KR101507315B1 - An acrylic emulsion resin composition and the making method thereof - Google Patents
An acrylic emulsion resin composition and the making method thereof Download PDFInfo
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Abstract
Description
본 발명은 각종 테이프나 스티커, 라벨지, 필름, 인쇄물 등의 점착제로 사용되면서 동결 융해시 높은 안정성(安定性)을 지닌 친환경 아크릴 에멀젼수지 조성물 및 그 제조방법에 관한 것으로, 더욱 상세하게는 알킬기의 탄소수가 1 ~ 8인 아크릴산에스테르계 또는 메타아크릴산에스테르계 모노머와, 불포화 모노카르본산계 모노머를 유리전이온도가 -35 ~ -10℃이고 산가가 110 ~ 180mg-KOH/g으로 되도록 혼합한 모노머혼합물을 유화중합법으로 공중합시켜 수용성폴리머를 제조하는 단계와; 상기 수용성폴리머 100중량부에 대하여 알킬기의 탄소수가 1 ~ 14인 아크릴산에스테르계 또는 메타아크릴산에스테르계 모노머, 초산비닐계 모노머, 스티렌계 모노머 중 선택된 어느 하나 또는 둘 이상이 혼합된 베이스모노머 400 ~ 800중량부와, 불포화 모노카르본산계 모노머, 수산기를 갖는 아크릴계 모노머, 에폭시기를 함유하는 아크릴계 모노머 중 선택된 어느 하나 또는 둘 이상과 불포화 실란계 모노머를 혼합한 가교반응을 위한 관능성모노머혼합물 30 ~ 100중량부를 혼합하여 유화중합법으로 공중합시켜 아크릴에멀젼수지를 제조하는 단계를 통해 제조되는 것을 특징으로 하는 동해안정성을 지닌 아크릴 에멀젼수지 조성물 및 그 제조방법에 관한 것이다.
The present invention relates to an eco-friendly acrylic emulsion resin composition having high stability at the time of freezing and thawing while being used as a pressure-sensitive adhesive for various tapes, stickers, label sheets, films and printed matter, and more specifically, Of 1 to 8 and an unsaturated monocarboxylic acid monomer so as to have a glass transition temperature of -35 to -10 占 폚 and an acid value of 110 to 180 mg-KOH / g to obtain a monomer mixture Copolymerizing them by emulsion polymerization to prepare a water-soluble polymer; 400 to 800 weight parts of a base monomer in which one or more selected from acrylic acid ester or methacrylic ester monomers, vinyl acetate monomers and styrene monomers having an alkyl group of 1 to 14 carbon atoms per 100 parts by weight of the water-soluble polymer And 30 to 100 parts by weight of a functional monomer mixture for a crosslinking reaction in which an unsaturated monocarboxylic acid monomer, an acrylic monomer having a hydroxyl group, and an acrylic monomer containing an epoxy group is mixed with an unsaturated silane monomer And then copolymerizing the resultant mixture with an emulsion polymerization method to prepare an acrylic emulsion resin. The present invention also relates to a method for producing the acrylic emulsion resin composition.
일반적으로 아크릴 에멀젼수지 조성물은 수성으로 된 점성을 지닌 액체상태로, 포장산업용 테이프, 다목적 스티커 및 라벨용, 광고용 점착필름과 인쇄물, 가전용품 보호필름, 자동차 선팅필름, 폴리에틸렌필름과 페이퍼간 라미네이션접착 등각종 분야에 점착제로 활용되고 있으며, 이와 같은 아크릴 에멀젼수지 조성물은 통상적으로 유화중합법을 통해 제조되는데 물을 반응매체로 하여 완충제, 연쇄이동제 등 많은 혼합물을 가열하고, 물에 용해된 계면활성제와 각종 모노머를 배합한 후 교반하여 유화하며 개시제와 함께 적정 온도하에서 일정한 시간동안 적하하여 반응시키고, 반응개시 초부터 수지입자가 생성되면서 수중에 안정하게 분산된 상태로 존재하게 되며, 반응이 종료된 중간제품에는 필요에 따라 가소제, 가교제, 점착부여수지, 소포제 등 각종 첨가제를 첨가 혼합한 후 여과하여 아크릴 에멀젼수지 조성물을 완성하게 된다.
Generally, the acrylic emulsion resin composition is a liquid state having a water-based viscosity, and is used as a packaging tape, a multi-purpose sticker and a label, a commercial adhesive film and a printed product, a household electric appliance protective film, an automotive tacking film, a polyethylene film and a paper- These acrylic emulsion resin compositions are usually prepared by emulsion polymerization. Various mixtures such as buffering agents and chain transfer agents are heated with water as a reaction medium, and a surfactant dissolved in water and various kinds of surfactants The monomer is mixed and stirred to emulsify and reacted with the initiator dropwise at a suitable temperature for a certain period of time to be reacted. The resin particles are present in a state of being dispersed stably in the water as the resin particles are generated from the beginning of the reaction, A plasticizer, a crosslinking agent, a tackifier resin, a defoaming agent After addition of various additives mixed and filtered to thereby complete the acrylic emulsion resin composition.
상기 아크릴 에멀젼수지 조성물은 수중에서 만들어진 에멀젼타입으로 계면활성제가 형성하는 미셀내에서 생성되고 수지입자의 생성과 완성까지 모두 동일한 위치에서 이루어지며 완성된 아크릴 에멀젼수지 조성물은 평균입자가 0.2 ~ 5μm 범위의 소립자가 수중에 안정하게 분산된 상태로 존재하나, 기온 강하로 동결되면 미셀내에 존재하는 입자들은 안정성을 잃고 서로 충돌하여 깨지면서 외견상으로 물과 괴상의 덩어리로 분리되어 다시 원상회복되지 않아 점착성 등이 없어지면서 더이상 사용할 수 없는 불량품이 되는 문제점이 발생되며, 산업현장에서는 주로 동절기 육상운반이나 혹한지역 해외수출의 경우 큰 문제가 될 수 있고, 이외에도 업체의 휴무기간 동안 보온설비가 없는 경우나 야적장 등에 보관시 아크릴 에멀젼수지 조성물의 동결현상이 나타나게 된다.
The acrylic emulsion resin composition is an emulsion type which is made in water and is produced in the micelles formed by the surfactant and is formed at the same position until the production and completion of the resin particles. The finished acrylic emulsion resin composition has an average particle size of 0.2 to 5 μm Although the particles are dispersed stably in water, the particles in the micelles lose their stability when they are frozen at a temperature lowering. They collide with each other and break into apparent masses of water and massive particles, And it becomes a problem that it becomes a defective product that can no longer be used, and in the industrial field, it can be a big problem in case of transportation in the winter season or in the case of exporting to an overseas region in a harsh environment. In addition, Freezing phenomenon of acrylic emulsion resin composition It is displayed.
이러한 아크릴 에멀젼수지 조성물은 동해안정성을 보완하기 위하여 가소제나 고비점 용제를 첨가하고 있으나, 가소제는 일정범위 이상으로 첨가시 표면으로 용출되어 나오는 마이그레이션(migration)현상 발생으로 접착강도의 저하 등 물리적 성질이 낮아지고 고비점 용제의 첨가시에는 각종 악취발생 및 휘발성 유기화합물(VOC) 문제에 저촉되어 사용량에 큰 제한이 있는 문제점이 있었다.
In order to compensate for the stability of the East Sea, the acrylic emulsion resin composition is added with a plasticizer or a high boiling point solvent. However, when the plasticizer is added over a certain range, a migration phenomenon occurs, And when the high boiling point solvent is added, there arises a problem in that there is a great limitation in the use amount due to occurrence of various odor and volatile organic compound (VOC) problems.
또한, 아크릴 에멀젼수지 조성물에 관한 종래기술로서, 일본 특허공개공보 특공소 53-117033호에서는 평균분자량 3000 ~ 10,000인 수용성고분자를 만들기 위해 휘발성 유기용매인 메탄올과 에탄올을 사용하였으나, 이 경우 VOC문제 및 화기대책과 코스트업까지 부담을 주어 친환경적이지 못한 문제점이 있었으며, 일본 특허공개공보 특개소 62-227975호의 수성감압접착제와 특개소 63-256672호의 수성점착제 제조에서는 가교를 위한 관능성모노머로 N-Methylol acryl amide를 사용하였으며 상기 모노머는 에멀젼수지를 소재상에 도포 건조하면 우수한 가교특성으로 인해 강인한 도막을 형성하여 고분자의 물성향상에 큰 도움을 주고 있으나, 이 원료가 포함된 수지는 가열건조시 축합반응으로 인해 표면으로 유해한 포르마린이 검출되는 문제가 있어 환경과 위생적으로 사용상 제한을 받고 있다.
