KR20210146614A - Solventless photo cure adhesive composition and manufacturing method of solventless photo cure adhesive - Google Patents
Solventless photo cure adhesive composition and manufacturing method of solventless photo cure adhesive Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 230000001070 adhesive effect Effects 0.000 title claims description 31
- 239000000853 adhesive Substances 0.000 title claims description 30
- ILBBNQMSDGAAPF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-1-one Chemical compound CCC(=O)C1C=CC=CC1(C)O ILBBNQMSDGAAPF-UHFFFAOYSA-N 0.000 title 2
- 239000000178 monomer Substances 0.000 claims abstract description 121
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 88
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 53
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- 238000000034 method Methods 0.000 claims abstract description 21
- 238000000016 photochemical curing Methods 0.000 claims description 39
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- 239000004925 Acrylic resin Substances 0.000 claims description 22
- 229920000178 Acrylic resin Polymers 0.000 claims description 22
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 17
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 17
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 16
- 229920002554 vinyl polymer Polymers 0.000 claims description 16
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000001723 curing Methods 0.000 claims description 14
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 12
- -1 poly(ethylene glycol) Polymers 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 claims description 8
- 230000000977 initiatory effect Effects 0.000 claims description 8
- 230000001678 irradiating effect Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 125000004386 diacrylate group Chemical group 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229930006711 bornane-2,3-dione Natural products 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- LDUNNUKQPKEIJR-UHFFFAOYSA-N 4,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C.C1CC2(C)C(=O)C(=O)C1C2(C)C LDUNNUKQPKEIJR-UHFFFAOYSA-N 0.000 claims description 2
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 abstract description 10
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- 239000003522 acrylic cement Substances 0.000 description 2
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- 239000002253 acid Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- B01J35/004—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
- C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F226/10—N-Vinyl-pyrrolidone
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
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Abstract
Description
본 발명은 무용제형 광경화 점착제 조성물 및 무용제형 광경화 점착제의 제조방법에 관한 것으로, 더욱 구체적으로는 광촉매를 포함하여 첨가제 없이 광조사를 통해 중합 및 경화가 가능한 무용제형 광경화 점착제 조성물 및 무용제형 광경화 점착제의 제조방법을 제공한다.The present invention relates to a solvent-free photo-curing pressure-sensitive adhesive composition and a method for producing a solvent-free photo-curing pressure-sensitive adhesive, and more particularly, to a solvent-free photo-curable pressure-sensitive adhesive composition and solvent-free type that can be polymerized and cured through light irradiation without additives including a photocatalyst A method for manufacturing a photocurable pressure-sensitive adhesive is provided.
광경화 점착제는 디스플레이 산업, 전기전자 산업, 반도체 산업 등 여러 산업분야에 널리 사용되고 있다. 특히 2개 이상의 상이한 소재 또는 부품을 서로 접합하기 위해서는 양쪽 모두 점착력이 우수한 점착제를 사용하여야 한다.The photocurable adhesive is widely used in various industrial fields such as the display industry, the electrical and electronic industry, and the semiconductor industry. In particular, in order to bond two or more different materials or parts to each other, an adhesive having excellent adhesive strength must be used for both.
디스플레이의 경우, 터치 스크린 패널 및 액정 모듈로 구성되며, 상기 터치 스크린 패널은 도전성 필름 및 투명 기재 등의 적층 구조를 갖는다. 이때, 상기 터치 스크린 패널의 적층 구조에 대해 각 층을 부착하는 경우 점착제가 사용되며, 상기 터치 스크린 패널과 액정 모듈을 부착하는 경우에도 점착제가 사용된다. 이러한 용도의 점착제는 터치 민감도, 시인성 등의 물성을 저하시키지 않으면서 우수한 점착성을 구현해야 한다. In the case of a display, it is composed of a touch screen panel and a liquid crystal module, and the touch screen panel has a laminated structure of a conductive film and a transparent substrate. In this case, an adhesive is used when attaching each layer to the laminated structure of the touch screen panel, and an adhesive is also used when attaching the touch screen panel and the liquid crystal module. The pressure-sensitive adhesive for this purpose should implement excellent adhesion without degrading physical properties such as touch sensitivity and visibility.
전기전자 산업 및 반도체 산업에서는 부품의 경박단소화가 요구되는 PC, 노트북, MP3, 핸드폰, PDA, 휴대용 AV 기기와 같은 각종 모바일 단말기기의 핵심부품인 반도체 웨이퍼 제조 공정에도 이용되고 있다. In the electrical and electronic industry and semiconductor industry, it is also used in the semiconductor wafer manufacturing process, which is a core component of various mobile terminal devices such as PC, notebook, MP3, mobile phone, PDA, and portable AV equipment that require light, thin, and compact parts.
광경화 점착제는 적용 분야 및 용도에 따라 요구되는 물성에 차이가 있으므로, 광경화 점착제의 물성을 조절할 수 있는 광경화 점착제 조성물의 개발이 필요하였다. Since the photo-curable pressure-sensitive adhesive has different properties required depending on the field of application and use, it was necessary to develop a photo-curable pressure-sensitive adhesive composition capable of controlling the physical properties of the photo-curable pressure-sensitive adhesive.
또한, 기존의 광경화 점착제는 개시반응을 위해 균일분해에 의해 라디칼을 생성하는 광개시제를 사용하거나, 광촉매를 삼차 아민계열의 공개시제와 함께 사용하였으나, 이를 대체할 첨가제 없이 광전자 전달을 통해 중합 및 경화가 가능한 무용제형 광경화 점착제 조성물의 개발이 요구되었다.In addition, the conventional photo-curing pressure-sensitive adhesive uses a photoinitiator that generates radicals by homogeneous decomposition for the initiation reaction, or a photocatalyst is used together with a tertiary amine-based co-initiator. The development of a solvent-free photocurable pressure-sensitive adhesive composition that can be used was required.
본 발명은 광촉매를 포함하여 광개시제 또는 광촉매-공개시제의 첨가제 없이 광조사를 통해 중합 및 경화가 가능한 무용제형 광경화 점착제 조성물 및 무용제형 광경화 점착제의 제조방법을 제공하기 위한 것이다. An object of the present invention is to provide a solvent-free photocurable pressure-sensitive adhesive composition capable of polymerization and curing through light irradiation without an additive of a photoinitiator or a photocatalyst-coinitiator, including a photocatalyst, and a method for preparing a solvent-free photocurable pressure-sensitive adhesive.
본 발명은 조성물의 구성과 비율을 조절함으로써 광경화 점착제의 물성을 조절할 수 있는 광경화 점착제 조성물 및 무용제형 광경화 점착제의 제조방법을 제공하기 위한 것이다.An object of the present invention is to provide a photo-curable pressure-sensitive adhesive composition capable of controlling the physical properties of the photo-curing pressure-sensitive adhesive by adjusting the composition and ratio of the composition, and a method for producing a solvent-free type photo-curing pressure-sensitive adhesive.
본 발명이 해결하고자 하는 과제는 이상에서 언급한 과제(들)로 제한되지 않으며, 언급되지 않은 또 다른 과제(들)는 이하의 기재로부터 당업자에게 명확하게 이해될 수 있을 것이다.The problem to be solved by the present invention is not limited to the problem(s) mentioned above, and another problem(s) not mentioned will be clearly understood by those skilled in the art from the following description.
상기 목적을 해결하기 위하여, 본 발명은 아크릴계 단량체와 광촉매를 포함하는 조성물에서, 상기 아크릴계 단량체는 질소 함유 비닐계 단량체를 포함하는 것을 특징으로 하는 무용제형 광경화 점착제 조성물을 제공한다.In order to solve the above object, the present invention provides a solvent-free photo-curing pressure-sensitive adhesive composition comprising an acrylic monomer and a photocatalyst, wherein the acrylic monomer includes a nitrogen-containing vinyl monomer.
본 발명의 일 실시예에 따르면, 상기 상기 아크릴계 단량체는, 유리전이온도(Tg)가 낮은 단량체로서 EHA(2-Ethylhexyl acrylate), n-BA(n-butyl acrylate) 중 하나; 유리전이온도(Tg)가 높은 단량체로서 IBOA(Isobornyl acrylate), MMA(methylmethacrylate) 중 하나; 기능성 단량체로서 AA(Acrylic acid), HEA(2-hydroxyethyl acrylate) 중 하나; 및 질소 함유 비닐계 단량체로서 NVP(N-Vinyl-Pyrrolidone), NVC(N-Vinyl-caprolactam) 중 하나;를 함유할 수 있다.According to an embodiment of the present invention, the acrylic monomer may include one of 2-ethylhexyl acrylate (EHA) and n-butyl acrylate (n-BA) as a monomer having a low glass transition temperature (Tg); One of IBOA (Isobornyl acrylate) and MMA (methylmethacrylate) as a monomer having a high glass transition temperature (Tg); One of AA (Acrylic acid) and HEA (2-hydroxyethyl acrylate) as a functional monomer; and one of N-Vinyl-Pyrrolidone (NVP) and N-Vinyl-caprolactam (NVC) as a nitrogen-containing vinylic monomer.
