료를 착색시켰으며, 착색된 수지는 상온으로 냉각하여 35%의 고형분을 갖는 파란색의 착색 수지를 얻었다. 얻어진 착색 수지 입자의 크기를 입자 분포계로 측정한 바 0.23 ㎛ 이었고 점도는 4.5 cps (25 ℃)이었다. 30 weight part of ion-exchange water was added to the four neck flask equipped with the thermometer, the stirrer, and the reflux condenser, and it heated up at 80 degreeC. In another Erlenmeyer flask, 2 parts by weight of sodium dodecyl sulfonate and 5 parts by weight of sodium polyoxyethylene ether sulfate were added to 30 parts by weight of ion-exchanged water, stirred, and dissolved, followed by mono-2- (meth) prepared in Example 1 above. 4 parts by weight of chryloyl) ethyl maleic acid ester, 32 parts by weight of styrene, 5 parts by weight of methyl methacrylate, 1 part by weight of 2-hydroxyethyl methacrylate, and 8 parts by weight of acrylonitrile were added and sufficiently stirred to emulsify. 0.2 part by weight of ammonium persulfate was added as an initiator to prepare an emulsion. The emulsion was added dropwise to the four neck flask heated to 80 ° C. for 2 hours and then subjected to a polymerization reaction for 5 hours. To the obtained emulsion polymer, a mixture of 1 part by weight of Basic Blue 3 (Kyungin Chemical), 1 part by weight of sodium alkylnaphthalenesulfonate and 20 parts by weight of ion-exchanged water was added at room temperature, and gradually heated to 90 ° C. over 1 hour. The colored resin was cooled to room temperature to obtain a blue colored resin having a solid content of 35%. It was 0.23 micrometer and the viscosity was 4.5 cps (25 degreeC) when the size of the obtained colored resin particle was measured with the particle distribution meter.
상기에 의해 제조된 착색 수지 150 중량부에 에틸렌글리콜 30 중량부 및 이온교환수 120 중량부를 혼합 교반시켜 파란색의 필기구용 잉크를 얻었다.30 parts by weight of ethylene glycol and 120 parts by weight of ion-exchanged water were mixed and stirred to 150 parts by weight of the colored resin prepared as described above to obtain a blue writing instrument ink.
실시예 4. 착색 수지의 제조Example 4. Preparation of Colored Resin
온도계, 교반기, 환류 냉각기를 구비한 4구 플라스크에 이온교환수 50 중량부를 가하고 80 ℃로 승온하였다. 또 다른 삼각 플라스크에 이온교환수 40 중량부에 도데실설폰산나트륨 4 중량부와 폴리옥시에틸렌에테르황산나트륨 3 중량부를 가하여 교반하여 녹인 후, 여기에 상기 실시예 1에 의해 제조된 모노-2-(메타크릴로일)에틸 말레산 에스테르 4 중량부와 스티렌 30 중량부, 메틸 메타크릴레이트 7 중량부, 2-히드록시에틸 메타크릴레이트 1 중량부, 아크릴로니트릴 8 중량부, 염료로 베이직 엘로우 40(경인화학 제품) 2 중량부를 첨가하고 충분히 교반하여 유화시키고 개시제로서 암모늄 퍼설페이트 0.3 중량부를 가하여 유화액을 제조하였다. 유화액을 상기 80 ℃로 승온한 4구 플라스크에 2 시간 동안 적가한 후 5 시간 중합 반응을 시켰다. 반응이 끝난 후, 얻어진 노란색의 착색 수지에 염료로 베이직 블루 3(경인화학 제품) 1 중량부, 도데실설폰산 나트륨 1 중량부 및 이온교환수 10 중량부의 혼합물을 상온에서 첨가하여 1 시간에 걸쳐 서서히 90 ℃로 승온시켜 착색시키고, 상온으로 냉각하여 35 %의 고형분을 갖는 연두색의 착색 수지를 얻었다. 얻어진 착색 수지 입자의 크기를 입자 분포계로 측정한 바 0.25 ㎛이었고 점도는 3.5 cps (25 ℃)이었다. 50 weight part of ion-exchange water was added to the four neck flask equipped with the thermometer, the stirrer, and the reflux condenser, and it heated up at 80 degreeC. In another Erlenmeyer flask, 4 parts by weight of sodium dodecyl sulfonate and 3 parts by weight of sodium polyoxyethylene ether sulfate were added to 40 parts by weight of ion-exchanged water, stirred, and dissolved therein, followed by mono-2- (meta) prepared in Example 1 above. 