As a conventional technique relating to an acrylic emulsion resin composition, Japanese Patent Laid-Open Publication No. 53-117033 discloses that methanol and ethanol, which are volatile organic solvents, are used to make a water-soluble polymer having an average molecular weight of 3000 to 10,000. In this case, In the manufacture of aqueous pressure-sensitive adhesives of Japanese Patent Laid-Open Publication No. 62-227975 and aqueous pressure-sensitive adhesives of Japanese Patent Application No. 63-256672, N-Methylol is used as a functional monomer for crosslinking. acrylamide was used. The monomer was applied and dried on the emulsion resin to form a strong coating film due to excellent crosslinking property, which greatly contributes to improvement of the physical properties of the polymer. However, , There is a problem that the harmful formalin is detected on the surface, and thus the environment and hygienic Getting the clean and jerk limit.
본 발명은 상기와 같은 문제점들을 해결하기 위한 것으로 아크릴산에스테르계 또는 메타아크릴산에스테르계 모노머와 불포화 모노카르본산계 모노머를 유리전이온도가 -35 ~ -10℃이고 산가가 110 ~ 180mg-KOH/g으로 되도록 혼합한 모노머혼합물을 유화중합법으로 공중합시켜 수용성폴리머를 제조한 다음 상기 수용성폴리머의 표면에 베이스모노머와 가교반응을 위한 관능성모노머혼합물을 유화중합법으로 공중합시켜 부착함으로써 온도강하에 따른 동결시 수용성폴리머 부분만 동결되고 표면에 부착된 에멀젼수지 입자들은 서로 충돌하지 않고 원상태를 유지하여 융해시 수용성폴리머가 녹으면 에멀젼수지 입자들의 유동성이 되살아나 원래의 분산상태를 유지하면서 점착성이 원상복원되도록 하는 아크릴에멀젼수지를 제조하는 것에 그 목적이 있다.
SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide an acrylic ester-based or methacrylic ester-based monomer and an unsaturated monocarboxylic acid monomer having a glass transition temperature of -35 to -10 ° C and an acid value of 110 to 180 mg-KOH / g The water-soluble polymer is copolymerized by emulsion polymerization to prepare a water-soluble polymer. Then, a functional monomer mixture for crosslinking reaction with the base monomer is copolymerized on the surface of the water-soluble polymer by emulsion polymerization, Only the water-soluble polymer part is frozen and the emulsion resin particles attached to the surface do not collide with each other and maintain the original state, and when the water-soluble polymer melts when the water-soluble polymer melts, the fluidity of the emulsion resin particles is restored, And an object thereof is to produce an emulsion resin.
이러한 목적을 달성하기 위하여 알킬기의 탄소수가 1 ~ 8인 아크릴산에스테르계 또는 메타아크릴산에스테르계 모노머와, 불포화 모노카르본산계 모노머를 유리전이온도가 -35 ~ -10℃이고 산가가 110 ~ 180mg-KOH/g으로 되도록 혼합한 모노머혼합물을 유화중합법으로 공중합시켜 수용성폴리머를 제조하는 단계와; 상기 수용성폴리머 100중량부에 대하여 알킬기의 탄소수가 1 ~ 14인 아크릴산에스테르계 또는 메타아크릴산에스테르계 모노머, 초산비닐계 모노머, 스티렌계 모노머 중 선택된 어느 하나 또는 둘 이상이 혼합된 베이스모노머 400 ~ 800중량부와, 불포화 모노카르본산계 모노머, 수산기를 갖는 아크릴계 모노머, 에폭시기를 함유하는 아크릴계 모노머 중 선택된 어느 하나 또는 둘 이상과 불포화 실란계 모노머를 혼합한 가교반응을 위한 관능성모노머혼합물 30 ~ 100중량부를 혼합하여 유화중합법으로 공중합시켜 아크릴에멀젼수지를 제조하는 단계를 통해 제조된 것에 본 발명의 특징이 있다.
In order to achieve this object, an acrylic ester-based or methacrylic ester-based monomer having an alkyl group of 1 to 8 carbon atoms and an unsaturated monocarboxylic acid based monomer having a glass transition temperature of -35 to -10 ° C and an acid value of 110 to 180 mg-KOH / g to prepare a water-soluble polymer by copolymerizing the monomer mixture by emulsion polymerization; 400 to 800 weight parts of a base monomer in which one or more selected from acrylic acid ester or methacrylic ester monomers, vinyl acetate monomers and styrene monomers having an alkyl group of 1 to 14 carbon atoms per 100 parts by weight of the water-soluble polymer And 30 to 100 parts by weight of a functional monomer mixture for a crosslinking reaction in which an unsaturated monocarboxylic acid monomer, an acrylic monomer having a hydroxyl group, and an acrylic monomer containing an epoxy group is mixed with an unsaturated silane monomer And then copolymerizing them by emulsion polymerization to prepare an acrylic emulsion resin.
상기와 같이 본 발명에 의하면 계면활성제의 사용비율을 최소화하고 부족한 계면활성제의 역할을 수용성폴리머로 대체함으로써 온도강하에 따른 동결시 수용성폴리머 부분만 동결되고 표면에 부착된 에멀젼수지 입자들은 서로 충돌하지 않고 원상태를 유지하여 융해시 수용성폴리머가 녹으면 에멀젼수지 입자들의 유동성이 되살아나 원래의 분산상태를 유지하면서 점착성이 원상복원되어 반복적인 동결 융해시에도 높은 동해안정성(凍解安定性)을 지닌 아크릴 에멀젼수지 조성물을 제공할 수 있는 효과가 있다.
As described above, according to the present invention, when the ratio of the surfactant is minimized and the role of the insufficient surfactant is replaced by the water-soluble polymer, only the water-soluble polymer portion is frozen during the freezing due to the temperature drop, and the emulsion resin particles attached to the surface do not collide with each other When the water-soluble polymer is melted at the time of melting, the fluidity of the emulsion resin particles is restored, and the adhesive property is restored to the original state while maintaining the original dispersed state. Thus, the acrylic emulsion resin having high freeze- There is an effect that the composition can be provided.
도 1은 본 발명에 따른 실시예와 비교예들의 동결융해에 따른 실험결과사진 1 is a photograph showing experimental results of freezing and thawing of Examples and Comparative Examples according to the present invention
본 발명은 각종 테이프나 스티커, 라벨지, 필름, 인쇄물 등의 점착제로 사용되면서 동결 융해시 높은 안정성(安定性)을 지닌 친환경 아크릴 에멀젼수지 조성물 및 그 제조방법에 관한 것으로, 더욱 상세하게는 수용성폴리머를 제조하는 단계와 아크릴에멀젼수지를 제조하는 단계를 통해 계면활성제의 사용비율을 최소화하고 부족한 계면활성제의 역할을 수용성폴리머로 대체함으로써 온도강하에 따른 동결시 수용성폴리머 부분만 동결되고 표면에 부착된 에멀젼수지 입자들은 서로 충돌하지 않고 원상태를 유지하여 융해시 수용성폴리머가 녹으면 에멀젼수지 입자들의 유동성이 되살아나 원래의 분산상태를 유지하면서 점착성이 원상복원되어 반복적인 동결 융해시에도 높은 동해안정성(凍解安定性)을 지닌 친환경적 아크릴 에멀젼수지 조성물을 제공하게 된다.
The present invention relates to an eco-friendly acrylic emulsion resin composition having high stability at the time of freezing and thawing while being used as a pressure-sensitive adhesive for various tapes, stickers, label sheets, films and printed matter, and more particularly, And the emulsion resin attached to the surface of the water-soluble polymer part is frozen in the freezing according to the temperature drop by replacing the role of the insufficient surfactant with the water-soluble polymer by minimizing the use ratio of the surfactant through the step of preparing the acrylic emulsion resin When the water-soluble polymer melts, the flowability of the emulsion resin particles is restored, and the adhesive property is restored to the original state while maintaining the original dispersed state. Thus, even when repeated freezing and thawing is performed, high dynamic stability ) As an antistatic agent, It is.
상기 수용성폴리머를 제조하는 단계는 알킬기의 탄소수가 1 ~ 8인 아크릴산에스테르계 또는 메타아크릴산에스테르계 모노머와, 불포화 모노카르본산계 모노머를 유리전이온도가 -35 ~ -10℃이고 산가가 110 ~ 180mg-KOH/g으로 되도록 일정비율로 혼합한 모노머혼합물을 통상의 유화중합법으로 공중합시켜 1차적으로 수용성폴리머를 제조하는 것으로, 반응기 내에 물과 계면활성제를 넣어 용해하고 개시제(촉매)와 함께 상기 모노머혼합물을 동시 적하하여 교반하면서 중합반응으로 얻어지는 중합물에 암모니아수 등의 알카리성염을 가하여 중화한 후 물을 가하여 완전히 수용화시켜 수용성폴리머를 얻게 된다.
The step of preparing the water-soluble polymer comprises reacting an acrylic ester-based or methacrylic ester-based monomer having an alkyl group of 1 to 8 carbon atoms with an unsaturated monocarboxylic acid monomer at a glass transition temperature of -35 to -10 ° C and an acid value of 110 to 180 mg -KOH / g in a predetermined ratio so that the water-soluble polymer is first copolymerized by emulsion polymerization to form a water-soluble polymer. Water and a surfactant are added to the reactor to dissolve the monomer and the initiator (catalyst) While the mixture is simultaneously added dropwise and stirred, the polymerizable compound is neutralized by adding an alkaline salt such as ammonia water to the polymerized product, and then water is added thereto to obtain a water-soluble polymer.