본 발명의 일 실시예에 따르면, 상기 광촉매는 4DP-IPN, 4Cz-IPN, 에오신(eosin Y), 캄포르퀴논(Camphorquinone) 중 하나일 수 있다.According to an embodiment of the present invention, the photocatalyst may be one of 4DP-IPN, 4Cz-IPN, eosin Y, and camphorquinone.
본 발명의 일 실시예에 따르면, 상기 유리전이온도(Tg)가 낮은 단량체는 50 ~ 80 mol%; 상기 유리전이온도(Tg)가 높은 단량체는 5 ~ 30 mol%; 상기 기능성 단량체는 5 ~ 20 mol%; 및 상기 질소 함유 비닐계 단량체는 5 ~ 30 mol%;를 함유할 수 있다.According to an embodiment of the present invention, the monomer having a low glass transition temperature (Tg) is 50 to 80 mol%; The monomer having a high glass transition temperature (Tg) is 5 to 30 mol%; The functional monomer is 5 to 20 mol%; and 5 to 30 mol% of the nitrogen-containing vinylic monomer.
본 발명의 일 실시예에 따르면, 상기 광촉매는 10 ~ 100 ppm 으로 함유할 수 있다.According to an embodiment of the present invention, the photocatalyst may be contained in an amount of 10 to 100 ppm.
또한, 본 발명은 질소 함유 비닐계 단량체를 포함한 아크릴계 단량체와 광촉매를 포함한 조성물에 광조사를 하여 합성된 아크릴 수지에 다관능성 단량체를 혼합한 무용제형 광경화 점착제 조성물을 제공한다.In addition, the present invention provides a solvent-free photo-curing pressure-sensitive adhesive composition in which a polyfunctional monomer is mixed with an acrylic resin synthesized by irradiating a composition including an acrylic monomer including a nitrogen-containing vinyl monomer and a photocatalyst with light.
본 발명의 일 실시예에 따르면, 상기 아크릴 수지는, 광촉매와 미반응된 아크릴 단량체를 함유할 수 있다.According to an embodiment of the present invention, the acrylic resin may contain a photocatalyst and an unreacted acrylic monomer.
본 발명의 일 실시예에 따르면, 상기 다관능성 단량체는 PEGDA(poly(ethylene glycol) diacrylate) 일 수 있다. According to an embodiment of the present invention, the polyfunctional monomer may be PEGDA (poly(ethylene glycol) diacrylate).
또한, 본 발명은 상기 아크릴계 단량체와 광촉매를 포함한 조성물에 광조사를 하여 합성된 아크릴 수지에 다관능성 단량체를 혼합한 무용제형 광경화 점착제 조성물에 광조사를 하여 경화된 것을 특징으로 하는 무용제형 광경화 점착제 조성물을 제공한다.In addition, the present invention is a solvent-free photocuring, characterized in that cured by irradiating light to a solvent-free photocuring pressure-sensitive adhesive composition in which a polyfunctional monomer is mixed with an acrylic resin synthesized by irradiating the composition containing the acrylic monomer and the photocatalyst with light A pressure-sensitive adhesive composition is provided.
본 발명의 일 실시예에 따르면, 상기 광조사는 자외선 또는 가시광선 중 선택된 하나 이상을 이용할 수 있다.According to an embodiment of the present invention, the light irradiation may use at least one selected from ultraviolet light or visible light.
또한, 본 발명은, 질소 함유 비닐계 단량체를 포함한 아크릴계 단량체와 광촉매를 혼합하는 단계(a 단계); 1차 광조사를 통해 아크릴 수지를 합성하는 단계(b 단계); 상기 합성된 아크릴 수지에 다관능성 단량체를 혼합한 후 2차 광조사를 하는 단계(c 단계);를 포함하는 무용제형 광경화 점착제의 제조방법을 제공한다.In addition, the present invention, mixing a photocatalyst with an acrylic monomer including a nitrogen-containing vinyl monomer (step a); synthesizing an acrylic resin through primary light irradiation (step b); After mixing the polyfunctional monomer with the synthesized acrylic resin, the step (c step) of performing secondary light irradiation; provides a method for producing a solvent-free photo-curing pressure-sensitive adhesive comprising a.
본 발명의 일 실시예에 따르면, 상기 아크릴계 단량체는, 유리전이온도(Tg)가 낮은 단량체로서 EHA(2-Ethylhexyl acrylate), n-BA(n-butyl acrylate) 중 하나를 50 ~ 80 mol%; 유리전이온도(Tg)가 높은 단량체로서 IBOA(Isobornyl acrylate), MMA(methylmethacrylate) 중 하나를 5 ~ 30 mol%; 기능성 단량체로서 AA(Acrylic acid), HEA(2-hydroxyethyl acrylate) 중 하나를 5 ~ 20 mol%; 및 질소 함유 비닐계 단량체로서 NVP(N-Vinyl-Pyrrolidone), NVC(N-Vinyl-caprolactam) 중 하나를 5 ~ 30 mol%;로 함유할 수 있다.According to an embodiment of the present invention, the acrylic monomer, as a monomer having a low glass transition temperature (Tg), one of EHA (2-ethylhexyl acrylate), n-BA (n-butyl acrylate) 50 ~ 80 mol%; 5 ~ 30 mol% of either IBOA (Isobornyl acrylate) or MMA (methylmethacrylate) as a monomer having a high glass transition temperature (Tg); 5 to 20 mol% of either AA (Acrylic acid) or HEA (2-hydroxyethyl acrylate) as a functional monomer; and one of NVP (N-Vinyl-Pyrrolidone) and NVC (N-Vinyl-caprolactam) as a nitrogen-containing vinylic monomer in an amount of 5 to 30 mol%;
본 발명의 일 실시예에 따르면, 상기 광촉매는 4DP-IPN, 4Cz-IPN, 에오신(eosin Y), 캄포르퀴논(Camphorquinone) 중 하나를 10 ~ 100 ppm 으로 함유할 수 있다.According to an embodiment of the present invention, the photocatalyst may contain one of 4DP-IPN, 4Cz-IPN, eosin Y, and camphorquinone in an amount of 10 to 100 ppm.
본 발명의 일 실시예에 따르면, 상기 다관능성 단량체는 PEGDA(poly(ethylene glycol) diacrylate) 일 수 있다.According to an embodiment of the present invention, the polyfunctional monomer may be PEGDA (poly(ethylene glycol) diacrylate).
본 발명의 일 실시예에 따르면, 상기 광조사는 자외선 또는 가시광선 중 선택된 하나 이상을 이용할 수 있다.According to an embodiment of the present invention, the light irradiation may use at least one selected from ultraviolet light or visible light.
본 발명의 일 실시예에 따르면, 상기 1차 광조사에 의해 중합반응이 일어나고, 상기 2차 광조사에 의해 경화반응이 일어날 수 있다.According to an embodiment of the present invention, a polymerization reaction may occur by the primary light irradiation, and a curing reaction may occur by the secondary light irradiation.
본 발명의 일 실시예에 따르면, 상기 질소 함유 비닐계 단량체가 광촉매의 개시반응을 촉진하고, 중합반응의 구성성분이 될 수 있다.According to an embodiment of the present invention, the nitrogen-containing vinyl-based monomer may promote the initiation reaction of the photocatalyst and become a component of the polymerization reaction.
본 발명의 일 실시예에 따르면, 상기 b단계의 1차 광조사를 통해 아크릴 수지를 합성하는 전환율은 5 ~ 20 % 일 수 있다.According to an embodiment of the present invention, the conversion rate for synthesizing the acrylic resin through the primary light irradiation in step b may be 5 to 20%.
본 발명에 의한 무용제형 광경화 점착제 조성물 및 무용제형 광경화 점착제 제조방법은, 소모성 광개시제를 함유하지 않고, 광촉매를 포함하여 광전자 전달 반응 사이클을 통해 라디칼을 생성하므로 광개시제와는 달리 중합과정 중 소모되지 않는 효과가 있다.The solvent-free photocurable pressure-sensitive adhesive composition and the solvent-free photocurable pressure-sensitive adhesive manufacturing method according to the present invention do not contain a consumable photoinitiator and contain a photocatalyst to generate radicals through a photoelectron transfer reaction cycle. has no effect.