4 parts by weight of chryloyl) ethyl maleic ester and 30 parts by weight of styrene, 7 parts by weight of methyl methacrylate, 1 part by weight of 2-hydroxyethyl methacrylate, 8 parts by weight of acrylonitrile, and basic yellow 40 Kyungin Chemical Products) 2 parts by weight was added and sufficiently stirred to emulsify, and 0.3 parts by weight of ammonium persulfate was added as an initiator to prepare an emulsion. The emulsion was added dropwise to the four neck flask heated to 80 ° C. for 2 hours and then subjected to a polymerization reaction for 5 hours. After the reaction was completed, a mixture of 1 part by weight of Basic Blue 3 (Kyungin Chemical), 1 part by weight of sodium dodecylsulfonic acid, and 10 parts by weight of ion-exchanged water was added to the obtained yellow colored resin at room temperature. It heated up at 90 degreeC, colored, and cooled to normal temperature, and obtained the yellowish green colored resin which has 35% of solid content. It was 0.25 micrometer and the viscosity was 3.5 cps (25 degreeC) when the size of the obtained colored resin particle was measured with the particle distribution meter.
실시예 5. 착색 수지 제조Example 5. Colored resin preparation
온도계, 교반기, 환류 냉각기를 구비한 4구 플라스크에 이온교환수 40 중량부를 가하고 80 ℃로 승온하였다. 또 다른 삼각 플라스크에 이온교환수 40 중량부에 도데실설폰산나트륨 3 중량부와 폴리옥시에틸렌에테르황산나트륨 5 중량부를 가하여 교반하여 녹인 후, 여기에 상기 실시예 1에 의해 제조된 모노-2-(메타크릴로일)에틸 말레산 에스테르 5 중량부와 스티렌 32 중량부, 2-히드록시에틸 메타크릴레이트 1 중량부, 아크릴로니트릴 12 중량부, 베이직 레드 14(유신제품) 1 중량부를 첨가하고 충분히 교반하여 유화시키고 개시제로서 암모늄 퍼설페이트 0.3 중량부를 가하여 유화액을 제조하였다. 유화액을 상기 80 ℃로 승온한 4구 플라스크에 2 시간 동안 적가한 후 5 시간 중합 반응시켜 염료를 수지에 착색시켰다. 착색된 수지는 상온으로 냉각하여 35%의 고형분을 갖는 핑크색의 착색 수지를 얻었다. 얻어진 착색 수지 입자의 크기를 입자 분포계로 측정한 바 0.27 ㎛ 이었고 점도는 3.5 cps (25 ℃)이었다. 40 weight part of ion-exchange water was added to the four neck flask provided with the thermometer, the stirrer, and the reflux condenser, and it heated up at 80 degreeC. In another Erlenmeyer flask, 3 parts by weight of sodium dodecyl sulfonate and 5 parts by weight of sodium polyoxyethylene ether sulfate were added to 40 parts by weight of ion-exchanged water, stirred, and dissolved therein, followed by mono-2- (meta) prepared in Example 1 above. 5 parts by weight of chryloyl) ethyl maleic ester, 32 parts by weight of styrene, 1 part by weight of 2-hydroxyethyl methacrylate, 12 parts by weight of acrylonitrile, and 1 part by weight of Basic Red 14 (newly produced), and stir sufficiently Emulsification was carried out, and 0.3 part by weight of ammonium persulfate was added as an initiator to prepare an emulsion. The emulsion was added dropwise to the four-necked flask heated to 80 ° C. for 2 hours and then polymerized for 5 hours to color the dye on the resin. The colored resin was cooled to room temperature to obtain a pink colored resin having a solid content of 35%. The particle size of the obtained colored resin particles was measured by a particle distribution meter and found to be 0.27 µm and a viscosity of 3.5 cps (25 ° C).