상기 모노머혼합물은 알킬기의 탄소수가 1 ~ 8인 아크릴산에스테르계 또는 메타아크릴산에스테르계 모노머 중 선택된 어느 하나 또는 둘 이상과, 이에 공중합가능한 불포화 모노카르본산계 모노머가 일정비율로 혼합된 것으로, 상기 아크릴산에스테르계 모노머는 아크릴산메틸, 아크릴산에틸, 아크릴산부틸, 아크릴산펜틸, 아크릴산헥실, 아크릴산-2-에틸헥실, 아크릴산헵틸, 아크릴산옥틸이고, 메타아크릴산에스테르계 모노머는 메타아크릴산메틸, 메타아크릴산에틸, 메타아크릴산부틸, 메타아크릴산펜틸, 메타아크릴산헥실, 메타아크릴산-2-에틸헥실, 메타아크릴산헵틸, 메타아크릴산옥틸 중 선택된 어느 하나 또는 둘 이상이 사용되며, 상기 불포화 모노카르본산계 모노머는 아크릴산, 메타아크릴산, 크로톤산 중 선택된 어느 하나 또는 둘 이상이 사용되는데, 상기 모노머혼합물은 아크릴산에스테르계 또는 메타아크릴산에스테르계 모노머와 불포화 모노카르본산계 모노머를 일정비율로 혼합하여 유리전이온도가 -35 ~ -10℃ 범위내에 해당되는 것을 사용하게 된다.
Wherein the monomer mixture is a mixture of any one or more selected from acrylic acid ester or methacrylic ester monomers having an alkyl group of 1 to 8 carbon atoms and an unsaturated monocarboxylic acid monomer copolymerizable therewith at a certain ratio, And the methacrylic acid ester monomer is at least one monomer selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, isobutyl acrylate, isobutyl acrylate, One or two or more selected from pentyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, heptyl methacrylate and octyl methacrylate are used, and the unsaturated monocarboxylic acid monomer is selected from acrylic acid, methacrylic acid, One or more selected There is for the monomer mixture is a mixture of acrylic acid ester or methacrylic acid ester-based monomer and the unsaturated monocarboxylic acid-based monomer at a predetermined ratio to be used has a glass transition temperature falling within the range of -35 ~ -10 ℃.
상기 모노머혼합물은 유리전이온도가 -10℃를 초과하는 경우에는 완성된 아크릴에멀젼수지의 점착성(Tack)이 저하되는 문제점이 발생되고 유리전이온도가 -35℃미만일 경우에는 아크릴에멀젼수지의 접착력과 응집력이 낮아지는 문제점이 발생된다.
When the glass transition temperature of the monomer mixture is higher than -10 캜, the tack of the finished acrylic emulsion resin is lowered. When the glass transition temperature is lower than -35 캜, the adhesion and cohesion of the acrylic emulsion resin Is lowered.
또한, 상기 모노머혼합물은 불포화 모노카르본산계 모노머의 첨가량에 의해 산가가 결정되며, 산가의 범위는 110 ~ 180mg-KOH/g으로, 110mg-KOH/g미만일 경우에는 제조된 수용성폴리머를 아크릴에멀젼수지를 제조하는 단계에 사용시 균일하고 이상적인 중합반응을 할 수 없게 되고, 180mg-KOH/g를 초과하는 경우에는 중합반응에 이상이 없으나 완성된 아크릴에멀젼수지의 점착성이 너무 저하되는 문제점이 발생된다.
When the acid value of the monomer mixture is in the range of 110 to 180 mg-KOH / g and less than 110 mg-KOH / g, the prepared water-soluble polymer is dissolved in an acrylic emulsion resin It is impossible to carry out a uniform and ideal polymerization reaction in the step of preparing the acrylic emulsion resin. If it exceeds 180 mg-KOH / g, there is no abnormality in the polymerization reaction but the adhesion of the finished acrylic emulsion resin is deteriorated too much.
상기와 같이 유리전이온도와 산가에 따라 모노머혼합물을 이루는 아크릴산에스테르계 또는 메타아크릴산에스테르계 모노머와 불포화 모노카르본산계 모노머의 혼합비율이 결정된다.
As described above, the mixing ratio of the acrylate ester-based or methacrylate ester-based monomer and the unsaturated monocarboxylic acid-based monomer constituting the monomer mixture is determined depending on the glass transition temperature and the acid value.
상기 아크릴에멀젼수지를 제조하는 단계는 수용성폴리머 100중량부에 대하여 알킬기의 탄소수가 1 ~ 14인 아크릴산에스테르계 또는 메타아크릴산에스테르계 모노머, 초산비닐계 모노머, 스티렌계 모노머 중 선택된 어느 하나 또는 둘 이상이 혼합된 베이스모노머 400 ~ 800중량부와, 불포화 모노카르본산계 모노머, 수산기를 갖는 아크릴계 모노머, 에폭시기를 함유하는 아크릴계 모노머 중 선택된 어느 하나 또는 둘 이상과 불포화 실란계 모노머를 혼합한 가교반응을 위한 관능성모노머혼합물 30 ~ 100중량부를 2차적으로 아크릴에멀젼수지를 제조하는 것으로, 반응기 내에 수용성폴리머가 일정량 투입된 상태에서 물과 계면활성제를 넣어 용해하고 개시제(촉매)와 함께 일정량의 베이스모노머와 가교반응을 위한 관능성모노머혼합물을 적하하여 교반하면서 중합반응으로 아크릴에멀젼수지를 얻게 된다.
The step of preparing the acrylic emulsion resin may be carried out by mixing at least one selected from an acrylate ester or methacrylate ester monomer, a vinyl acetate monomer and a styrene monomer having an alkyl group of 1 to 14 carbon atoms per 100 parts by weight of the water- And 400 to 800 parts by weight of a mixed base monomer and at least one selected from an unsaturated monocarboxylic acid monomer, an acrylic monomer having a hydroxyl group, and an acrylic monomer containing an epoxy group, and an unsaturated silane monomer, And 30 to 100 parts by weight of a mixture of a monomer and a monomer is mixed with water and a surfactant in a state in which a certain amount of a water-soluble polymer is added to the reactor, and a crosslinking reaction with a certain amount of a base monomer together with an initiator Is added dropwise and stirred, The polymerization reaction is obtained an acrylic emulsion resin.
상기 베이스모노머는 알킬기의 탄소수가 1 ~ 14인 아크릴산에스테르계 또는 메타아크릴산에스테르계 모노머와, 초산비닐계 모너머와, 스티렌계모노머 중 선택된 어느 하나 또는 둘 이상이 혼합된 것으로, 상기 아크릴산에스테르계 모노머는 아크릴산메틸, 아크릴산에틸, 아크릴산부틸, 아크릴산펜틸, 아크릴산헥실, 아크릴산-2-에틸헥실, 아크릴산헵틸, 아크릴산옥틸, 아크릴산노닐, 아크릴산데실, 아크릴산운데실, 아크릴산도데실, 아크릴산트리데실, 아크릴산테트라데실이고, 상기 메타아크릴산에스테르계 모노머는 메타아크릴산메틸, 메타아크릴산에틸, 메타아크릴산부틸, 메타아크릴산펜틸, 메타아크릴산헥실, 메타아크릴산-2-에틸헥실, 메타아크릴산헵틸, 메타아크릴산옥틸, 메타아크릴산노닐, 메타아크릴산데실, 메타아크릴산운데실, 메타아크릴산도데실, 메타아크릴산트리데실, 메타아크릴산테트라데실 중 선택된 어느 하나 또는 둘 이상이 사용되며, 상기 초산비닐계 모노머는 비닐아세테이트, 베르사틱산 중 선택된 어느 하나 또는 둘 이상이 사용되고, 상기 스티렌계 모너머는 스티렌, 알파메틸스티렌, 파라메틸스티렌 중 선택된 어느 하나 또는 둘 이상이 사용되는데, 상기 베이스모노머는 수용성폴리머 100중량부에 대하여 400 ~ 800중량부의 범위로 첨가혼합되며, 베이스모노머가 400중량부 미만으로 첨가되는 경우에는 최종 생성물인 아크릴에멀젼수지의 점착성이 매우 저하되어 접착력이 없어지고 800중량부를 초과하여 첨가되는 경우에는 점착성은 상승되나 접착성과 응집성이 현저하게 저하되는 문제점이 발생된다.