본 발명에 의한 무용제형 광경화 점착제 조성물 및 무용제형 광경화 점착제 제조방법은, 광촉매-공개시제를 첨가제로 함유하지 않으므로, 첨가제 용출의 문제점이 발생하지 않는 효과가 있다.The solvent-free photocurable pressure-sensitive adhesive composition and the solvent-free photocurable pressure-sensitive adhesive manufacturing method according to the present invention do not contain a photocatalyst-openitiator as an additive, so that the problem of additive elution does not occur.
본 발명에 의한 무용제형 광경화 점착제 조성물 및 무용제형 광경화 점착제 제조방법은, 질소 함유 비닐계 단량체를 함유하여 광촉매의 개시반응을 촉진하는 동시에 중합반응에도 참여하는 효과가 있다.The solvent-free photo-curable pressure-sensitive adhesive composition and the solvent-free photo-curable pressure-sensitive adhesive manufacturing method according to the present invention contain a nitrogen-containing vinylic monomer to promote the initiation reaction of the photocatalyst and have the effect of participating in the polymerization reaction.
본 발명에 의한 무용제형 광경화 점착제 조성물 및 무용제형 광경화 점착제 제조방법은 조성물의 구성과 비율을 조절함으로써 광경화 점착제의 물성을 조절할 수 있는 효과가 있다.The solvent-free photo-curable pressure-sensitive adhesive composition and the solvent-free photo-curable pressure-sensitive adhesive manufacturing method according to the present invention have the effect of controlling the physical properties of the photo-curing pressure-sensitive adhesive by adjusting the composition and ratio of the composition.
본 발명의 효과는 상기한 효과로 한정되는 것은 아니며, 본 발명의 상세한 설명 또는 특허청구범위에 기재된 발명의 구성으로부터 추론 가능한 모든 효과를 포함하는 것으로 이해되어야 한다.It should be understood that the effects of the present invention are not limited to the above-described effects, and include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.
도 1a는 본 발명의 일실시예에 따른 광촉매 라디칼 생성 메커니즘을 나타내고, 도 1b는 종래기술의 광개시제 라디칼 생성 메커니즘을 나타내며, 도 1c는 종래기술의 광촉매-공개시제 라디칼 생성 메커니즘을 나타낸 것이다.
도 2는 본 발명의 일실시예에 따른 무용제형 광경화 점착제의 제조방법을 나타낸 것이다.
도 3은 본 발명의 일실시예에 따른 무용제형 광경화 점착제의 기계적 강도 및 점탄성을 측정하는 방법을 나타낸 것으로, 도 3b는 전단강도를 측정하는 방법, 도 3b는 180도 박리강도를 측정하는 방법, 도 3c는 초기 점착력 테스트를 하는 방법, 도 3d는 점탄성을 측정하는 전단 샌드위치 클램프(shear sandwich clamp)의 모식도를 나타낸 것이다.
도 4a는 본 발명의 일실시예에 따른 무용제형 광경화 점착제의 질소 함유 비닐계 단량체 함량에 따른 경화율, 도 4b는 본 발명의 일실시예에 따른 무용제형 광경화 점착제의 광촉매 함량에 따른 경화율을 나타낸 그래프이다.
도 5a는 본 발명의 일실시예에 따른 무용제형 광경화 점착제의 질소 함유 비닐계 단량체 함량에 따른 변형-하중 곡선, 도 5b는 본 발명의 일실시예에 따른 무용제형 광경화 점착제의 유리전이온도에 따른 변형-하중 곡선을 나타낸 그래프이다.
도 6a는 본 발명의 일실시예에 따른 무용제형 광경화 점착제의 질소 함유 비닐계 단량체 함량에 따른 박리강도 곡선, 도 6b는 본 발명의 일실시예에 따른 무용제형 광경화 점착제의 유리전이온도에 따른 박리강도 곡선, 도 6c는 본 발명의 일실시예에 따른 무용제형 광경화 점착제의 질소 함유 비닐계 단량체 함량에 따른 초기 점착력 곡선, 도 6d는 본 발명의 일실시예에 따른 무용제형 광경화 점착제의 유리전이온도에 따른 초기 점착력 곡선을 나타낸 그래프이다.
도 7a는 본 발명의 일실시예에 따른 무용제형 광경화 점착제의 질소 함유 비닐계 단량체 함량에 따른 함량별 진동수-저장탄성률 곡선, 도 7b는 본 발명의 일실시예에 따른 무용제형 광경화 점착제의 유리전이온도에 따른 진동수-저장탄성률 곡선을 나타낸 그래프이다.
도 8a는 점착제의 점탄성 윈도우로서, 점탄성에 따른 특징 및 적용 가능 분야를 나타낸 것이고, 도 8b는 본 발명의 일실시예에 따른 무용제형 광경화 점착제의 질소 함유 비닐계 단량체 함량에 따른 점탄성 윈도우, 도 8c는 본 발명의 일실시예에 따른 무용제형 광경화 점착제의 유리전이온도에 따른 점탄성 윈도우를 나타낸 것이다.1A shows a photocatalytic radical generating mechanism according to an embodiment of the present invention, FIG. 1B shows a prior art photoinitiator radical generating mechanism, and FIG. 1C shows a prior art photocatalytic-coinitiator radical generating mechanism.
2 is a view showing a method of manufacturing a non-solvent-type photo-curing pressure-sensitive adhesive according to an embodiment of the present invention.
Figure 3 shows a method for measuring the mechanical strength and viscoelasticity of the solvent-free photocurable pressure-sensitive adhesive according to an embodiment of the present invention, Figure 3b is a method of measuring shear strength, Figure 3b is a method of measuring 180 degree peel strength , FIG. 3c is a method of performing an initial adhesion test, and FIG. 3d is a schematic diagram of a shear sandwich clamp for measuring viscoelasticity.
Figure 4a is a curing rate according to the nitrogen-containing vinyl monomer content of the non-solvent type photo-curing pressure-sensitive adhesive according to an embodiment of the present invention, Figure 4b is curing according to the photocatalyst content of the solvent-free type photo-curing pressure-sensitive adhesive according to an embodiment of the present invention This is a graph showing the rate.
Figure 5a is a strain-load curve according to the nitrogen-containing vinyl monomer content of the solvent-free photocuring pressure-sensitive adhesive according to an embodiment of the present invention, Figure 5b is the glass transition temperature of the solvent-free photocuring pressure-sensitive adhesive according to an embodiment of the present invention It is a graph showing the strain-load curve according to
Figure 6a is a peel strength curve according to the nitrogen-containing vinyl-based monomer content of the non-solvent-type photo-curing pressure-sensitive adhesive according to an embodiment of the present invention, Figure 6b is the glass transition temperature of the solvent-free photo-curing pressure-sensitive adhesive according to an embodiment of the present invention 6c is an initial adhesive strength curve according to the nitrogen-containing vinyl monomer content of the solvent-free photocurable adhesive according to an embodiment of the present invention, and FIG. 6d is a solvent-free photocurable adhesive according to an embodiment of the present invention. It is a graph showing the initial adhesive force curve according to the glass transition temperature of
7a is a frequency-storage modulus curve for each content according to the nitrogen-containing vinylic monomer content of the solvent-free photocurable pressure-sensitive adhesive according to an embodiment of the present invention, and FIG. 7b is a solvent-free photocurable adhesive according to an embodiment of the present invention. It is a graph showing the frequency-storage modulus curve according to the glass transition temperature.
Figure 8a is a viscoelastic window of the pressure-sensitive adhesive, showing the characteristics and applicable fields according to the viscoelasticity, Figure 8b is a viscoelastic window according to the nitrogen-containing vinyl monomer content of the solvent-free photocuring pressure-sensitive adhesive according to an embodiment of the present invention, Fig. 8c shows the viscoelastic window according to the glass transition temperature of the solvent-free photocurable pressure-sensitive adhesive according to an embodiment of the present invention.
본 발명을 상세하게 설명하기 전에, 본 명세서에서 사용된 용어나 단어는 통상적이거나 사전적인 의미로 무조건 한정하여 해석되어서는 아니되며, 본 발명의 발명자가 자신의 발명을 가장 최선의 방법으로 설명하기 위해서 각종 용어의 개념을 적절하게 정의하여 사용할 수 있고, 더 나아가 이들 용어나 단어는 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야 함을 알아야 한다.Before describing the present invention in detail, the terms or words used in this specification should not be construed as being unconditionally limited to their ordinary or dictionary meanings, and in order for the inventor of the present invention to explain his invention in the best way It should be understood that the concepts of various terms can be appropriately defined and used, and furthermore, these terms or words should be interpreted as meanings and concepts consistent with the technical idea of the present invention.