실시예 6. 착색 수지 제조Example 6. Preparation of Colored Resin
온도계, 교반기, 환류 냉각기를 구비한 4구 플라스크에 이온교환수 40 중량부를 가하고 80 ℃로 승온하였다. 또 다른 삼각 플라스크에 이온교환수 40 중량부에 도데실설폰산나트륨 3 중량부와 폴리옥시에틸렌에테르황산나트륨 5 중량부를 가하여 교반하여 녹인 후, 여기에 상기 실시예 1에 의해 제조된 모노-2-(메타크릴로일)에틸 말레산 에스테르 6 중량부와 스티렌 26 중량부, 2-히드록시에틸 메타크릴레이트 2 중량부, 아크릴로니트릴 16 중량부, 베이직 엘로우 40(경인화학 제품) 2 중량부를 첨가하고 충분히 교반하여 유화시키고 개시제로서 암모늄 퍼설페이트 0.3 중량부를 가하여 유화액을 제조하였다. 유화액을 상기 80 ℃로 승온한 4구 플라스크에 2 시간 동안 적가한 후 5 시간 중합 반응을 시켜 염료를 수지에 착색시켰다. 착색된 수지는 상온으로 냉각하여 35%의 고형분을 갖는 노란색의 착색 수지를 얻었다. 얻어진 착색 수지 입자의 크기를 입자 분포계로 측정한 바 0.15 ㎛이었고 점도는 3.5 cps (25 ℃)이었다. 40 weight part of ion-exchange water was added to the four neck flask provided with the thermometer, the stirrer, and the reflux condenser, and it heated up at 80 degreeC. In another Erlenmeyer flask, 3 parts by weight of sodium dodecyl sulfonate and 5 parts by weight of sodium polyoxyethylene ether sulfate were added to 40 parts by weight of ion-exchanged water, stirred, and dissolved therein, followed by mono-2- (meta) prepared in Example 1 above. 6 parts by weight of chryloyl) ethyl maleic ester, 26 parts by weight of styrene, 2 parts by weight of 2-hydroxyethyl methacrylate, 16 parts by weight of acrylonitrile, and 2 parts by weight of Basic Yellow 40 (Kyungin Chemical) The emulsion was prepared by stirring to emulsify and adding 0.3 parts by weight of ammonium persulfate as an initiator. The emulsion was added dropwise to the four-necked flask heated to 80 ° C. for 2 hours and then polymerized for 5 hours to color the dye on the resin. The colored resin was cooled to room temperature to obtain a yellow colored resin having a solid content of 35%. It was 0.15 micrometer and the viscosity was 3.5 cps (25 degreeC) when the size of the obtained colored resin particle was measured with the particle distribution meter.
실시예 7. 착색 수지 제조Example 7. Colored resin preparation
온도계, 교반기, 환류 냉각기를 구비한 4구 플라스크에 이온교환수 50 중량부를 가하고 80 ℃로 승온하였다. 또 다른 삼각 플라스크에 이온교환수 50 중량부에 도데실설폰산나트륨 1 중량부와 폴리옥시에틸렌에테르황산나트륨 7 중량부를 가하여 교반하여 녹인 후, 여기에 상기 실시예 1에 의해 제조된 모노-2-(메타크릴로일)에틸 말레산 에스테르 3 중량부와 스티렌 30 중량부, 2-히드록시에틸 메타크릴레이트 2 중량부, 아크릴로니트릴 15 중량부, 베이직 바이올렛 11(경인화학 제품) 2 중량부를 첨가하고 충분히 교반하여 유화시키고 개시제로서 암모늄 퍼설페이트 0.3 중량부를 가하여 유화액을 제조하였다. 유화액을 상기 80 ℃로 승온한 4구 플라스크에 2 시간 동안 적가한 후 5 시간 중합 반응을 시켜 염료를 수지에 착색시켰다. 착색된 수지는 상온으로 냉각하여 35%의 고형분을 갖는 붉은 자주색의 착색 수지를 얻었다. 얻어진 착색 수지 입자의 크기를 입자 분포계로 측정한 바 0.2 ㎛ 이었고 점도는 3.5 cps (25 ℃)이었다. 50 weight part of ion-exchange water was added to the four neck flask equipped with the thermometer, the stirrer, and the reflux condenser, and it heated up at 80 degreeC. To another Erlenmeyer flask, 1 part by weight of sodium dodecyl sulfonate and 7 parts by weight of polyoxyethylene ether sulfate were added to 50 parts by weight of ion-exchanged water, and stirred and dissolved therein, followed by mono-2- (meta) prepared in Example 1 above. 3 parts by weight of chryloyl) ethyl maleic ester, 30 parts by weight of styrene, 2 parts by weight of 2-hydroxyethyl methacrylate, 15 parts by weight of acrylonitrile, 2 parts by weight of Basic Violet 11 (Kyungin Chemical) The emulsion was prepared by stirring to emulsify and adding 0.3 parts by weight of ammonium persulfate as an initiator. The emulsion was added dropwise to the four-necked flask heated to 80 ° C. for 2 hours and then polymerized for 5 hours to color the dye on the resin. The colored resin was cooled to room temperature to obtain a reddish purple colored resin having a solid content of 35%. It was 0.2 micrometer and the viscosity was 3.5 cps (25 degreeC) when the size of the obtained colored resin particle was measured with the particle distribution meter.