The base monomer is a mixture of at least one selected from an acrylate ester or methacrylate ester monomer having an alkyl group of 1 to 14 carbon atoms, a vinyl acetate monomer, and a styrene monomer, and the acrylic ester monomer Is preferably a polymer having at least one of methyl acrylate, ethyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, And the methacrylic ester monomer is selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate Decyl acrylate, undecyl methacrylate, meta-arc At least one selected from the group consisting of vinyl acetate and versatilic acid is used as the vinyl acetate-based monomer, and the styrene-based monomer is at least one selected from the group consisting of vinyl acetate, Styrene, alpha methyl styrene, and paramethyl styrene. The base monomer is added and mixed in a range of 400 to 800 parts by weight based on 100 parts by weight of the water-soluble polymer. When the base monomer is less than 400 parts by weight When the emulsion is added, the acrylic emulsion resin, which is the final product, is very low in adhesiveness, and when it is added in an amount exceeding 800 parts by weight, the tackiness is increased but the adhesiveness and cohesiveness are remarkably lowered.
상기 관능성모노머혼합물은 가교반응을 통해 아크릴에멀젼수지에 점착성을 부여하기 위한 것으로, 불포화 실란계 모노머가 불포화 모노카르본산계 모노머, 수산기를 갖는 아크릴계 모노머, 에폭시기를 함유하는 아크릴계 모노머 중 선택된 어느 하나 또는 둘 이상과 중합을 통해 코폴리머를 형성하면서 상온 또는 가열건조시 외첨 경화제 없이도 스스로 가교반응을 통해 가교구조를 형성(self crosslinking type)하게 되는데, 이에 해당되는 불포화 실란계 모노머는 비닐트리메톡시실란, 비닐트리에톡시실란, 3-메타크릴옥시프로필트리메톡시실란, 3-메타크릴옥시프로필트리에톡시실란 중 선택된 어느 하나 또는 둘 이상이 사용되며, 상기 불포화 모노카르본산계 모노머는 아크릴산, 메타아크릴산, 크로톤산 중 선택된 어느 하나 또는 둘 이상이 사용되고, 상기 수산기를 갖는 아크릴계 모노머는 2-히드록시에틸아크릴레이트, 2-히드록시에틸메타아크릴레이트, 2-히드록시프로필아크릴레이트, 2-히드록시프로필메타아크릴레이트 중 선택된 어느 하나 또는 둘 이상이 사용되며, 상기 에폭시기를 함유하는 아크릴계 모노머는 글리시딜아크릴레이트, 글리시딜메타크릴레이트가 사용되는데, 상기 불포화 실란계 모노머는 분자말단에 존재하는 3개의 메톡시기(-OCH3)가 수산기(-OH)나 카르복실기(-COOH)와 결합하여 축합(탈수)되면서 가교구조를 형성하게 된다.
The functional monomer mixture is used for imparting tackiness to the acrylic emulsion resin through a crosslinking reaction. It is preferable that the unsaturated silane monomer is any one selected from an unsaturated monocarboxylic acid monomer, an acrylic monomer having a hydroxyl group, and an acrylic monomer containing an epoxy group A self-crosslinking type is formed through self-crosslinking reaction at room temperature or heating and drying without external curing agent, and the unsaturated silane-based monomer corresponding to the crosslinking structure is vinyltrimethoxysilane, Vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane, and the unsaturated monocarboxylic acid-based monomer is selected from the group consisting of acrylic acid, methacrylic acid , And crotonic acid are used, The acrylic monomer having a hydroxyl group may be any one or two or more selected from among 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate, Glycidyl acrylate and glycidyl methacrylate are used as the acrylic monomer containing an epoxy group. In the unsaturated silane-based monomer, the three methoxy groups (-OCH 3 ) present at the molecular ends are replaced by a hydroxyl group (-OH) Or a carboxyl group (-COOH) to be condensed (dehydrated) to form a crosslinked structure.
상기 관능성모노머혼합물은 불포화 실란계 모노머 12 ~ 24중량부와, 불포화 모노카르본산계 모노머, 수산기를 갖는 아크릴계 모노머, 에폭시기를 함유하는 아크릴계 모노머 중 선택된 어느 하나 또는 둘 이상의 혼합물 18 ~ 76중량부가 혼합되어 수용성폴리머 100중량부에 대하여 30 ~ 100중량부의 범위로 사용되며, 30중량부 미만으로 첨가혼합되면 최종 생성물인 아크릴에멀젼수지의 가교력이 부족하여 최종 점착제품의 응집력이 저하되어 사용할 수 없게 되고, 100중량부를 초과하면 최종 생성물의 점착성(Tack)이 저하되는 문제점이 발생된다.
The functional monomer mixture is prepared by mixing 12 to 24 parts by weight of an unsaturated silane-based monomer and 18 to 76 parts by weight of a mixture of any one selected from an unsaturated monocarboxylic acid monomer, an acrylic monomer having a hydroxyl group, and an acrylic monomer containing an epoxy group, When the amount of the water-soluble polymer is less than 30 parts by weight based on 100 parts by weight of the water-soluble polymer, the crosslinking ability of the acrylic emulsion resin as a final product is insufficient and the cohesive force of the final pressure- And if it exceeds 100 parts by weight, the tack of the final product is lowered.
또한, 본 발명에서는 복합 가교반응을 위하여 관능성모노머혼합물로 아크릴아미드계 모노머 16 ~ 32중량부가 포함된 공중합체에 아디프산 디하이드라지드(adipic dihydrazide) 8 ~ 20중량부를 혼합하여 아크릴에멀젼수지를 제조함으로써 상온 또는 가열건조시 외첨 경화제 없이도 스스로 가교반응을 통해 가교구조를 형성(self crosslinking type)하도록 할 수 있는데, 상기 아크릴아미드계 모노머는 아크릴아미드, 메타크릴아미드, 디아세톤아크릴아미드 중 선택된 어느 하나 또는 둘 이상이 사용되며 아크릴아미드계 모노머의 케톤기(-C=O) 1개가 아디프산 디하이드라지드의 2개의 아미노기(-NH2) 말단에 결합하여 축합(탈수)반응으로 가교구조를 형성하게 된다.
Also, in the present invention, 8 to 20 parts by weight of adipic dihydrazide is mixed with a copolymer containing 16 to 32 parts by weight of an acrylamide monomer as a functional monomer mixture for a complex crosslinking reaction to obtain an acrylic emulsion resin A crosslinking structure can be formed through self-crosslinking reaction at room temperature or by heating and drying without using an external hardener. The acrylamide-based monomer may be selected from acrylamide, methacrylamide, and diacetone acrylamide One or two or more ketone groups (-C═O) of the acrylamide-based monomer are bonded to the two amino group (-NH 2 ) ends of the adipic acid dihydrazide and condensation (dehydration) .
상기 복합 가교반응시 본 발명에서는 수용성폴리머 100중량부에 대하여 베이스모노머 400 ~ 800중량부와, 관능성모노머혼합물로 불포화 모노카르본산계 모노머, 수산기를 갖는 아크릴계 모노머, 에폭시기를 갖는 아크릴계 모노머 중 선택된 어느 하나 또는 둘 이상과 불포화 실란계 모노머 14 ~ 68중량부와 아크릴아미드계 모노머 16 ~ 32중량부를 혼합한 다음 유화중합법으로 공중합시킨 후 반응기를 40 ~ 60℃로 냉각한 상태에서 아디프산 디하이드라지드(adipic dihydrazide) 8 ~ 20중량부를 혼합하여 복합 가교반응을 통해 아크릴에멀젼수지가 얻어지도록 되어 있다.
In the complex crosslinking reaction, in the present invention, 400 to 800 parts by weight of a base monomer is mixed with 100 parts by weight of a water-soluble polymer, and an acrylic monomer having an unsaturated monocarboxylic acid monomer, an acrylic monomer having a hydroxyl group and an epoxy group as a functional monomer mixture 14 to 68 parts by weight of an unsaturated silane-based monomer and 16 to 32 parts by weight of an acrylamide-based monomer are copolymerized by emulsion polymerization, and then the reactor is cooled to 40 to 60 DEG C, And 8-20 parts by weight of adipic dihydrazide are mixed to obtain an acrylic emulsion resin through a complex crosslinking reaction.
상기와 같이 수용성폴리머와 베이스모노머와 관능성모노머혼합물을 중합반응으로 공중합시켜 완성된 아크릴에멀젼수지는 유리전이온도가 -60℃ ~ -30℃ 범위내에 해당되는데, 유리전이온도가 -30℃를 초과하면 점착성이 부족하여 바탕소재에 부착하였을 경우 뜨거나 이탈되는 문제가 있어 제품화가 불가능하고, -60℃ 미만인 경우에는 접착성과 응집력이 너무 저하되어 본 발명의 사용목적에 적합하지 않게 된다.
As described above, the acrylic emulsion resin obtained by copolymerizing the water-soluble polymer, the base monomer and the functional monomer mixture by polymerization reaction has a glass transition temperature within the range of -60 ° C. to -30 ° C. When the glass transition temperature exceeds -30 ° C. If it is adhered to a base material, there is a problem that it is floated or released, so that it can not be commercialized. When it is less than -60 ° C, adhesion and cohesive force are too low and it is not suitable for the purpose of use of the present invention.