즉, 본 명세서에서 사용된 용어는 본 발명의 바람직한 실시예를 설명하기 위해서 사용되는 것일 뿐이고, 본 발명의 내용을 구체적으로 한정하려는 의도로 사용된 것이 아니며, 이들 용어는 본 발명의 여러 가지 가능성을 고려하여 정의된 용어임을 알아야 한다.That is, the terms used herein are only used to describe preferred embodiments of the present invention, and are not used for the purpose of specifically limiting the content of the present invention, and these terms represent various possibilities of the present invention. It should be understood that the term has been defined taking into account.
또한, 본 명세서에 있어서, 단수의 표현은 문맥상 명확하게 다른 의미로 지시하지 않는 이상, 복수의 표현을 포함할 수 있으며, 유사하게 복수로 표현되어 있다고 하더라도 단수의 의미를 포함할 수 있음을 알아야 한다.In addition, in the present specification, it should be noted that, unless the context clearly indicates otherwise, the expression in the singular may include a plurality of expressions, and even if it is similarly expressed in plural, it may include the meaning of the singular. do.
본 명세서의 전체에 걸쳐서 어떤 구성 요소가 다른 구성 요소를 "포함" 또는 "함유" 한다고 기재하는 경우에는, 특별히 반대되는 의미의 기재가 없는 한 임의의 다른 구성 요소를 제외하는 것이 아니라 임의의 다른 구성 요소를 더 포함할 수도 있다는 것을 의미할 수 있다.Throughout this specification, when it is stated that a component "includes" or "contains" another component, it does not exclude any other component, unless otherwise stated otherwise. It may mean that it may include more elements.
또한, 이하에서, 본 발명을 설명함에 있어서, 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 구성, 예를 들어, 종래 기술을 포함하는 공지기술에 대한 상세한 설명은 생략될 수도 있다.In addition, in the following, in describing the present invention, a detailed description of a configuration determined that may unnecessarily obscure the gist of the present invention, for example, a detailed description of the known technology including the prior art may be omitted.
본 발명은 아크릴계 단량체와 광촉매를 포함하고, 상기 아크릴계 단량체는 질소 함유 비닐계 단량체를 포함하는 무용제형 광경화 점착제 조성물을 제공한다.The present invention provides a solvent-free photo-curing pressure-sensitive adhesive composition comprising an acrylic monomer and a photocatalyst, wherein the acrylic monomer includes a nitrogen-containing vinyl monomer.
본 발명에 따른 무용제형 광경화 점착제 조성물에 포함된 광촉매가 광조사에 반응하여 라디칼을 생성하는 매커니즘은 도 1a에 나타내었고, 종래의 기술에서 광개시제를 사용하는 광경화 점착제의 광개시제 라디칼 생성 메커니즘은 도 1b로 나타내었고, 종래의 기술에서 공개시제(co-initiator)를 첨가제로 사용하는 광촉매를 포함한 광경화 점착제의 광촉매-공개시제 라디칼 생성 메커니즘은 도 1c로 나타내었다. The mechanism by which the photocatalyst included in the solvent-free photocurable pressure-sensitive adhesive composition according to the present invention generates radicals in response to light irradiation is shown in FIG. 1b, the photocatalyst-co-initiator radical generation mechanism of a photo-curing pressure-sensitive adhesive including a photocatalyst using a co-initiator as an additive in the prior art is shown in FIG. 1c.
종래의 광개시제를 사용하는 광경화 점착제는 균일분해(hemolytic cleavage)를 통해 라디칼을 생성하는 소모성 광개시제를 사용하였으나, 광촉매를 사용하는 경우에는 광전자 전달 반응 사이클을 통해 라디칼을 생성하므로 중합과정 중 소모되지 않는다는 장점이 있다. 따라서 기존에 사용되던 광개시제는 0.1 ~ 1 중량%를 첨가하였으나, 본 발명에 따른 광촉매를 사용하는 경우 광촉매 첨가량을 ppm 단위로 낮출 수 있다. 또한 종래에는 광촉매와 함께 공개시제를 첨가제로 사용하여 개시반응을 촉진하였으나, 본 발명에서는 공개시제의 첨가제 없이, 질소 함유 비닐계 모노머를 첨가하여 광촉매의 개시반응을 촉진하는 동시에 중합반응의 구성성분이 되는 장점이 있다. 따라서, 첨가제 용출 등의 문제점이 발생하지 않는다.Conventional photo-curing adhesives using a photoinitiator use a consumable photoinitiator that generates radicals through hemolytic cleavage. There are advantages. Therefore, the conventionally used photoinitiator was added in an amount of 0.1 to 1% by weight, but when the photocatalyst according to the present invention is used, the amount of the photocatalyst can be lowered in ppm units. In addition, in the prior art, the initiation reaction was promoted by using a co-initiator as an additive together with a photocatalyst, but in the present invention, without the co-initiator additive, nitrogen-containing vinylic monomers are added to promote the initiation reaction of the photocatalyst and at the same time, the constituents of the polymerization reaction are has the advantage of being Therefore, problems such as dissolution of additives do not occur.
본 발명의 일 실시예에 따르면, 상기 아크릴계 단량체는, 유리전이온도(Tg)가 낮은 단량체로서 EHA(2-Ethylhexyl acrylate), n-BA(n-butyl acrylate) 중 하나; 유리전이온도(Tg)가 높은 단량체로서 IBOA(Isobornyl acrylate), MMA(methylmethacrylate) 중 하나; 기능성 단량체로서 AA(Acrylic acid), HEA(2-hydroxyethyl acrylate) 중 하나; 및 질소 함유 비닐계 단량체로서 NVP(N-Vinyl-Pyrrolidone), NVC(N-Vinyl-caprolactam) 중 하나;를 함유할 수 있다. According to an embodiment of the present invention, the acrylic monomer may include one of 2-Ethylhexyl acrylate (EHA) and n-butyl acrylate (n-BA) as a monomer having a low glass transition temperature (Tg); One of IBOA (Isobornyl acrylate) and MMA (methylmethacrylate) as a monomer having a high glass transition temperature (Tg); One of AA (Acrylic acid) and HEA (2-hydroxyethyl acrylate) as a functional monomer; and one of N-Vinyl-Pyrrolidone (NVP) and N-Vinyl-caprolactam (NVC) as a nitrogen-containing vinylic monomer.
더욱 바람직하게는, 상기 아크릴계 단량체는, 유리전이온도(Tg)가 낮은 단량체로서 EHA(2-Ethylhexyl acrylate), 유리전이온도(Tg)가 높은 단량체로서 IBOA(Isobornyl acrylate), 기능성 단량체로서 AA(Acrylic acid) 및 및 질소 함유 비닐계 단량체로서 NVP(N-Vinyl-Pyrrolidone), NVC(N-Vinyl-caprolactam) 중 하나를 함유할 수 있다. More preferably, the acrylic monomer is EHA (2-Ethylhexyl acrylate) as a low glass transition temperature (Tg) monomer, IBOA (Isobornyl acrylate) as a high glass transition temperature (Tg) monomer, AA (Acrylic) as a functional monomer acid) and, as a nitrogen-containing vinylic monomer, one of NVP (N-Vinyl-Pyrrolidone) and NVC (N-Vinyl-caprolactam) may be contained.
EHA, IBOA, AA 및 질소 함유 비닐계 단량체로서 N-Vinyl-monomer의 구조식은 아래 구조식 1 ~ 4와 같다. Structural formulas of N-Vinyl-monomer as EHA, IBOA, AA and nitrogen-containing vinylic monomers are as shown in
[구조식 1][Structural Formula 1]
[구조식 2][Structural Formula 2]
[구조식 3][Structural Formula 3]
[구조식 4][Structural Formula 4]
본 발명의 일 실시예에 따르면, 상기 광촉매는 4DP-IPN, 4Cz-IPN, 에오신(eosin Y), 캄포르퀴논(Camphorquinone) 중 하나일 수 있다. 광촉매는 4DP-IPN, 4Cz-IPN, 에오신(eosin Y), 캄포르퀴논(Camphorquinone)의 구조식은 아래 구조식 5 ~ 8과 같다.According to an embodiment of the present invention, the photocatalyst may be one of 4DP-IPN, 4Cz-IPN, eosin Y, and camphorquinone. The photocatalyst is 4DP-IPN, 4Cz-IPN, eosin (eosin Y), camphorquinone (Camphorquinone)
[구조식 5][Structural Formula 5]
[구조식 6][Structural Formula 6]
[구조식 7][Structural Formula 7]
[구조식 8][Structural Formula 8]
본 발명의 일 실시예에 따르면, 상기 유리전이온도(Tg)가 낮은 단량체는 50 ~ 80 mol%; 상기 유리전이온도(Tg)가 높은 단량체는 5 ~ 30 mol%; 상기 기능성 단량체는 5 ~ 20 mol%; 및 상기 질소 함유 비닐계 단량체는 5 ~ 30 mol%;를 함유할 수 있다. 더욱 바람직하게는 상기 유리전이온도(Tg)가 낮은 단량체는 60 ~ 70 mol%; 상기 유리전이온도(Tg)가 높은 단량체는 5 ~ 20 mol%; 상기 기능성 단량체는 5 ~ 10 mol%; 및 상기 질소 함유 비닐계 단량체는 10 ~ 30 mol%;를 함유할 수 있다.According to an embodiment of the present invention, the monomer having a low glass transition temperature (Tg) is 50 to 80 mol%; The monomer having a high glass transition temperature (Tg) is 5 to 30 mol%; The functional monomer is 5 to 20 mol%; and 5 to 30 mol% of the nitrogen-containing vinylic monomer. More preferably, the monomer having a low glass transition temperature (Tg) is 60 to 70 mol%; The monomer having a high glass transition temperature (Tg) is 5 to 20 mol%; The functional monomer is 5 to 10 mol%; and 10 to 30 mol% of the nitrogen-containing vinylic monomer.