실시예 8. 착색 수지 제조Example 8. Preparation of Colored Resin
온도계, 교반기, 환류 냉각기를 구비한 4구 플라스크에 이온교환수 50 중량부를 가하고 80 ℃로 승온하였다. 또 다른 삼각 플라스크에 이온교환수 50 중량부에 도데실설폰산나트륨 3 중량부와 폴리옥시에틸렌에테르황산나트륨 5 중량부를 가하여 교반하여 녹인 후, 여기에 상기 실시예 1에 의해 제조된 모노-2-(메타크릴로일)에틸 말레산 에스테르 7 중량부와 스티렌 30 중량부, 2-히드록시에틸 메타크릴레이트 2 중량부, 아크릴로니트릴 12 중량부, 베이직 엘로우 40(경인화학 제품) 1 중량부를 첨가하고 충분히 교반하여 유화시키고 개시제로서 암모늄 퍼설페이트 0.3 중량부를 가하여 유화액을 제조하였다. 유화액을 상기 80 ℃로 승온한 4구 플라스크에 2 시간 동안 적가한 후 5 시간 중합 반응을 시켜 염료를 수지에 착색시켰다. 착색된 수지는 상온으로 냉각하여 35%의 고형분을 갖는 주황색의 착색 수지를 얻었다. 얻어진 착색 수지 입자의 크기를 입자 분포계로 측정한 바 0.15 ㎛ 이었고 점도는 3.5 cps (25 ℃)이었다. 50 weight part of ion-exchange water was added to the four neck flask equipped with the thermometer, the stirrer, and the reflux condenser, and it heated up at 80 degreeC. To another Erlenmeyer flask, 3 parts by weight of sodium dodecyl sulfonate and 5 parts by weight of sodium polyoxyethylene ether sulfate were added to 50 parts by weight of ion-exchanged water, stirred, and dissolved, followed by mono-2- (meth) prepared in Example 1 above. 7 parts by weight of chryloyl) ethyl maleic ester, 30 parts by weight of styrene, 2 parts by weight of 2-hydroxyethyl methacrylate, 12 parts by weight of acrylonitrile, and 1 part by weight of Basic Yellow 40 (Kyungin Chemical) The emulsion was prepared by stirring to emulsify and adding 0.3 parts by weight of ammonium persulfate as an initiator. The emulsion was added dropwise to the four-necked flask heated to 80 ° C. for 2 hours and then polymerized for 5 hours to color the dye on the resin. The colored resin was cooled to room temperature to obtain an orange colored resin having a solid content of 35%. It was 0.15 micrometer and the viscosity was 3.5 cps (25 degreeC) when the size of the obtained colored resin particle was measured with the particle distribution meter.