또한, 본 발명에서는 중합반응을 위한 계면활성제로서, 페놀을 포함하지 않는 계면활성제 중 비이온성 계면활성제로 각종 알코올류, 메르캅탄류, 폴리에틸렌옥시드가 부가된 라우릴에테르로서 국내 동남합성(주)의 상품명 LE-1030(EO.20몰부가), LE-1025(EO.15몰부가)와, 폴리에틸렌옥시드 부가된 세틸에테르로서 국내 동남합성(주)의 상품명 CE-1025(EO.15몰부가) 및 한농화성(주)의 상품명 KOREMUL-FN(EO,PO 40몰부가) 등이 사용되며, 음이온성 계면활성제로는 소듐도데실설포네이트가 주성분인 국내 동남합성(주)의 상품명 EU-SA 210l(50% SDBS), 100% Flake형 소듐라우릴설페이트, 소듐데실설페이트, 메타크록시알킬 소디움설포네이트가 주성분인 일본국 산요화성(주)의 상품명 ELEMINOL JS-2, ELEMINOL JS-20, ELEMINOL RS-30 등이 사용된다.In the present invention, as the surfactant for the polymerization reaction, a nonionic surfactant among phenol-free surfactants, lauryl ether having various alcohols, mercaptans, and polyethylene oxide added thereto, CE-1025 (EO, 15 moles) of LE-1025 (EO.20 molar addition), LE-1030 (EO.20 molar addition) and polyethylene oxide addition cetyl ether, And KOREMUL-FN (EO, PO 40 moles of addition) of Hannong Chemical Co., Ltd. are used. As the anionic surfactant, EU-SA 210l (trade name, product of Southeast Chemical Co., Ltd.), which is mainly composed of sodium dodecylsulfonate, ELEMINOL JS-2, ELEMINOL JS-20, ELEMINOL RS (trade name, manufactured by Sanyo Chemical Industries, Ltd., Japan), which is a main ingredient of sodium lauryl sulfate, sodium decyl sulfate and methacryloxyalkylsulfonate, -30 < / RTI >
상기 비이온성 계면활성제와 음이온성 계면활성제는 경우에 따라 비이온성 계면활성제 단독 또는 음이온성 계면활성제와 병용하여 사용하게 된다.
The nonionic surfactant and the anionic surfactant may be used in combination with a nonionic surfactant or an anionic surfactant, as the case may be.
또한, 본 발명에서는 중합반응을 위한 개시제(촉매)로서, 소듐퍼설페이트, 포타슘퍼설페이트, 소듐비설페이트 등이 일정량 첨가 사용된다.
In the present invention, a certain amount of sodium persulfate, potassium persulfate, sodium bisulfate or the like is added as an initiator (catalyst) for the polymerization reaction.
한편, 본 발명에서는 점착 3물성(접착력, 점착력, 응집력)의 조정을 위해 점착부여수지가 첨가될 수 있는데, 상기 점착부여수지는 수용성폴리머 100중량부에 대하여 40 ~ 80중량부 첨가혼합되며, 이러한 점착부여수지로는 Dibasic acid modified rosin ester 성분의 제품으로 미국 Hercules사의 상품명 Pentalyn 269가 사용되고, 쿠마론인덴수지 성분의 제품으로 국내 코오롱석유(주)의 상품명 HIKOTACK C-90과 C-120이 사용되며, 일본국 Arakawa Chemical사의 상품명 Super Ester E-70, E-730-55, E-865, E-865NT 등이 사용된다.
In the present invention, an adhesion-imparting resin may be added for adjusting the adhesive properties (adhesion, cohesion and cohesion). The adhesion-imparting resin is added and mixed in an amount of 40 to 80 parts by weight based on 100 parts by weight of the water-soluble polymer. As the tackifier resin, Pentalyn 269, a product of Hercules, USA, is used as a product of dibasic acid modified rosin ester, and products of coumaroneindene resin are commercially available under the trade names HIKOTACK C-90 and C-120 of Kolon Petroleum Co., , Super Ester E-70, E-730-55, E-865 and E-865NT manufactured by Arakawa Chemical Co., Ltd. of Japan.
본 발명에 따른 구체적인 실시예는 다음과 같다.A specific embodiment according to the present invention is as follows.
< 실시예 1 >≪ Example 1 >
반응기 내에 물 142g, 비이온성 계면활성제(한국 한농화성(주), 상품명 KOREMUL-FN) 2.4g, n-도데실메르캅탄(n-dodecyl mercaptan) 1.6g, 에탄올 3g, 음이온성 계면활성제(일본 Sanyo화성(주), 상품명 Eleminol RS-30) 1.2g을 넣어 75℃까지 가온하면서 교반시켜 용해하고 30분간 질소가스로 치환 후 개시제(촉매)로 3% 포타슘퍼설페이트(Potassium persulfate) 수용액 19.4g과, 에틸아크릴레이트(Ethyl acrylate) 40g, 부틸아크릴레이트(Butyl acrylate) 33g, 아크릴산(Acrylic acid) 18g으로 이루어진 산가가 153mg-KOH/g이고 유리전이온도 -21.2℃인 모노머혼합물을 적하하되, 적하개시 30분 후 반응기의 내부온도를 80℃로 가온하면서 3시간 30분 동안 연속적하하며, 적하종료 후 반응기를 냉각하여 40℃가 되면 25% 암모니아수 28g을 첨가하여 중화한 후 물 60g을 가하여 수용화시켜 수용성폴리머를 얻는다.In the reactor, 142 g of water, 2.4 g of a nonionic surfactant (trade name KOREMUL-FN, manufactured by Hanjin Chemical Co., Ltd.), 1.6 g of n-dodecyl mercaptan, 3 g of ethanol and 3 g of an anionic surfactant (Product name: Eleminol RS-30), and the mixture was stirred and dissolved while being heated to 75 占 폚. After replacing with nitrogen gas for 30 minutes, 19.4 g of 3% potassium persulfate aqueous solution as an initiator (catalyst) 40 g of ethyl acrylate, 33 g of butylacrylate and 18 g of acrylic acid was 153 mg-KOH / g After 30 minutes from the start of the dropwise addition, the internal temperature of the reactor was kept at 80 DEG C for 3 hours and 30 minutes. After completion of the dropwise addition, the reactor was cooled to 25 DEG C at 40 DEG C, 28 g of ammonia water is added to neutralize and then 60 g of water is added thereto to obtain a water-soluble polymer.
다음으로, 수용성폴리머 100g에 물 150g, 비이온성 계면활성제(한국 한농화성(주), 상품명 KOREMUL-FN) 15g를 넣어 72℃로 가온하면서 교반 용해한 후 개시제(촉매)로 10% 소듐퍼설페이트(Sodium persulfate) 수용액 30g 및 5% 소듐비설파이트(Sodium bisulfite) 수용액 30g과, 베이스모노머로서 부틸아크릴레이트(Buthyl acrylate) 172g, 2-에틸헥실아크릴레이트(2-Ethylhexyl acrylate) 360g, 도데실아크릴레이트(Dodecyl acrylate) 123g, 메틸메타아크릴레이트(Methyl methacrylate) 33g과, 관능성모노머혼합물로서 2-히드록시에틸메타아크릴레이트(2-Hydroxyethyl methacrylate) 38g, 메타아크릴산(Methacrylic acid) 7.2g, 3-메타크릴옥시트리메톡시실란(3-methacryloxy trimethoxy silane) 1.5g과, 디아세톤아크릴아미드(diacetone acrylamide) 19g를 적하하되, 적하개시 30분 후 반응기의 내부온도를 80℃로 가온하면서 3시간 30분 동안 연속적하하며, 적하종료 후 반응기를 냉각하여 50℃가 되면 아디프산 디하이드라지드(Adipic dihydrazide) 9.69g을 첨가하고 균일하게 분산하여 유리전이온도 -44℃인 아크릴에멀젼수지를 얻었다.
Next, 150 g of water and 15 g of a nonionic surfactant (trade name KOREMUL-FN) were added to 100 g of the water-soluble polymer, and the mixture was stirred and dissolved while being heated to 72 캜. 10% sodium persulfate 30 g of sodium persulfate aqueous solution and 30 g of an aqueous solution of 5% sodium bisulfite and 172 g of buthyl acrylate as a base monomer, 360 g of 2-ethylhexyl acrylate and 300 g of dodecyl acrylate acrylate, 33 g of methyl methacrylate, 38 g of 2-hydroxyethyl methacrylate as a functional monomer mixture, 7.2 g of methacrylic acid, 3 g of 3-methacryloxy 1.5 g of 3-methacryloxy trimethoxy silane and 19 g of diacetone acrylamide were dropwise added thereto. After 30 minutes from the start of the dropwise addition, the internal temperature of the reactor was raised to 80 ° C, And, and, to cool the reactor after completion of the addition when the 50 ℃ adipic acid di-hydrazide (Adipic dihydrazide) 9.69g was added to and uniformly dispersed to obtain an acrylic emulsion resin with a glass transition temperature of -44 ℃.