본 발명의 일 실시예에 따르면, 상기 광촉매는 10 ~ 100 ppm 으로 함유할 수 있다.According to an embodiment of the present invention, the photocatalyst may be contained in an amount of 10 to 100 ppm.
또한, 본 발명은 질소 함유 비닐계 단량체를 포함한 아크릴계 단량체와 광촉매를 포함한 조성물에 광조사를 하여 합성된 아크릴 수지에 다관능성 단량체를 혼합한 무용제형 광경화 점착제 조성물을 제공하다.In addition, the present invention provides a solvent-free photocurable pressure-sensitive adhesive composition in which a polyfunctional monomer is mixed with an acrylic resin synthesized by irradiating a composition including an acrylic monomer including a nitrogen-containing vinylic monomer and a photocatalyst with light.
본 발명의 일 실시예에 따르면, 상기 질소 함유 비닐계 단량체를 포함한 아크릴계 단량체와 광촉매를 포함한 조성물에 광조사를 하여 합성된 아크릴 수지는, 광촉매와 미반응된 아크릴 단량체를 함유한다.According to an embodiment of the present invention, the acrylic resin synthesized by irradiating the composition including the acrylic monomer including the nitrogen-containing vinyl monomer and the photocatalyst with light contains the photocatalyst and the unreacted acrylic monomer.
본 발명의 일 실시예에 따르면, 상기 다관능성 단량체는 PEGDA(poly(ethylene glycol) diacrylate) 인 것이 바람직하다.According to an embodiment of the present invention, the polyfunctional monomer is preferably PEGDA (poly(ethylene glycol) diacrylate).
또한, 본 발명은 상기 질소 함유 비닐계 단량체를 포함한 아크릴계 단량체와 광촉매를 포함한 조성물에 광조사를 하여 합성된 아크릴 수지에 다관능성 단량체를 혼합한 무용제형 광경화 점착제 조성물에 광조사를 하여 경화된 무용제형 광경화 점착제 조성물을 제공한다.In addition, the present invention is a solvent-free photocurable pressure-sensitive adhesive composition in which a polyfunctional monomer is mixed with an acrylic resin synthesized by light irradiation to a composition including an acrylic monomer and a photocatalyst including the nitrogen-containing vinylic monomer, cured by light irradiation Provided is a formulation photo-curing pressure-sensitive adhesive composition.
본 발명의 일 실시예에 따르면, 상기 광조사는 자외선 또는 가시광선 중 선택된 하나 이상을 이용한 것일 수 있으며, 바람직하게는 자외선 및 가시광선을 조사할 수 있다.According to an embodiment of the present invention, the light irradiation may use one or more selected from ultraviolet or visible light, preferably ultraviolet and visible light.
또한, 본 발명은 질소 함유 비닐계 단량체를 포함한 아크릴계 단량체와 광촉매를 혼합하는 단계(a 단계); 1차 광조사를 통해 아크릴 수지를 합성하는 단계(b 단계); 상기 합성된 아크릴 수지에 다관능성 단량체를 혼합한 후 2차 광조사를 하는 단계(c 단계); 를 포함하는 무용제형 광경화 점착제의 제조방법을 제공한다.In addition, the present invention comprises the steps of mixing an acrylic monomer and a photocatalyst including a nitrogen-containing vinyl monomer (step a); synthesizing an acrylic resin through primary light irradiation (step b); mixing the polyfunctional monomer with the synthesized acrylic resin and then performing secondary light irradiation (step c); It provides a method for producing a solvent-free photo-curing pressure-sensitive adhesive comprising a.
도 2에는 본 발명의 일 실시예에 따른 무용제형 광경화 점착제 제조방법을 나타내었다. 아크릴계 단량체와 광촉매를 혼합하고, 1차 광조사를 통해 벌크 중합을 실시하여 일정 점도(~수천 cPs) 이상의 아크릴 수지가 합성되게 된다. 아크릴 수지는 중합된 고분자 사슬과 미반응 아크릴 단량체가 혼합되어 있는 형태로 벌크 중합의 전환율은 5 ~ 20 % 이다. 이 아크릴 수지에 다관능성 단량체를 경화제로 혼합한 후 코팅하고, 이에 2차 광조사를 통해 아크릴 점착제를 제조한다. 종래의 기술에서 광촉매는 공개시제를 첨가제로 사용하여 개시반응을 촉진하는데 반하여, 본 발명에서는 질소 함유 비닐계 모노머를 첨가하여 광촉매의 개시반응을 촉진하는 동시에 중합 반응의 구성성분이 된다. 2 shows a method for manufacturing a non-solvent-type photocurable pressure-sensitive adhesive according to an embodiment of the present invention. An acrylic resin having a certain viscosity (~ several thousand cPs) or higher is synthesized by mixing an acrylic monomer and a photocatalyst, and performing bulk polymerization through primary light irradiation. The acrylic resin is a mixture of polymerized polymer chains and unreacted acrylic monomers, and the conversion rate of bulk polymerization is 5 to 20%. A polyfunctional monomer is mixed with the acrylic resin as a curing agent and coated, and then an acrylic pressure-sensitive adhesive is prepared through secondary light irradiation. In the prior art, the photocatalyst uses a coinitiator as an additive to promote the initiation reaction, whereas in the present invention, nitrogen-containing vinylic monomer is added to promote the initiation reaction of the photocatalyst and at the same time become a component of the polymerization reaction.
본 발명의 일 실시예에 따르면, 상기 아크릴계 단량체는, 유리전이온도(Tg)가 낮은 단량체로서 EHA(2-Ethylhexyl acrylate), n-BA(n-butyl acrylate) 중 하나를 50 ~ 80 mol%; 유리전이온도(Tg)가 높은 단량체로서 IBOA(Isobornyl acrylate), MMA(methylmethacrylate) 중 하나를 5 ~ 30 mol%; 기능성 단량체로서 AA(Acrylic acid), HEA(2-hydroxyethyl acrylate) 중 하나를 5 ~ 20 mol%; 및 질소 함유 비닐계 단량체로서 NVP(N-Vinyl-Pyrrolidone), NVC(N-Vinyl-caprolactam) 중 하나를 5 ~ 30 mol%;로 함유할 수 있고, 바람직하게는 구조식 1로 나타낸 EHA을 60 ~ 70 mol%; 유리전이온도(Tg)가 높은 단량체로서 구조식 2로 나타낸 IBOA를 5 ~ 20 mol%; 기능성 단량체로서 구조식 3으로 나타낸 AA를 5 ~ 10 mol%; 및 질소 함유 비닐계 단량체로서 구조식 4로 나타낸 NVP, NVC 중 하나를 10 ~ 30 mol%;를 함유할 수 있다. 상기 아크릴계 단량체는 상기 함유량 범위 미만인 경우 점착 필름의 응집력 및 기계적 물성 저하가 발생할 수 있고, 상기 함유량 범위를 초과하는 경우 점착 필름의 Tg 증가로 인한 점착력이 저하되는 문제가 발생할 수 있다.According to an embodiment of the present invention, the acrylic monomer, as a monomer having a low glass transition temperature (Tg), one of EHA (2-ethylhexyl acrylate), n-BA (n-butyl acrylate) 50 ~ 80 mol%; 5 ~ 30 mol% of either IBOA (Isobornyl acrylate) or MMA (methylmethacrylate) as a monomer having a high glass transition temperature (Tg); 5 to 20 mol% of either AA (Acrylic acid) or HEA (2-hydroxyethyl acrylate) as a functional monomer; and 5 to 30 mol% of one of NVP (N-Vinyl-Pyrrolidone) and NVC (N-Vinyl-caprolactam) as a nitrogen-containing vinylic monomer; preferably, EHA represented by
본 발명의 일 실시예에 따르면, 상기 광촉매는 4DP-IPN, 4Cz-IPN, 에오신(eosin Y), 캄포르퀴논(Camphorquinone) 중 하나를 10 ~ 100 ppm 으로 함유할 수 있고, 상기 광촉매들은 구조식 5 내지 8로 나타내었다. 상기 광촉매는 상기 함유량 범위 미만인 경우 중합속도 저해 및 필름 경화 속도 저해가 발생할 수 있고, 상기 함유량 범위를 초과하는 경우의 중합속도가 저해되고 점착제의 투명도가 떨어지는 단점이 발생할 수 있다. According to an embodiment of the present invention, the photocatalyst may contain one of 4DP-IPN, 4Cz-IPN, eosin Y, and camphorquinone in an amount of 10 to 100 ppm, and the photocatalysts are
본 발명의 일 실시예에 따르면, 상기 아크릴 수지에 혼합하는 다관능성 단량체로는 PEGDA(poly(ethylene glycol) diacrylate)를 이용하는 것이 바람직하다. PEGDA는 상기 b 단계에서 합성된 아크릴 수지에 대비 0 초과 10 이하 중량%로 첨가하는 것이 바람직하다. PEGDA의 첨가량이 10 중량% 초과 시 높은 경화밀도로 인한 점착 물성 저하가 발생할 수 있다.According to an embodiment of the present invention, it is preferable to use poly(ethylene glycol) diacrylate (PEGDA) as the polyfunctional monomer to be mixed with the acrylic resin. PEGDA is preferably added in an amount of more than 0 and 10% by weight compared to the acrylic resin synthesized in step b. When the amount of PEGDA added exceeds 10% by weight, a decrease in adhesive properties may occur due to a high curing density.