비교예 1. 착색 수지 제조Comparative Example 1. Production of colored resin
온도계, 교반기, 환류 냉각기를 구비한 4구 플라스크에 이온교환수 100 중량부를 가하고 도데실설폰산나트륨 2 중량부와 폴리옥시에틸렌 노닐 페닐 에테르 0.5 중량부를 가하여 교반하여 녹인 후, 여기에 스티렌 32 중량부, 아크릴로니트릴 15 중량부, 메타크릴산 3 중량부를 첨가하고 30분간 교반하여 유화시키고 개시제로서 과유산암모늄 0.2 중량부를 가하여 유화액을 제조하였다. 유화액을 70 ℃로 승온한 반응조(bath)에 세팅하여 2 시간 동안 적가한 후, 5 시간 중합 반응을 시켰다. 얻어진 유화 중합체 100 중량부에 염료로 베이직 엘로우 40(호도가야 제품) 2 중량부, 도데실설폰산나트륨 1 중량부, 폴리옥시에틸렌 노닐 페닐 에테르 1 중량부 및 이온교환수 20 중량부의 혼합물을 상온에서 첨가하여 1 시간에 걸쳐 서서히 90 ℃로 승온시키고 1시간 착색시킨 후, 착색된 수지는 상온으로 냉각하여 35%의 고형분을 갖는 노란색의 착색 수지를 얻었다. 얻어진 착색 수지 입자의 크기를 입자 분포계로 측정한 바 0.21 ㎛이었고, 점도는 3.1 cps (25 ℃)이었다.100 parts by weight of ion-exchanged water was added to a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and 2 parts by weight of sodium dodecyl sulfonate and 0.5 parts by weight of polyoxyethylene nonyl phenyl ether were added thereto, stirred, and dissolved, followed by 32 parts by weight of styrene, 15 parts by weight of acrylonitrile and 3 parts by weight of methacrylic acid were added thereto, stirred for 30 minutes to emulsify, and 0.2 parts by weight of ammonium persulfate was added as an initiator to prepare an emulsion. The emulsion was set in a bath heated to 70 ° C. and added dropwise for 2 hours, followed by a polymerization reaction for 5 hours. A mixture of 2 parts by weight of Basic Yellow 40 (manufactured by Hodogaya), 1 part by weight of sodium dodecyl sulfonate, 1 part by weight of polyoxyethylene nonyl phenyl ether, and 20 parts by weight of ion-exchanged water are added to 100 parts by weight of the obtained emulsion polymer at room temperature. After gradually raising the temperature to 90 ° C over 1 hour and coloring for 1 hour, the colored resin was cooled to room temperature to obtain a yellow colored resin having a solid content of 35%. It was 0.21 micrometer, and the viscosity was 3.1 cps (25 degreeC) when the size of the obtained colored resin particle was measured with the particle distribution meter.
비교예 2. 착색 수지 제조Comparative Example 2. Preparation of Colored Resin
온도계, 교반기, 환류 냉각기를 구비한 4구 플라스크에 이온교환수 50 중량부를 가하고 과유산칼륨 0.3 중량부, 도데실설폰산나트륨 1 중량부, 도데실벤젠설폰산나트륨 1 중량부를 가하여 교반하여 녹인 후, 여기에 스티렌 20.4 중량부, 메틸 메타크릴레이트 7 중량부, 메타크릴로니트릴 6 중량부, 메타크릴산 3.7 중량부, 글리시딜 메타크릴레이트 2.9 중량부를 첨가하고 30분간 교반하여 유화시키고 반응촉진제로서 N,N-디에틸에탄올아민 0.1 중량부를 가하여 유화액을 제조하였다. 유화액을 반응조(bath)에 세팅하고 80 ℃로 승온한 후 5 시간 중합 반응을 시켰다. 얻어진 유화 중합체 100 중량부에 염료로 베이직 엘로우 40(호도가야 제품) 2 중량부, 도데실설폰산나트륨 1.5 중량부, 폴리옥시에틸렌 노닐 페닐 에테르 1 중량부 및 이온교환수 30 중량부의 혼합물을 상온에서 첨가하여 1 시간에 걸쳐 서서히 90 ℃로 승온시키고 1시간 착색시킨 후, 착색된 수지는 상온으로 냉각하여 35%의 고형분을 갖는 노란색의 착색 수지를 얻었다. 얻어진 착색 수지 입자의 크기를 입자 분포계로 측정한 바 0.14㎛이었고, 점도는 3.6 cps (25 ℃)이었다.50 parts by weight of ion-exchanged water was added to a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 0.3 parts by weight of potassium perperate, 1 part by weight of sodium dodecyl sulfonate, and 1 part by weight of sodium dodecylbenzenesulfonate were dissolved by stirring. 