< 실시예 2 >≪ Example 2 >
반응기 내에 물 142g, 비이온성 계면활성제(한국 동남합성(주), 상품명 LE-30) 5.4g, n-도데실메르캅탄(n-dodecyl mercaptan) 2.0g, 에탄올 3g, 음이온성 계면활성제(한국 동남합성(주), 상품명 EU-SA 210L) 2.2g을 넣어 75℃까지 가온하면서 교반시켜 용해하고 30분간 질소가스로 치환 후 개시제(촉매)로 3% 포타슘퍼설페이트(Potassium persulfate) 수용액 19.4g과, 에틸아크릴레이트(Ethyl acrylate) 20g, 부틸아크릴레이트(Butyl acrylate) 53g, 메타아크릴산(Methacrylic acid) 18g로 이루어진 산가가 128mg-KOH/g이고 유리전이온도 -25℃인 모노머혼합물을 적하하되, 적하개시 30분 후 반응기의 내부온도를 80℃로 가온하면서 3시간 30분 동안 연속적하하며, 적하종료 후 반응기를 냉각하여 40℃가 되면 25% 암모니아수 28g을 첨가하여 중화한 후 물 60g을 가하여 수용화시켜 수용성폴리머를 얻는다.In the reactor, 142 g of water, 5.4 g of a nonionic surfactant (trade name: LE-30, manufactured by Dongnam Chemical Industries, Ltd.), 2.0 g of n-dodecyl mercaptan, 3 g of ethanol and an anionic surfactant (Product name: EU-SA 210L), and the mixture was stirred and dissolved while being heated to 75 캜. After replacing with nitrogen gas for 30 minutes, 19.4 g of 3% potassium persulfate aqueous solution as an initiator (catalyst) 20 g of ethyl acrylate, 53 g of butylacrylate and 18 g of methacrylic acid was 128 mg-KOH / g After 30 minutes from the start of the dropwise addition, the internal temperature of the reactor was kept at 80 DEG C for 3 hours and 30 minutes. After the completion of the dropwise addition, the reactor was cooled to 25 DEG C at 40 DEG C, 28 g of ammonia water is added to neutralize and then 60 g of water is added thereto to obtain a water-soluble polymer.
다음으로, 수용성폴리머 100g에 물 180g, 비이온성 계면활성제(한국 동남합성(주), 상품명 LE-30) 15g를 넣어 72℃로 가온하면서 교반 용해한 후 개시제(촉매)로 10% 소듐퍼설페이트(Sodium persulfate) 수용액 30g 및 5% 소듐비설파이트(Sodium bisulfite) 수용액 30g과, 베이스모노머로서 부틸아크릴레이트(Buthyl acrylate) 139g, 2-에틸헥실아크릴레이트(2-Ethylhexyl acrylate) 324g, 도데실메타아크릴레이트(Dodecyl methacrylate) 123g, 메틸메타아크릴레이트(Methyl methacrylate) 103g과, 관능성모노머혼합물로서 2-히드록시에틸메타아크릴레이트(2-Hydroxyethyl methacrylate) 38g, 아크릴산(acrylic acid) 7g, 3-메타크릴옥시프로필트리메톡시실란(3-methacryloxypropyl trimethoxy silane) 2g과, 디아세톤아크릴아미드(diacetone acrylamide) 19g를 적하하되, 적하개시 30분 후 반응기의 내부온도를 80℃로 가온하면서 3시간 30분 동안 연속적하하며, 적하종료 후 반응기를 냉각하여 50℃가 되면 아디프산 디하이드라지드(Adipic dihydrazide) 9.7g을 첨가하고 균일하게 분산하여 유리전이온도 -41℃인 아크릴에멀젼수지를 얻었다.
Next, 15 g of a nonionic surfactant (trade name: LE-30, manufactured by Dongnam Chemical Industries, Ltd.) was added to 100 g of the water-soluble polymer, and the mixture was stirred and dissolved while being heated to 72 캜. 10% sodium persulfate 30 g of sodium persulfate aqueous solution and 30 g of an aqueous solution of 5% sodium bisulfite and 139 g of butyl acrylate as a base monomer, 324 g of 2-ethylhexyl acrylate, Dodecyl methacrylate), 103 g of methyl methacrylate, 38 g of 2-hydroxyethyl methacrylate as a functional monomer mixture, 7 g of acrylic acid, 3 g of 3-methacryloxypropyl 2 g of 3-methacryloxypropyl trimethoxy silane and 19 g of diacetone acrylamide were dropped. After 30 minutes from the start of the dropwise addition, the internal temperature of the reactor was raised to 80 ° C for 3 hours and 30 minutes After completion of the dropwise addition, the reactor was cooled. When the temperature reached 50 占 폚, 9.7 g of adipic dihydrazide was added and uniformly dispersed to obtain an acrylic emulsion resin having a glass transition temperature of -41 占 폚.
< 실시예 3 >≪ Example 3 >
반응기 내에 물 142g, 비이온성 계면활성제(한국 한농화성(주), 상품명 KOREMUL-FN) 5.4g, n-도데실메르캅탄(n-dodecyl mercaptan) 2.0g, 에탄올 3g, 음이온성 계면활성제(일본 Sanyo화성(주), 상품명 Eleminol RS-30) 2.2g을 넣어 75℃까지 가온하면서 교반시켜 용해하고 30분간 질소가스로 치환 후 개시제(촉매)로 3% 포타슘퍼설페이트(Potassium persulfate) 수용액 19.4g과, 에틸아크릴레이트(Ethyl acrylate) 20g, 부틸아크릴레이트(Butyl acrylate) 53g, 메타아크릴산(Methacrylic acid) 12g, 아크릴산(Acrylic acid) 6g으로 이루어진 산가가 137mg-KOH/g이고 유리전이온도 -25℃인 모노머혼합물을 적하하되, 적하개시 30분 후 반응기의 내부온도를 80℃로 가온하면서 3시간 30분 동안 연속적하하며, 적하종료 후 반응기를 냉각하여 40℃가 되면 25% 암모니아수 28g을 첨가하여 중화한 후 물 60g을 가하여 수용화시켜 수용성폴리머를 얻는다.In the reactor, 142 g of water, 5.4 g of a nonionic surfactant (trade name KOREMUL-FN, manufactured by Hanjin Cement Co., Ltd.), 2.0 g of n-dodecyl mercaptan, 3 g of ethanol and 3 g of an anionic surfactant (Product name: Eleminol RS-30), and the mixture was stirred and dissolved while being heated to 75 占 폚. After replacing with nitrogen gas for 30 minutes, 19.4 g of 3% potassium persulfate aqueous solution as an initiator (catalyst) 20 g of ethyl acrylate, 53 g of butylacrylate, 12 g of methacrylic acid and 6 g of acrylic acid was 137 mg-KOH / g After 30 minutes from the start of the dropwise addition, the internal temperature of the reactor was kept at 80 DEG C for 3 hours and 30 minutes. After the completion of the dropwise addition, the reactor was cooled to 25 DEG C at 40 DEG C, 28 g of ammonia water is added to neutralize and then 60 g of water is added thereto to obtain a water-soluble polymer.
다음으로, 수용성폴리머 100g에 물 180g, 비이온성 계면활성제(한국 한농화성(주), 상품명 KOREMUL-FN) 18g를 넣어 72℃로 가온하면서 교반 용해한 후 개시제(촉매)로 10% 소듐퍼설페이트(Sodium persulfate) 수용액 30g 및 5% 소듐비설파이트(Sodium bisulfite) 수용액 30g과, 베이스모노머로서 부틸아크릴레이트(Buthyl acrylate) 137g, 2-에틸헥실아크릴레이트(2-Ethylhexyl acrylate) 409g, 도데실메타아크릴레이트(Dodecyl methacrylate) 137g, 메틸메타아크릴레이트(Methyl methacrylate) 32g과, 관능성모노머혼합물로서 2-히드록시에틸아크릴레이트(2-Hydroxyethyl acrylate) 40g, 아크릴산(acrylic acid) 11.4g, 3-메타크릴옥시프로필트리메톡시실란(3-methacryloxypropyl trimethoxy silane) 11.4g를 적하하되, 적하개시 30분 후 반응기의 내부온도를 80℃로 가온하면서 3시간 30분 동안 연속적하하며, 적하종료 후 반응기를 냉각하여 50℃가 되면 점착부여수지(일본 Arakawa Chemical사, 상품명 Super Ester E-70) 60g을 첨가하고 균일하게 분산하여 유리전이온도 -47.4℃인 아크릴에멀젼수지를 얻었다.
Next, 180 g of water and 18 g of a nonionic surfactant (trade name KOREMUL-FN) were added to 100 g of the water-soluble polymer, and the mixture was stirred and dissolved while being heated to 72 캜. 10% sodium persulfate 30 g of an aqueous solution of sodium persulfate and 30 g of an aqueous solution of 5% sodium bisulfite and 137 g of butyl acrylate as a base monomer, 409 g of 2-ethylhexyl acrylate and 40 g of dodecylmethacrylate Dodecyl methacrylate (137 g), 32 g of methyl methacrylate, 40 g of 2-hydroxyethyl acrylate, 11.4 g of acrylic acid, 3 g of 3-methacryloxypropyl acrylate as a functional monomer mixture After 30 minutes from the start of the dropwise addition, 11.4 g of 3-methacryloxypropyl trimethoxy silane was dropwise added. The internal temperature of the reactor was kept at 80 ° C. for 3 hours and 30 minutes. After completion of the dropwise addition, When the 50 ℃ tackifier (Arakawa Chemical Japan Corporation, trade name: Super Ester E-70) was added to 60g and uniformly dispersed to obtain an acrylic emulsion resin with a glass transition temperature of -47.4 ℃.
