WO2015190799A1 - Composition de résine photodurcissable - Google Patents

Composition de résine photodurcissable Download PDF

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Publication number
WO2015190799A1
WO2015190799A1 PCT/KR2015/005767 KR2015005767W WO2015190799A1 WO 2015190799 A1 WO2015190799 A1 WO 2015190799A1 KR 2015005767 W KR2015005767 W KR 2015005767W WO 2015190799 A1 WO2015190799 A1 WO 2015190799A1
Authority
WO
WIPO (PCT)
Prior art keywords
acrylate
diacrylate
resin
triacrylate
resin composition
Prior art date
Application number
PCT/KR2015/005767
Other languages
English (en)
Korean (ko)
Inventor
송준용
신승협
최미경
지석환
최준호
김용우
Original Assignee
주식회사 동진쎄미켐
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 동진쎄미켐 filed Critical 주식회사 동진쎄미켐
Priority to CN201580031176.6A priority Critical patent/CN106459316B/zh
Priority claimed from KR1020150081069A external-priority patent/KR102381307B1/ko
Publication of WO2015190799A1 publication Critical patent/WO2015190799A1/fr

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Classifications

    • 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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G

Definitions

  • the present invention relates to a photocurable resin composition, and more particularly, to a photocurable resin composition capable of high-speed curing including an acrylamide monomer and having excellent coating property, adhesiveness and acid resistance.
  • the photolithography method used for realizing a fine pattern in an LCD process or a semiconductor process for manufacturing a conventional display has a circuit line width (or pattern line width) determined by the wavelength of light used in an exposure process.
  • circuit line width or pattern line width
  • the exposure, the post-exposure bake, the development, the post-development bake, the etching and the cleaning process have to be performed every time the pattern is formed, it takes a long time and the process is very complicated.
  • costly parts such as expensive exposure apparatus used for improving performance have been a problem.
  • micropatterns based on printed electronics have emerged.
  • various methods using printing techniques have also been attempted.
  • the roll process technology is low in production cost and can be manufactured on a flexible substrate such as film, which can be applied to a flexible display.
  • micropattern forming materials suitable for printing techniques has been actively conducted.
  • Printed electronic-based micropattern forming technology uses UV lamps or UV-LED lamps based on ultraviolet (UV) light sources for low-cost equipment and rapid productivity. It must be a base, and because it is a continuous process, fast curing speed by light is essential.
  • viscosity is one of important factors when determining the composition of the composition. That is, the composition capable of forming a micropattern in a printed electronic process is required to maintain a low material viscosity in order to realize a micropattern as a solvent-free material that is photocurable, and requires excellent curing speed, adhesive strength, and acid resistance.
  • the present invention is capable of high-speed photocuring based on the acrylamide monomer, photocurable resin for forming a fine pattern suitable for printed electronic processes having excellent adhesion, acid resistance and peeling properties for alkali solvents It is an object to provide a composition.
  • the present invention to achieve the above object
  • photocurable resin composition comprising a.
  • the present invention provides a method for forming a fine pattern, characterized in that for printing the conductive composition on a substrate and exposed.
  • the present invention provides a display manufactured by applying the fine pattern forming method.
  • the photocurable resin composition of the present invention can be applied to a printed electronics-based process by including an acrylamide monomer, thereby eliminating the need for a bake and development process used in conventional photolithography. It is possible to reduce investment cost by using UV curing machine, and it is advantageous to make flexible display based on roll process.
  • the photocurable composition of the present invention is capable of high-speed photocuring through excellent curing degree for UV photocuring to maximize the advantages of the printing process, and exhibits excellent coating properties, adhesion and acid resistance to various base substrates, It can be applied to flexible displays as well as LCD and OLED glass.