20.4 parts by weight of styrene, 7 parts by weight of methyl methacrylate, 6 parts by weight of methacrylonitrile, 3.7 parts by weight of methacrylic acid, and 2.9 parts by weight of glycidyl methacrylate were added and stirred for 30 minutes to emulsify it as a reaction promoter. 0.1 part by weight of N, N-diethylethanolamine was added to prepare an emulsion. The emulsion was set in a bath, heated to 80 ° C., and subjected to a polymerization reaction for 5 hours. A mixture of 2 parts by weight of Basic Yellow 40 (manufactured by Hodogaya), 1.5 parts by weight of sodium dodecyl sulfonate, 1 part by weight of polyoxyethylene nonyl phenyl ether, and 30 parts by weight of ion-exchanged water are added to 100 parts by weight of the obtained emulsion polymer at room temperature. After gradually raising the temperature to 90 ° C over 1 hour and coloring for 1 hour, the colored resin was cooled to room temperature to obtain a yellow colored resin having a solid content of 35%. It was 0.14 micrometer, and the viscosity was 3.6 cps (25 degreeC) when the size of the obtained colored resin particle was measured with the particle distribution meter.
비교예 3. 착색 수지 제조Comparative Example 3. Preparation of Colored Resin
온도계, 교반기, 환류 냉각기를 구비한 4구 플라스크에 이온교환수 75 중량부를 가하고 과유산칼륨 0.3 중량부, 도데실설폰산나트륨 1 중량부, 폴리옥시에틸렌노닐페닐에테르 3 중량부를 가하여 80 ℃로 승온하였다. 여기에 스티렌 24 중량부, 아크릴로니트릴 20 중량부, 메타크릴산 4 중량부, 글리시딜 메타크릴레이트 3 중량부와 반응촉진제로서 N,N-디에틸에탄올아민 0.1 중량부를 첨가하고 30분간 교반하여 유화액을 제조하였다. 유화액을 80 ℃로 승온한 4구 플라스크에 세팅하고 2시간에 걸쳐 첨가하고 3 시간 중합 반응을 시켰다. 얻어진 유화 중합체 100 중량부에 염료로 베이직 엘로우 40(호도가야 제품) 1.5 중량부, 도데실설폰산나트륨 1.5 중량부, 이온교환수 30 중량부의 혼합물을 상온에서 첨가하여 1 시간에 걸쳐 서서히 90 ℃로 승온시키고 1시간 착색시킨 후, 착색된 수지는 상온으로 냉각하여 35%의 고형분을 갖는 노란색의 착색 수지를 얻었다. 얻어진 착색 수지 입자의 크기를 입자 분포계로 측정한 바 0.12 ㎛이었고, 점도는 3.7 cps (25 ℃)이었다.75 parts by weight of ion-exchanged water was added to a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 0.3 parts by weight of potassium peroxide, 1 part by weight of sodium dodecyl sulfonate, and 3 parts by weight of polyoxyethylene nonylphenyl ether were heated to 80 ° C. . To this, 24 parts by weight of styrene, 20 parts by weight of acrylonitrile, 4 parts by weight of methacrylic acid, 3 parts by weight of glycidyl methacrylate, and 0.1 parts by weight of N, N-diethylethanolamine as reaction accelerators were stirred for 30 minutes. To prepare an emulsion. The emulsion was set in a four-necked flask heated to 80 ° C, added over 2 hours, and subjected to a polymerization reaction for 3 hours. A mixture of 1.5 parts by weight of Basic Yellow 40 (manufactured by Hodogaya), 1.5 parts by weight of sodium dodecyl sulfonate, and 30 parts by weight of ion-exchanged water was added to 100 parts by weight of the obtained emulsion polymer at room temperature, and gradually heated to 90 ° C over 1 hour. After coloring for 1 hour, the colored resin was cooled to room temperature to obtain a yellow colored resin having a solid content of 35%. It was 0.12 micrometer, and the viscosity was 3.7 cps (25 degreeC) when the size of the obtained colored resin particle was measured with the particle distribution meter.