< 실시예 4 ><Example 4>
실시예1과 동일한 방법으로 수용성폴리머를 얻는 다음 상기 수용성폴리머 100g에 물 180g, 비이온성 계면활성제(한국 한농화성(주), 상품명 KOREMUL-FN) 18g를 넣어 72℃로 가온하면서 교반 용해한 후 개시제(촉매)로 10% 소듐퍼설페이트(Sodium persulfate) 수용액 30g 및 5% 소듐비설파이트(Sodium bisulfite) 수용액 30g과, 베이스모노머로서 에틸아크릴레이트(Ethyl acrylate) 19g, 부틸아크릴레이트(Buthyl acrylate) 99g, 2-에틸헥실아크릴레이트(2-Ethylhexyl acrylate) 406g, 도데실메타아크릴레이트(Dodecyl methacrylate) 123g, 스티렌(styrene) 70g과, 관능성모노머혼합물로서 2-히드록시에틸아크릴레이트(2-Hydroxyethyl acrylate) 40g, 아크릴산(Acrylic acid) 11.4g, 3-메타크릴옥시프로필트리메톡시실란(3-methacryloxypropyl trimethoxy silane) 11.4g를 적하하되, 적하개시 30분 후 반응기의 내부온도를 80℃로 가온하면서 3시간 30분 동안 연속적하하며, 적하종료 후 반응기를 냉각하여 50℃가 되면 점착부여수지(미국 Hercules사의 상품명 Pentalyn 269) 60g을 첨가하고 균일하게 분산하여 유리전이온도 -49.7℃인 아크릴에멀젼수지를 얻었다.
180 g of water and 18 g of a nonionic surfactant (trade name: KOREMUL-FN) were added to 100 g of the water-soluble polymer in the same manner as in Example 1, and the mixture was stirred and dissolved while being heated to 72 캜. 30 g of an aqueous solution of 10% sodium persulfate and 30 g of an aqueous solution of 5% sodium bisulfite as a catalyst and 19 g of ethyl acrylate as a base monomer, 99 g of butylacrylate, 406 g of 2-ethylhexyl acrylate, 123 g of dodecyl methacrylate, 70 g of styrene and 40 g of 2-hydroxyethyl acrylate as a functional monomer mixture , 11.4 g of acrylic acid and 11.4 g of 3-methacryloxypropyl trimethoxy silane were dropped. After 30 minutes from the start of the dropwise addition, the internal temperature of the reactor was raised to 80 ° C., After the dropping, the reactor was cooled. When the temperature reached 50 ° C, 60 g of a tackifier resin (Pentalyn 269 available from Hercules, USA) was added and uniformly dispersed to obtain an acrylic emulsion resin having a glass transition temperature of -49.7 ° C .
< 비교예 1> ≪ Comparative Example 1 &
현재 시판되고 있는 본 출원인(성림크로바(주))의 아크릴에멀젼수지, 상품명 SR-1300B을 비교예 1로 사용하였으며, 비교예 1의 주성분은 부틸아크릴레이트(Butyl acrylate)와 2-에틸헥실아크릴레이트(2-Ethylhexyl acrylate)이고 메틸메타아크릴레이트(Methyl methacrylate)와 아크릴산(Acrylic acid)을 기타 성분으로 포함하여 스티커 라벨용 점착제로 사용되는 제품이다.
The acrylic emulsion resin (SR-1300B) of the present applicant (Seongrim CROBA Co., Ltd.) currently marketed was used as Comparative Example 1, and the main component of Comparative Example 1 was butyl acrylate and 2-ethylhexyl acrylate (2-Ethylhexyl acrylate), Methyl methacrylate and Acrylic acid as other ingredients, and is used as a sticker for sticker labels.
< 비교예 2 >≪ Comparative Example 2 &
국내에서 현재 시판되고 있는 태일화학(주)의 아크릴에멀젼수지, 상품명 TI-711을 비교예 2로 사용하였으며, 비교예 2의 주성분은 부틸아크릴레이트(Butyl acrylate)와 2-에틸헥실아크릴레이트(2-Ethylhexyl acrylate)이고 스티렌(Styrene)과 2-히드록시에틸메타아크릴레이트(2-Hydroxyethyl methacrylate)와 아크릴산(Acrylic acid)을 기타 성분으로 포함하여 필름과 페이퍼간의 라미네이션 접착제로 사용되는 제품이다.
The acrylic emulsion resin commercially available from Taeil Chemical Co., Ltd., trade name TI-711, which is currently available in the country, was used as Comparative Example 2, and the main component of Comparative Example 2 was butyl acrylate (2-ethylhexyl acrylate) -Ethylhexyl acrylate. It is used as lamination adhesive between film and paper, including styrene, 2-hydroxyethyl methacrylate and acrylic acid as other components.
< 비교예 3 >≪ Comparative Example 3 &
국내에서 현재 시판되고 있는 영은화학(주)의 아크릴에멀젼수지, 제품명 HM-300을 비교예 3으로 사용하였으며, 비교예 3의 주성분은 부틸아크릴레이트(Butyl acrylate)와 2-에틸헥실아크릴레이트(2-Ethylhexyl acrylate)이고 비닐아세테이트(Vinyl acetate)와 아크릴산(Acrylic acid)을 기타 성분으로 포함하여 PE필름과 페이퍼간 접착제 또는 라벨용 점착제로 사용되는 제품이다.
The acrylic emulsion resin commercially available from Yukun Chemical Co., Ltd., HM-300, which is currently available in Korea, was used as Comparative Example 3, and the main components of Comparative Example 3 were butyl acrylate (2-ethylhexyl acrylate) -Ethylhexyl acrylate. It contains vinyl acetate and acrylic acid as other components and is used as adhesive between PE film and paper or adhesive for label.
< 실험예 ><Experimental Example>
상기와 같이 제조된 실시예 1 ~ 4의 아크릴에멀젼수지와 비교예 1 내지 3의 아크릴에멀젼수지를 사용하여 동결전 원액상태의 점착 3물성(접착력, 점착력, 응집력)을 각각 측정하고, 영하 15℃로 3일간 동결시킨 다음 융해시켜 점착 3물성을 재측정하였다.
The adhesive three properties (adhesion, cohesion and cohesive force) of the acrylic emulsion resin of Examples 1 to 4 and the acrylic emulsion resins of Comparative Examples 1 to 3 in the stock solution before freezing were respectively measured, For 3 days, and then melted.
(1) 접착력 (Peel Adhesion)(1) Peel Adhesion
25μm두께의 폴리에스테르필름상에 시료를 각각 50μm 두께로 도포하고 120℃에서 3분간 건조하여 모의 테이프를 만든 다음 폴리에스테르필름의 폭을 1cm로 절단하고 이를 스테인레스 강판위에 부착 후 2kg 하중의 원통롤러로 2회 왕복 압착하여 부착하며, 부착된 모의 테이프를 180°방향으로 벗겨내면서 박리접착력(g/2.54cm)를 측정한다.
Each sample was coated on a 25 μm thick polyester film to a thickness of 50 μm and dried at 120 ° C. for 3 minutes to form a simulated tape. The width of the polyester film was cut to 1 cm and attached to a stainless steel plate. And the peeling adhesive force (g / 2.54 cm) was measured while peeling the attached simulated tape in the direction of 180 °.
(2) 점착력(Tack)(2) Adhesion (Tack)
J. Dow법에 따라 20℃, 상대습도 65%에서 경사각이 30도인 면에 10cm 길이로 각 시료를 도포하고, 경사 윗면 10cm 위치에서 직경이 다른 스틸볼을 크기순으로 차례로 굴려 점착면 상에서 10초 이상 정지하면 이때 최대 지름의 Ball No.를 표시한다.
Each sample was applied to a 10-cm-long surface at a slope angle of 30 ° at 20 ° C and 65% relative humidity according to the J. Dow method. The steel balls having different diameters were sequentially rolled in a 10 cm- If it stops abnormally, Ball No. of the maximum diameter is displayed at this time.
(3) 응집력(Cohesion)(3) Cohesion
접착력 테이스와 동일한 방법으로 모의 테이프를 만든 후 스테인레스 강판으로 된 시험판에 모의 테이프를 가로 25mm, 세로 25mm가 되도록 부착시킨 후 2kg 하중의 롤러로 1회 왕복 압착한 다음 40℃, 상대습도 65%에서 폴리에스테르필름에 1kg의 정하중을 걸어 60분 후 밀린 길이(mm)를 측정한다.