본 발명의 일 실시예에 따르면, 상기 광조사는 자외선 또는 가시광선 중 선택된 하나 이상을 이용한 것일 수 있으며, 바람직하게는 자외선 및 가시광선을 조사하는 것이다.According to an embodiment of the present invention, the light irradiation may be one or more selected from ultraviolet or visible light, preferably ultraviolet and visible light.
이하에서, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나, 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다. 하기의 실시예는 본 발명의 범위 내에서 당업자에 의해 적절히 수정, 변경될 수 있다.Hereinafter, the present invention will be described in more detail through examples. However, the following examples are provided to explain the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
실시예Example
실시예 1~15: 아크릴 점착제의 제조Examples 1-15: Preparation of acrylic adhesive
2-에틸헥실아크릴레이트(EHA), 아크릴산(AA), 이소보닐아크릴레이트(IBOA)와 N-비닐-피롤리돈(NVP) 및 광촉매를 각각 하기 표 1에 기재된 함량으로 용기에 투입하고, 혼합된 결과물에 가시광선 영역의 블루 LED를 1차 조사하여 아크릴 수지를 중합하였고, 이에 다관능성 단량체 PEGDA를 경화제로 혼합한 후 코팅하여 블루 LED를 2차 조사하여 아크릴 점착제를 제조하였다. 표 1의 광촉매제(PC)에서 a: 4DP-IPN, b: 4Cz-IPN, c: eosin Y 이다.2-ethylhexyl acrylate (EHA), acrylic acid (AA), isobornyl acrylate (IBOA), N-vinyl-pyrrolidone (NVP), and a photocatalyst are each added to the container in the amounts shown in Table 1 below, and mixed. The resultant product was first irradiated with a blue LED in the visible ray region to polymerize the acrylic resin, and the polyfunctional monomer PEGDA was mixed with a curing agent and coated to prepare an acrylic adhesive by second irradiating the blue LED. In the photocatalyst (PC) of Table 1, a: 4DP-IPN, b: 4Cz-IPN, c: eosin Y.
[표 1][Table 1]
실험예 1: 벌크중합 결과 측정Experimental Example 1: Measurement of bulk polymerization results
상기 실시예 1 ~ 15에서 제조된 아크릴 점착제에 대하여, 유리전이온도(Tgexp; Flory-Fox equation으로 계산하여 예상한 Tg), 반응시간(Reaction time), 벌크중합 전환율(Bulk conversion), 수평균 분자량(Mn), 고분자의 polydispersity index(Ð) 에 대하여 계산 또는 측정하였다. For the acrylic pressure-sensitive adhesive prepared in Examples 1 to 15, the glass transition temperature (Tg exp; Tg predicted by the Flory-Fox equation), the reaction time (Reaction time), the bulk conversion rate (Bulk conversion), number average The molecular weight (Mn) and the polydispersity index (Ð) of the polymer were calculated or measured.
그 결과는 표 2에서 볼 수 있듯이, 촉매 종류 및 조성에 따라 중합 속도를 조절할 수 있으며, 질소 함유 비닐계 단량체(boosting monomer) 함량이 늘어남에 따라 중합속도를 높일 수 있음을 확인하였다. As can be seen from Table 2, it was confirmed that the polymerization rate can be controlled according to the catalyst type and composition, and the polymerization rate can be increased as the nitrogen-containing vinyl-based monomer content is increased.
[표 2][Table 2]
실험예 2: 경화율 측정Experimental Example 2: Measurement of curing rate
상기 실시예 1 ~ 15에서 제조된 아크릴 점착제에 대하여, 아래 계산식 1과 같이 경화율을 계산하였다.For the acrylic pressure-sensitive adhesives prepared in Examples 1 to 15, the curing rate was calculated as in
[계산식 1][Formula 1]
그 결과는 도 4a 및 도 4b에서 볼 수 있듯이, 질소 함유 비닐계 단량체의 함량이 증가함에 따라 경화속도가 빨라지는 것을 알 수 있고, 광촉매 함량이 증가함에 다라 경화속도가 빨라지는 것을 확인하였다. As a result, as can be seen in FIGS. 4A and 4B , it can be seen that the curing speed increases as the content of the nitrogen-containing vinylic monomer increases, and it is confirmed that the curing speed increases as the photocatalyst content increases.
실험예 3: 기계적 강도 및 점착 물성 측정Experimental Example 3: Measurement of mechanical strength and adhesion properties
(1) 전단강도(One) shear strength
상기 실시예 1 ~ 15에서 제조된 아크릴 점착제에 대하여 도 3a와 같은 방법으로 전단강도를 측정하였다. 이 때, 점착제 두께 50 um, 점착 면적 25 mm X 25 mm, 측정속도 1 mm/s, 측정온도 23 ℃로 하였다. The shear strength of the acrylic pressure-sensitive adhesive prepared in Examples 1 to 15 was measured in the same manner as in FIG. 3A. At this time, the thickness of the adhesive was 50 um, the adhesive area was 25
(2) 180도 박리 강도(2) 180 degree peel strength
상기 실시예 1 ~ 15에서 제조된 아크릴 점착제에 대하여, 도 3b와 같은 방법으로 180도 박리 강도를 측정하였다. 이 때, 점착제 두께 50 um, 점착제 폭 1 cm, 기재는 SUS 304, 압착은 2 kg 롤러 2회 실시 후 24시간 방치하였고, 박리속도는 5 mm/s, 측정온도 23 ℃ 로 하였다. For the acrylic pressure-sensitive adhesives prepared in Examples 1 to 15, 180 degree peel strength was measured in the same manner as in FIG. 3B. At this time, the thickness of the adhesive was 50 um, the width of the adhesive was 1 cm, the substrate was SUS 304, and the compression was performed twice with a 2 kg roller, and then left for 24 hours, the peeling speed was 5 mm/s, and the measurement temperature was 23 °C.
상기와 같은 기계적 물성 측정결과는, 표 3과 도 5a, 도 5b에 나타내었다. 도 5a에서 볼 수 있듯이, 질소 함유 비닐계 단량체의 함량이 증가함에 따라 전단강도 및 연신율이 증가되며 고분자가 강인화(toughening) 되는 것을 확인하였고, 도 5b에서 볼 수 있듯이, 점착제의 유리전이 온도가 증가함에 따라 점착제의 전단강도 및 연신율이 향상되는 것을 확인하였다. 이를 통하여, 광촉매 조건 하에서도 조성물 구성의 비율을 달리하여 다양한 기계적 물성을 구현할 수 있음을 알 수 있다.The measurement results of the mechanical properties as described above are shown in Table 3 and FIGS. 5A and 5B. As can be seen in Fig. 5a, as the content of the nitrogen-containing vinylic monomer increased, it was confirmed that the shear strength and elongation were increased and the polymer was toughened, and as can be seen in Fig. 5b, the glass transition temperature of the pressure-sensitive adhesive was It was confirmed that the shear strength and elongation of the pressure-sensitive adhesive improved as it increased. Through this, it can be seen that various mechanical properties can be implemented by varying the composition ratio even under photocatalytic conditions.