시험예Test Example
상기 실시예 2 ∼ 8 및 비교예 1 ∼ 3에 의해 제조한 착색 수지의 내수성, 내약품성, 내용제성, 내광성, 가교성 및 저장안정성의 시험을 다음과 같은 방법으로 하였으며, 그 결과를 다음 표 1에 나타내었다.The water resistance, chemical resistance, solvent resistance, light resistance, crosslinkability and storage stability of the colored resins prepared according to Examples 2 to 8 and Comparative Examples 1 to 3 were tested by the following methods, and the results are shown in Table 1 below. Shown in
1. 내수성1.water resistance
착색 수지를 켄트지에 빠고다로 도포하고 건조시켜, 이 도포 용지를 물에 1분간 침적시켜, 용출하는지 않는지를 육안으로 확인하여 평가한다. 용출이라 함은 착색 수지가 도포된 종이에서 많고 적음에 관계없이 스며 나오는 것을 말한다. 표 1에서 o는 용출이 없는 것이고, x는 용출이 있는 것을 말한다.The colored resin is coated on kent paper and dried, and the coated paper is immersed in water for 1 minute and visually checked to evaluate whether or not it is eluted. Elution refers to the bleeding, regardless of whether there is much or little in paper coated with colored resin. In Table 1, o means no elution, and x means elution.
2. 내약품성2. Chemical resistance
착색 수지가 도포된 종이를 1% 염산 수용액(내산성) 및 1% 수산화나트륨 수용액(내알칼리성)에 각각 1분간 침적시켜, 용출하는지 않는지를 육안으로 확인하여 평가한다. The paper coated with the colored resin was dipped in 1% aqueous hydrochloric acid solution (acid resistance) and 1% aqueous sodium hydroxide solution (alkali resistance) for 1 minute, respectively, and visually checked to evaluate whether it eluted.
3. 내용제성3. Solvent resistance
착색 수지가 도포된 종이를 이소프로필 알코올에 각각 1분간 침적시켜, 용출하는지 않는지를 육안으로 확인하여 평가한다. The paper coated with the colored resin was immersed in isopropyl alcohol for 1 minute each, and visually checked to evaluate whether or not it eluted.
4. 내광성4. Light resistance
착색 수지가 도포된 종이를 카본아크페이더 미터로 자외선을 10시간 받은 것을 측정하여, JIS L-0841 블로우 스케일 8등급을 이용하여 퇴색 정도를 육안으로 확인한다. 1 ∼ 3 등급은 변퇴색이 심하여 실용적이지 못하므로 내광성을 x로, 4 등급 이상은 내광성을 o로 표시한다.The paper coated with the colored resin was measured for 10 hours by ultraviolet light with a carbon arc fader meter, and visually confirmed the degree of fading using JIS L-0841 blow scale grade 8. Grades 1 to 3 are discolored and are not practical, so the light resistance is x and the grade 4 or higher is light resistance o.
5. 가교판정5. Crosslinking Decision
착색 수지를 건조후 분말화하여, 테트라히드로퓨란(200 ml)중에 고체 분말(1 g)을 용해 후 여지를 이용하여 여과하여 불용해분이 있는지를 확인하여 가교의 유무를 판정한다. 용해하지 않고 불용해분이 있으면 가교되어 있는 것으로 판단한다.The colored resin is dried and powdered, and then dissolved in a solid powder (1 g) in tetrahydrofuran (200 ml) and filtered using a filter paper to check whether there is an insoluble content and to determine the presence or absence of crosslinking. If it does not melt | dissolve and there is insoluble content, it is judged that it is bridge | crosslinking.
6. 저장 안정성6. Storage stability
50 ℃의 항온조 중에 착색 수지를 밀폐시켜 유리 용기에 삽입하여 30일간 보관하여 이상이 있는지 없는지를 육안으로 확인하여 안정성을 평가한다. 이상이라함은 침전물의 발생, 겔화, 증점 등의 점도 변화가 발생하는 현상을 말한다.The colored resin is sealed in a thermostatic bath at 50 ° C., inserted into a glass container, stored for 30 days, and visually checked for abnormalities to evaluate stability. The above refers to a phenomenon in which viscosity changes such as generation of precipitates, gelation, and thickening occur.