  • the photocurable resin composition according to the present invention comprises a) acrylamide monomer, b) acrylic copolymer resin, c) ethylene monomer, d) a crosslinkable monomer having at least two or more ethylene-based double bonds, and e) a photopolymerization initiator. Characterized in that.
  • Acrylamide monomers that can be used in the present invention are acrylamide as acrylamide (Acrylol morpholine), dimethyl acrylamide (N, N-dimethyl acrylamide), diethyl acrylamide (N, N) -diethyl acrylamide) and a monomer comprising dimethylaminoethyl acrylate (N, N-dimethylamino ethylacrylate) of formula (4), a monomer comprising an acrylamide commonly used in the art and a group consisting of an acrylate containing an amino group It may be at least one selected from, and preferably may be selected from monomers containing acrylamide of the following formula (1) -4. In this case, it has more excellent high-speed photocuring, excellent adhesion, acid resistance and peeling property against alkali solvents.
  • examples of the monomer including acrylamide commonly used in the art include N, N-dimethylaminopropylacrylamide, N-isopropylacrylamide, diacetoneacrylamide, isobutoxymethylacrylamide, t-octyl Acrylamide etc. are mentioned,
  • examples of the acrylate containing the said amino group N, N-diethylaminoethyl acrylate, 7-amino-3,7- dimethyl octyl acrylate, etc. are mentioned.
  • the acrylamide monomer may be used in an amount of 1 to 50% by weight based on the total weight of the composition, preferably 1 to 50% by weight, more preferably 5 to 30% by weight. .
  • the amount of the monomer used is less than 1% by weight, effects such as curing rate and adhesive strength may not be seen, and when the amount of the monomer exceeds 50% by weight, it may cause stability problems of the composition.
  • the acrylic copolymer resin usable in the present invention is epoxy acrylate resin, urethane acrylate resin, polyester acrylate resin, silicone acrylate resin, amino acrylate resin, epoxy methacrylate resin, urethane methacrylate resin, polyester It may be at least one selected from the group consisting of methacrylate resin, silicone methacrylate resin, amino methacrylate resin, etc., and the amount thereof is used in an amount of 1 to 40% by weight, preferably 3 to 20% by weight, based on the total weight of the composition. It is recommended to use the amount in%. If the amount of the resin is less than 1% by weight, the resin may not exhibit the inherent properties such as adhesive strength and curing degree, and when the amount of the resin exceeds 40% by weight, the viscosity may be high and fluidity may be impaired. have.
  • Ethylene monomers usable in the present invention are methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, isoamyl acrylate, hexyl acrylate, heptyl acrylate Latex, octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, tetrahydrofurfuryl acrylate, erythritol acrylate, butoxy Ethyl acrylate, ethoxy diethylene glycol acrylate, pentaerythritol acrylate, dietrisitol acrylate, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, methoxy ethylene
  • the ethylene-based monomer is preferably used in an amount of 10 to 60% by weight, preferably 20 to 40% by weight based on the total weight of the composition.
  • amount of the ethylene-based monomer is less than 10% by weight, the viscosity of the composition is low and cannot be used as a printed electronic coating liquid, and when it exceeds 60% by weight, it may have a result contrary to material properties requiring fast curing.
  • crosslinkable monomers having at least two ethylenic double bonds
  • the crosslinkable monomer usable in the present invention is ethylene glycol diacrylate, traethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, niphene Tyl glycol diacrylate, 1, 3- butylene glycol diacrylate, tris (2-hydroxyethyl) isocyanate diacrylate, erythritol diacrylate, pentaerythritol diacrylate, dietrisitol diacrylate, di Pentaerythritol diacrylate, bis (hydroxymethyl) tricyclodecanediacrylate, bisphenol A diacrylate and derivatives, glycerin triacrylate, erythritol triacrylate, dietrisitol triacrylate, pentaerythritol triacrylate, Dipentaerythritol triacrylate, tris (2-hydroxyethyl) isocyare
  • the crosslinkable monomer is preferably used in 1 to 60% by weight, preferably 5 to 30% by weight based on the total weight of the composition.
  • the amount used is less than 1% by weight, the curing rate may be lowered due to a decrease in curing rate and a decrease in curing density.