A simulated tape was prepared in the same manner as the adhesion tester, and then a simulated tape was attached to a test plate made of stainless steel to have a width of 25 mm and a length of 25 mm. The test tape was then cyclically pressed once with a roller having a load of 2 kg, The ester film is subjected to a static load of 1 kg, and the length (mm) after 60 minutes is measured.
접착력(g/2.54cm)
Adhesion (g / 2.54 cm)
점착력(Ball No.)
Adhesion (Ball No.)
응집력(mm)
Cohesion (mm)
실시예 1
Example 1
Before freezing
After freeze-thawing
실시예 2
Example 2
Before freezing
After freeze-thawing
실시예 3
Example 3
Before freezing
After freeze-thawing
실시예 4
Example 4
Before freezing
After freeze-thawing
비교예 1
Comparative Example 1
Before freezing
After freeze-thawing
비교예 2
Comparative Example 2
Before freezing
After freeze-thawing
비교예 3
Comparative Example 3
Before freezing
After freeze-thawing
상기 실험에서는 본 발명의 실시예 1 ~ 4는 표 1 및 도 1에서와 같이 동결전,후 물성변화가 거의 없어 우수한 동해안정성을 나타내었으며, 비교예 1 내지 3은 모두 동결전 원액상태에서는 바탕소재에 도포시 코팅성이 좋고 점착성이 양호하였으나 동결 융해 후에는 제품 불량화로 도 1에 도시된 바와 같이 코팅면에 매끄러운 감이 없어지고 거칠어지면서 균일하게 도포되지 않아 표 1에서와 같이 접착력, 점착력, 응집력을 측정할 수 없어 동해안정성이 매우 떨어지는 것을 알 수 있었다.In Examples 1 to 4 of the present invention, as shown in Table 1 and FIG. 1, there was almost no change in physical properties before and after freezing, showing excellent dynamic stability. In Comparative Experiments 1 to 3, The coated surface was good in coating property and good in tackiness, but after the freezing and thawing, as shown in Fig. 1 due to product deterioration, there was no smooth feeling on the coated surface and the coating was not uniformly coated with roughness. As shown in Table 1, It was found that the stability of the frozen sea was very poor.
Claims (9)
An acrylic ester-based or methacrylic ester-based monomer having an alkyl group of 1 to 8 carbon atoms and an unsaturated monocarboxylic acid-based monomer so that the glass transition temperature is -35 to -10 DEG C and the acid value is 110 to 180 mg-KOH / g Copolymerizing the monomer mixture by emulsion polymerization to prepare a water-soluble polymer; 400 to 800 weight parts of a base monomer in which one or more selected from acrylic acid ester or methacrylic ester monomers, vinyl acetate monomers and styrene monomers having an alkyl group of 1 to 14 carbon atoms per 100 parts by weight of the water-soluble polymer And 30 to 100 parts by weight of a functional monomer mixture for a crosslinking reaction in which an unsaturated monocarboxylic acid monomer, an acrylic monomer having a hydroxyl group, and an acrylic monomer containing an epoxy group is mixed with an unsaturated silane monomer Wherein the acrylic emulsion resin is prepared by mixing and copolymerizing with an emulsion polymerization method to prepare an acrylic emulsion resin.
The composition according to claim 1, wherein the functional monomer mixture comprises 12 to 24 parts by weight of an unsaturated silane-based monomer, and at least one selected from an unsaturated monocarboxylic acid monomer, an acrylic monomer having a hydroxyl group, and an acrylic monomer containing an epoxy group And 18 to 76 parts by weight of the acrylic emulsion resin composition is mixed.
An acrylic ester-based or methacrylic ester-based monomer having an alkyl group of 1 to 8 carbon atoms and an unsaturated monocarboxylic acid-based monomer so that the glass transition temperature is -35 to -10 DEG C and the acid value is 110 to 180 mg-KOH / g Copolymerizing the monomer mixture by emulsion polymerization to prepare a water-soluble polymer; 400 to 800 weight parts of a base monomer in which one or more selected from acrylic acid ester or methacrylic ester monomers, vinyl acetate monomers and styrene monomers having an alkyl group of 1 to 14 carbon atoms per 100 parts by weight of the water-soluble polymer And 14 to 68 parts by weight of a mixture of an unsaturated monocarboxylic acid monomer, an acrylic monomer having a hydroxyl group, and an acrylic monomer containing an epoxy group and / or an unsaturated silane monomer as a functional monomer mixture for a crosslinking reaction And 16 to 32 parts by weight of an acrylamide monomer are copolymerized by emulsion polymerization and 8 to 20 parts by weight of adipic acid dihydrazide is added to prepare an acrylic emulsion resin. By weight based on the weight of the acrylic emulsion resin composition.
[6] The method according to claim 1 or 3, wherein the unsaturated monocarboxylic acid monomer is selected from acrylic acid, methacrylic acid, and crotonic acid, and the vinyl acetate-based monomer is selected from vinyl acetate and versatic acid Wherein at least one selected from styrene, alphamethylstyrene, and para-methylstyrene is used as the styrene-based monomer, wherein at least one selected from the group consisting of styrene, alphamethylstyrene, and para-methylstyrene is used.
The method according to any one of claims 1 to 3, wherein the unsaturated silane-based monomer is selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Triethoxysilane, and the unsaturated monocarboxylic acid monomer is selected from acrylic acid, methacrylic acid and crotonic acid, and the acrylic monomer having a hydroxyl group is selected from the group consisting of 2-hydro Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate are used, and the acrylic monomer containing the epoxy group is selected from glycidyl acrylate, Acrylic acid esters having an East Sea stability, characterized by the use of glycidyl methacrylate, Method of producing a paper composition.
The acrylic emulsion resin composition according to claim 1 or 3, wherein the acryl emulsion resin is prepared by mixing 40 to 80 parts by weight of a tackifier resin with respect to 100 parts by weight of the water-soluble polymer. ≪ / RTI >
An acrylic ester-based or methacrylic ester-based monomer having an alkyl group of 1 to 8 carbon atoms and an unsaturated monocarboxylic acid-based monomer so that the glass transition temperature is -35 to -10 DEG C and the acid value is 110 to 180 mg-KOH / g Copolymerizing the monomer mixture by emulsion polymerization to prepare a water-soluble polymer; 400 to 800 weight parts of a base monomer in which one or more selected from acrylic acid ester or methacrylic ester monomers, vinyl acetate monomers and styrene monomers having an alkyl group of 1 to 14 carbon atoms per 100 parts by weight of the water-soluble polymer And 12 to 24 parts by weight of an unsaturated silane-based monomer as a functional monomer mixture for a crosslinking reaction, and an acrylic monomer containing an unsaturated monocarboxylic acid monomer, a hydroxyl group, and an epoxy group And 18 to 76 parts by weight of an acrylic emulsion resin, and then copolymerizing the mixture with an emulsion polymerization method to prepare an acrylic emulsion resin.
An acrylic ester-based or methacrylic ester-based monomer having an alkyl group of 1 to 8 carbon atoms and an unsaturated monocarboxylic acid-based monomer so that the glass transition temperature is -35 to -10 DEG C and the acid value is 110 to 180 mg-KOH / g Copolymerizing the monomer mixture by emulsion polymerization to prepare a water-soluble polymer; 400 to 800 weight parts of a base monomer in which one or more selected from acrylic acid ester or methacrylic ester monomers, vinyl acetate monomers and styrene monomers having an alkyl group of 1 to 14 carbon atoms per 100 parts by weight of the water-soluble polymer And 14 to 68 parts by weight of a mixture of an unsaturated monocarboxylic acid monomer, an acrylic monomer having a hydroxyl group, and an acrylic monomer containing an epoxy group and / or an unsaturated silane monomer as a functional monomer mixture for a crosslinking reaction And 16 to 32 parts by weight of an acrylamide monomer are copolymerized by emulsion polymerization and 8 to 20 parts by weight of adipic acid dihydrazide is added to prepare an acrylic emulsion resin. By weight of the acrylic emulsion resin composition.
The acrylic emulsion resin composition according to claim 7 or 8, wherein the acrylic emulsion resin is prepared by mixing 40 to 80 parts by weight of a tackifier resin with respect to 100 parts by weight of the water-soluble polymer. .
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| KR20180080755A (en) * | 2017-01-05 | 2018-07-13 | (주)시그마소재 | Flame retardant styrofoam produced by using flame retardant vinyl acetate polymer emulsion resin |
| CN108440704A (en) * | 2018-02-28 | 2018-08-24 | 中山市巴德富化工科技有限公司 | A kind of resistance to boiling water height attachment two-component acrylicester lotion and preparation method thereof |
| KR101964008B1 (en) * | 2018-08-21 | 2019-04-01 | 주식회사 쌍곰켐 | Superior acrylic emulsion adhesive composition is freeze and thawing for tile adhesive |
| EP3514184A1 (en) | 2018-01-18 | 2019-07-24 | Kansai Altan Boya Sanayi ve Ticaret Anonim Sirketi | Alkali-soluble emulsion resin and production method |
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