상기 표 1에 나타난 바와 같이, 본 발명에 따른 실시예 2 ∼ 8의 착색 수지는 가교제 및 산성관능기로 실시예 1의 말레산 모노(메타)아크릴에스테르를 사용함으로써, 내수성, 내산성, 내알카리성, 내용제성, 내광성, 저장안정성, 가교성이 우수함을 확인할 수 있었다.As shown in Table 1, the colored resins of Examples 2 to 8 according to the present invention are used in the maleic acid mono (meth) acrylic ester of Example 1 as a crosslinking agent and an acidic functional group. It was confirmed that the solvent resistance, light resistance, storage stability, and crosslinkability were excellent.
상술한 바와 같이, 본 발명에 따른 착색 수지용 수성 분산체는 종래 수용성 염료의 단점인 내수성과 내광성에서 비약적으로 좋은 물성을 가지고 있으며, 이런 수성 분산체에 염료를 흡착시킨 착색 수지는 기존 공중합체 라텍스에 염료를 흡착시키는 방법들에서 도출되었던 단점인 내용제성, 내알칼리성의 문제점을 해결할 뿐만 아니라 감열지나 감압지에서 소색이나 변색이 없다. 또한, 선명한 색조를 나타내고 내광성이 높으며 많은 색을 나타내는데 적합하므로, 본 발명의 착색 수지는 필기구나 인쇄잉크, 마킹펜용 잉크 등에 매우 유용하며, 그 외에도 날염 및 수성 도료에 유용하게 사용될 수 있다. 그리고, 본 발명의 착색 수지는 가격이 저렴한 단량체를 이용하여 매우 우수한 물성을 나타내므로 원가 절감 효과가 높고, 국내 자체 생산으로 관련 기술 확보함으로서 새로운 잉크 원제 개발에 시너지 효과를 기대할 수 있다.As described above, the aqueous dispersion for colored resins according to the present invention has excellent properties in terms of water resistance and light resistance, which are disadvantages of conventional water-soluble dyes, and the colored resin obtained by adsorbing dye to such aqueous dispersions is conventional copolymer latex. It not only solves the problems of solvent resistance and alkali resistance, which are the drawbacks of the dye adsorption methods, but it does not discolor or discolor in thermal paper or pressure-sensitive paper. In addition, since it is a vivid color tone, high light resistance, and suitable for displaying many colors, the colored resin of the present invention is very useful for writing, printing ink, marking pen ink, and the like, and can be useful for printing and water-based paints. In addition, since the colored resin of the present invention exhibits very excellent physical properties by using a monomer having a low cost, the cost reduction effect is high, and synergistic effects can be expected in developing new ink raw materials by securing related technologies in domestic production.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6005023A (en) * | 1996-12-27 | 1999-12-21 | E.I. Du Pont Nemours And Company | Ink jet inks containing branched polymer dispersants and emulsion polymer additives |
| US6020400A (en) * | 1996-12-27 | 2000-02-01 | E. I. Du Pont De Nemours And Company | Ink jet inks containing emulsion polymer additives stabilized with structured polymers |
| EP1046686A2 (en) * | 1999-04-21 | 2000-10-25 | Hewlett-Packard Company | Preparation of improved inks for ink-jet printers |
| KR20010012240A (en) * | 1997-05-07 | 2001-02-15 | 미츠비시엔피츠가부시키가이샤 | Aqueous pigment-based ball-point ink having white color tone |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6005023A (en) * | 1996-12-27 | 1999-12-21 | E.I. Du Pont Nemours And Company | Ink jet inks containing branched polymer dispersants and emulsion polymer additives |
| US6020400A (en) * | 1996-12-27 | 2000-02-01 | E. I. Du Pont De Nemours And Company | Ink jet inks containing emulsion polymer additives stabilized with structured polymers |
| KR20010012240A (en) * | 1997-05-07 | 2001-02-15 | 미츠비시엔피츠가부시키가이샤 | Aqueous pigment-based ball-point ink having white color tone |
| EP1046686A2 (en) * | 1999-04-21 | 2000-10-25 | Hewlett-Packard Company | Preparation of improved inks for ink-jet printers |
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