[표 3][Table 3]
(3) 초기 점착력 테스트(3) Initial adhesion test
상기 실시예 1 ~ 15에서 제조된 아크릴 점착제에 대하여, 도 3c와 같은 방법으로 초기 점착력 테스트 하였다. 이 때, 점착제 두께 50 um, 점착제 폭 1 cm, 기재는 SUS 304, 박리속도는 5 mm/s, 측정온도 23 ℃로 하였다.The acrylic adhesives prepared in Examples 1 to 15 were tested for initial adhesion in the same manner as in FIG. 3C . At this time, the thickness of the adhesive was 50 um, the width of the adhesive was 1 cm, the substrate was SUS 304, the peeling rate was 5 mm/s, and the measurement temperature was 23°C.
초기 점착력 테스트 결과는 표 4와 도 6a ~ 도 6d 에 나타내었다. 도 6a, 도 6b, 도 6c에서, 질소 함유 비닐계 단량체의 함량이 증가함에 따라 박리강도 및 초기 점착력이 증가하나, 30 mol% 에서는 높은 모듈러스로 인해 초기 점착력이 다소 저하됨을 확인하였다. 도 6d는 점착제의 유리전이 온도가 증가함에 따라 박리강도와 초기 점착력이 증가하나 높은 유리전이 온도에서는 박리강도에서 stick slip 현상이 발생하며 초기 점착력이 저하되는 현상이 발생함을 알 수 있다. The initial adhesion test results are shown in Table 4 and FIGS. 6A to 6D . 6a, 6b, and 6c, peel strength and initial adhesive strength increased as the content of the nitrogen-containing vinylic monomer increased, but at 30 mol%, it was confirmed that the initial adhesive strength was somewhat lowered due to the high modulus. 6d shows that the peel strength and initial adhesive strength increase as the glass transition temperature of the pressure-sensitive adhesive increases, but at a high glass transition temperature, the stick slip phenomenon occurs in the peel strength and the initial adhesive strength decreases.
[표 4][Table 4]
실험예 4: 점탄성 측정Experimental Example 4: Measurement of viscoelasticity
상기 실시예 1 ~ 15에서 제조된 아크릴 점착제에 대하여, 동적 기계 분석(Dynamic mechanical analysis)을 이용하여 점탄성을 측정하였다. 이 때 샘플 크기는 10 mm X 10 mm X 0.8 mm (l,w,t), 샘플 경화 조건은 0.3 mW/cm2, 60분으로 하였고, 진동수는 0.01 ~ 100 Hz, 측정 모드는 전단 샌드위치 클램프(shear sandwich clamp; strain = 1%)으로 하였다. 도 3d는 전단 샌드위치 클램프의 모식도를 나타내고, 노란색으로 표시된 것이 샘플이다.Viscoelasticity of the acrylic adhesives prepared in Examples 1 to 15 was measured using dynamic mechanical analysis. At this time, the sample size was 10
그 결과 도 7a와 도 7b에서 볼 수 있듯이, 질소 함유 비닐계 단량체의 함량이 증가함에 따라 저장 탄성률이 향상되는 것을 확인하였고, 점착제의 유리전이 온도가 증가함에 따라 저장 탄성률이 향상되는 것을 확인할 수 있었다.As a result, as can be seen in FIGS. 7a and 7b, it was confirmed that the storage elastic modulus was improved as the content of the nitrogen-containing vinylic monomer increased, and it was confirmed that the storage elastic modulus was improved as the glass transition temperature of the adhesive increased. .
또한, 도 8a의 점착제의 점탄성 윈도우를 통해 점탄성에 따른 특징 및 적용 가능 분야를 확인할 수 있다. 도 8b ~ 도 8c는 본 발명의 실시예에 따른 점착제의 점탄성 윈도우를 나타낸 것으로, 도 8b는 질소 함유 비닐계 단량체 함량에 따른 점탄성 윈도우를, 도 8c는 유리전이온도에 따른 점탄성 윈도우를 보여준다.In addition, through the viscoelastic window of the pressure-sensitive adhesive of FIG. 8A, characteristics and applicable fields according to viscoelasticity can be confirmed. 8b to 8c show the viscoelastic window of the pressure-sensitive adhesive according to an embodiment of the present invention. FIG. 8b shows the viscoelastic window according to the nitrogen-containing vinylic monomer content, and FIG. 8c shows the viscoelastic window according to the glass transition temperature.
점착제는 반고체 상태에서 물체에 부착 및 탈착이 가능한 고분자 재료로서, 점착제의 점탄성은 탈부착시 물성을 예측할 수 있는 중요한 요소이다. 도 8a ~ 도 8c의 점탄성 윈도우를 통해 본 발명에 따른 무용제형 광경화 점착제의 적용 가능한 분야를 예측할 수 있다. A pressure-sensitive adhesive is a polymer material that can be attached to and detached from an object in a semi-solid state, and the viscoelasticity of the pressure-sensitive adhesive is an important factor in predicting the physical properties during attachment and detachment. Applicable fields of the solvent-free photocuring adhesive according to the present invention can be predicted through the viscoelastic window of FIGS. 8A to 8C .
질소 함유 비닐계 단량체의 함량과 점착제의 조성을 조절하여 점탄성 물성의 조절이 가능하며, 이에 따라 다양한 점탄성 윈도우의 구현이 가능하다. 본 발명의 실시예에 따라 제조된 무용제형 광경화 점착제의 점탄성 윈도우가 속하는 범위를 볼 때, 이형 코팅(release coatings), 일반 감압점착제(general PSA), 고전단 감압점착제(high shear PSA) 등의 다양한 분야에 적용할 수 있다.By controlling the content of the nitrogen-containing vinylic monomer and the composition of the pressure-sensitive adhesive, it is possible to control the viscoelastic properties, thereby realizing various viscoelastic windows. When looking at the range to which the viscoelastic window of the solvent-free photocurable pressure-sensitive adhesive prepared according to the embodiment of the present invention belongs, release coatings, general pressure-sensitive adhesives (general PSA), high shear pressure-sensitive adhesives (high shear PSA), etc. It can be applied in various fields.
따라서, 본 발명의 의한 무용제형 광경화 점착제 조성물 및 무용제형 광경화 점착제 제조방법은 조성물의 구성과 비율을 조절함으로써 광경화 점착제의 물성을 조절할 수 있음을 알 수 있다.Therefore, it can be seen that the solvent-free photo-curing pressure-sensitive adhesive composition and the solvent-free photo-curing pressure-sensitive adhesive manufacturing method according to the present invention can control the physical properties of the photo-curable pressure-sensitive adhesive by adjusting the composition and ratio of the composition.
지금까지 본 발명에 따른 무용제형 광경화 점착제와 그 조성물에 관한 구체적인 실시예에 관하여 설명하였으나, 본 발명의 범위에서 벗어나지 않는 한도 내에서는 여러 가지 실시 변형이 가능함은 자명하다.Although specific examples of the solvent-free photocurable pressure-sensitive adhesive and the composition thereof have been described so far according to the present invention, it is apparent that various implementation modifications are possible within the limits that do not depart from the scope of the present invention.
그러므로 본 발명의 범위는 설명된 실시예에 국한되어 정해져서는 안 되며, 후술하는 특허청구범위뿐만 아니라 이 특허청구범위와 균등한 것들에 의해 정해져야 한다.Therefore, the scope of the present invention should not be limited to the described embodiments, but should be defined by the following claims as well as the claims and equivalents.
즉, 전술된 실시예는 모든 면에서 예시적인 것이며, 한정적인 것이 아닌 것으로 이해되어야 하며, 본 발명의 범위는 상세한 설명보다는 후술될 특허청구범위에 의하여 나타내어지며, 그 특허청구범위의 의미 및 범위 그리고 그 등가 개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본 발명의 범위에 포함되는 것으로 해석되어야 한다.That is, it should be understood that the above-described embodiments are illustrative in all respects and not restrictive, and the scope of the present invention is indicated by the claims to be described later rather than the detailed description, and the meaning and scope of the claims; All changes or modifications derived from the concept of equivalents should be construed as being included in the scope of the present invention.
Claims (18)
상기 아크릴계 단량체는 질소 함유 비닐계 단량체를 포함하는 것을 특징으로 하는 무용제형 광경화 점착제 조성물.
In a composition comprising an acrylic monomer and a photocatalyst,
The acrylic monomer is a solvent-free photo-curing pressure-sensitive adhesive composition comprising a nitrogen-containing vinyl monomer.
상기 아크릴계 단량체는,
유리전이온도(Tg)가 낮은 단량체로서 EHA(2-Ethylhexyl acrylate), n-BA(n-butyl acrylate) 중 하나;
유리전이온도(Tg)가 높은 단량체로서 IBOA(Isobornyl acrylate), MMA(methylmethacrylate) 중 하나;
기능성 단량체로서 AA(Acrylic acid), HEA(2-hydroxyethyl acrylate) 중 하나; 및
질소 함유 비닐계 단량체로서 NVP(N-Vinyl-Pyrrolidone), NVC(N-Vinyl-caprolactam) 중 하나;를
함유하는 것을 특징으로 하는 무용제형 광경화 점착제 조성물.
According to claim 1,
The acrylic monomer is
One of EHA (2-Ethylhexyl acrylate) and n-BA (n-butyl acrylate) as a monomer having a low glass transition temperature (Tg);
One of IBOA (Isobornyl acrylate) and MMA (methylmethacrylate) as a monomer having a high glass transition temperature (Tg);
One of AA (Acrylic acid) and HEA (2-hydroxyethyl acrylate) as a functional monomer; and
One of NVP (N-Vinyl-Pyrrolidone) and NVC (N-Vinyl-caprolactam) as a nitrogen-containing vinylic monomer;
A solvent-free photocurable pressure-sensitive adhesive composition comprising:
상기 광촉매는 4DP-IPN, 4Cz-IPN, 에오신(eosin Y), 캄포르퀴논(Camphorquinone) 중 하나인 것을 특징으로 하는 무용제형 광경화 점착제 조성물.
According to claim 1,
The photocatalyst is one of 4DP-IPN, 4Cz-IPN, eosin Y, and camphorquinone.
상기 유리전이온도(Tg)가 낮은 단량체는 50 ~ 80 mol%;
상기 유리전이온도(Tg)가 높은 단량체는 5 ~ 30 mol%;
상기 기능성 단량체는 5 ~ 20 mol%; 및
상기 질소 함유 비닐계 단량체는 5 ~ 30 mol%;를
함유하는 것을 특징으로 하는 무용제형 광경화 점착제 조성물.
3. The method of claim 2,
The monomer having a low glass transition temperature (Tg) is 50 to 80 mol%;
The monomer having a high glass transition temperature (Tg) is 5 to 30 mol%;
The functional monomer is 5 to 20 mol%; and
The nitrogen-containing vinyl monomer is 5 to 30 mol%;
A solvent-free photocurable pressure-sensitive adhesive composition comprising:
상기 광촉매는 10 ~ 100 ppm 으로 함유하는 것을 특징으로 하는 무용제형 광경화 점착제 조성물.
5. The method of claim 4,
The photocatalyst is a solvent-free photo-curing pressure-sensitive adhesive composition, characterized in that it contains 10 to 100 ppm.
A solvent-free photo-curing pressure-sensitive adhesive composition, characterized in that a polyfunctional monomer is mixed with an acrylic resin synthesized by irradiating the composition of claim 1 with light.
상기 아크릴 수지는 광촉매와 미반응된 아크릴 단량체를 함유하는 것을 특징으로 하는 무용제형 광경화 점착제 조성물.
7. The method of claim 6,
The acrylic resin is a solvent-free photo-curing pressure-sensitive adhesive composition, characterized in that it contains a photocatalyst and unreacted acrylic monomer.
상기 다관능성 단량체는 PEGDA(poly(ethylene glycol) diacrylate) 인 것을 특징으로 하는 무용제형 광경화 점착제 조성물.
7. The method of claim 6,
The polyfunctional monomer is a solvent-free photocurable pressure-sensitive adhesive composition, characterized in that PEGDA (poly(ethylene glycol) diacrylate).
A solvent-free photo-curing pressure-sensitive adhesive composition, characterized in that the composition of claim 6 is cured by irradiation with light.
상기 광조사는 자외선 또는 가시광선 중 선택된 하나 이상을 이용하는 것을 특징으로 하는 무용제형 광경화 점착제 조성물.
10. The method of claim 6 or 9,
The light irradiation is a solvent-free photo-curing pressure-sensitive adhesive composition, characterized in that using at least one selected from ultraviolet or visible light.
1차 광조사를 통해 아크릴 수지를 합성하는 단계(b 단계);
상기 합성된 아크릴 수지에 다관능성 단량체를 혼합한 후 2차 광조사를 하는 단계(c 단계);
를 포함하는 것을 특징으로 하는 무용제형 광경화 점착제의 제조방법.
mixing an acrylic monomer including a nitrogen-containing vinylic monomer and a photocatalyst (step a);
synthesizing an acrylic resin through primary light irradiation (step b);
mixing the polyfunctional monomer with the synthesized acrylic resin and then performing secondary light irradiation (step c);
Method for producing a solvent-free photo-curing pressure-sensitive adhesive comprising a.
상기 아크릴계 단량체는,
유리전이온도(Tg)가 낮은 단량체로서 EHA(2-Ethylhexyl acrylate), n-BA(n-butyl acrylate) 중 하나를 50 ~ 80 mol%;
유리전이온도(Tg)가 높은 단량체로서 IBOA(Isobornyl acrylate), MMA(methylmethacrylate) 중 하나를 5 ~ 30 mol%;
기능성 단량체로서 AA(Acrylic acid), HEA(2-hydroxyethyl acrylate) 중 하나를 5 ~ 20 mol%; 및
질소 함유 비닐계 단량체로서 NVP(N-Vinyl-Pyrrolidone), NVC(N-Vinyl-caprolactam) 중 하나를 5 ~ 30 mol%;로
함유하는 것을 특징으로 하는 무용제형 광경화 점착제의 제조방법.
12. The method of claim 11,
The acrylic monomer is
50 ~ 80 mol% of either EHA (2-Ethylhexyl acrylate) or n-BA (n-butyl acrylate) as a monomer having a low glass transition temperature (Tg);
5 ~ 30 mol% of either IBOA (Isobornyl acrylate) or MMA (methylmethacrylate) as a monomer having a high glass transition temperature (Tg);
5 to 20 mol% of either AA (Acrylic acid) or HEA (2-hydroxyethyl acrylate) as a functional monomer; and
One of NVP (N-Vinyl-Pyrrolidone) and NVC (N-Vinyl-caprolactam) as a nitrogen-containing vinylic monomer is 5 to 30 mol%;
A method for producing a solvent-free photocuring pressure-sensitive adhesive, characterized in that it contains.
상기 광촉매는 4DP-IPN, 4Cz-IPN, 에오신(eosin Y), 캄포르퀴논(Camphorquinone) 중 하나를 10 ~ 100 ppm 으로 함유하는 것을 특징으로 하는 무용제형 광경화 점착제의 제조방법.
13. The method of claim 12,
The photocatalyst is 4DP-IPN, 4Cz-IPN, eosin (eosin Y), camphorquinone (Camphorquinone) one of 10 ~ 100 ppm Method for producing a solvent-free photo-curing adhesive, characterized in that it contains.
상기 다관능성 단량체는 PEGDA(poly(ethylene glycol) diacrylate) 인 것을 특징으로 하는 무용제형 광경화 점착제의 제조방법.
12. The method of claim 11,
The polyfunctional monomer is PEGDA (poly(ethylene glycol) diacrylate), characterized in that the manufacturing method of a solvent-free photo-curing adhesive.
상기 광조사는 자외선 또는 가시광선 중 선택된 하나 이상을 이용하는 것을 특징으로 하는 무용제형 광경화 점착제의 제조방법.
12. The method of claim 11,
The light irradiation is a method of manufacturing a solvent-free photo-curing pressure-sensitive adhesive, characterized in that using at least one selected from ultraviolet or visible light.
상기 1차 광조사에 의해 중합반응이 일어나고, 상기 2차 광조사에 의해 경화반응이 일어나는 것을 특징으로 하는 무용제형 광경화 점착제의 제조방법.
12. The method of claim 11,
A method for producing a solvent-free photocurable pressure-sensitive adhesive, characterized in that a polymerization reaction occurs by the primary light irradiation, and a curing reaction occurs by the secondary light irradiation.
상기 질소 함유 비닐계 단량체가 광촉매의 개시반응을 촉진하고, 중합반응의 구성성분이 되는 것을 특징으로 하는 무용제형 광경화 점착제의 제조방법.
17. The method of claim 16,
The method for producing a solvent-free photo-curing pressure-sensitive adhesive, characterized in that the nitrogen-containing vinyl-based monomer promotes the initiation reaction of the photocatalyst and becomes a component of the polymerization reaction.
상기 b단계의 1차 광조사를 통해 아크릴 수지를 합성하는 전환율은 5 ~ 20 % 인 것을 특징으로 하는 무용제형 광경화 점착제의 제조방법.12. The method of claim 11,
A method for producing a solvent-free photocurable pressure-sensitive adhesive, characterized in that the conversion rate for synthesizing the acrylic resin through the primary light irradiation in step b is 5 to 20%.
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