  • the amount is more than 60% by weight, high curing shrinkage and surface adhesion may be reduced.
  • Photopolymerization initiators usable in the present invention are 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylproriophenone, pt-butyltrichloroacetophenone, pt- Butyldichloroacetophenone, benzophenone, 4-chloroacetophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, 2,2 '-Dichloro-4-phenoxycetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( Acetophenone compounds such as 4-morpholinophenyl) -butan-1-one; Benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-pheny
  • the photopolymerization initiator is preferably used in an amount of 0.01 to 10% by weight, preferably 0.5 to 6% by weight based on the total weight of the composition.
  • the amount of the photopolymerization initiator is less than 0.1% by weight, photocuring may not be performed or may be slow to obtain a desired curing rate.
  • the amount of the photopolymerization initiator is more than 10% by weight, the coating film may be deteriorated due to the reaction inhibitory effect or the permeability of the material may decrease. Can happen.
  • compositions of the present invention are also suitable for various additives, such as antioxidants, ultraviolet absorbers, for moisture, UV and heat resistance, good coating and adhesion to substrates, etc., depending on the intended use of the material.
  • additives such as antioxidants, ultraviolet absorbers, for moisture, UV and heat resistance, good coating and adhesion to substrates, etc., depending on the intended use of the material.
  • UV absorber light stabilizer
  • heat polymerization inhibitor heat polymerization inhibitor
  • plasticizer silane coupling agent
  • leveling agent surface active agent ( Surfactant) and the like.
  • the present invention provides a method for forming a fine pattern, characterized in that the photocurable resin composition is printed on a substrate and then exposed.
  • the printing is a variety of printing processes commonly used in the art, for example, gravure off-set printing, gravure direct printing, screen printing, imprinting. Etc. may be applied, and as the substrate to which the conventional substrate may be applied, all conventional substrates may be applied, for example, glass substrates or plastic substrates may be applied.
  • ultraviolet rays As the light source used for the exposure, ultraviolet rays, visible rays, infrared rays, X-rays, electron beams, and the like may be used. Preferably, ultraviolet rays in the region of 190 to 450 nm may be used. In addition, a high temperature heat treatment process may be performed later to improve the use and properties of the film.
  • the photocurable composition including the acrylamide monomer of the present invention can be applied to a printed electronics-based process, eliminating the need for a bake and develop process used in conventional photolithography, and is not an expensive exposure machine, but a low-cost exposure machine. It is possible to reduce the investment cost by using UV curing machine, and it is possible to use the roll process, which has the advantage of producing a flexible display.
  • the photocurable composition of the present invention is capable of high-speed photocuring through excellent curing degree for UV photocuring to maximize the advantages of the printing process, PET (Poly Ethylene Terephthalate) that can be applied to flexible displays in addition to conventional LCD, OLED glass ) Excellent for various base substrates such as film, PC (Poly Carbonate) film, PI (Polyimide) film, Cu (Capper), ITO (Indium Tin OXxide), Al (Alumium), Mo (Moly) deposited on metal foil Coating properties, adhesion and acid resistance.
  • PET Poly Ethylene Terephthalate
  • PC Poly Carbonate
  • PI Polyimide
  • Cu Capper
  • ITO Indium Tin OXxide
  • Al Al
  • Mo Moly
  • Each component was mixed according to the composition of Table 1 below and uniformly mixed at room temperature for 6 hours or more to prepare a resin composition (unit: parts by weight).
  • each component used is as follows:
  • Acrylamide monomers Acryl morpholine of Formula 1 (ACMO, Acryloyl morpholine, manufactured by Kyojin Co., Ltd.), Dimethylacrylamide of Formula 2 (DMAA, N, N-Dimethyl acrylamide, manufactured by Kyojin Co., Ltd.);
  • Acrylic copolymer resin (polyester acrylate (PS420, Tetrafuntional Polyester acrylate, Miwon Specialty Chemical Co., Ltd. Korea);
  • Ethylenic monomers (glycidyl metaacrylate (Sigma Aldrich));
  • Crosslinkable monomers pentaerythritol triacrylate (PETA, Pentaerythritol triacrylate, Korea's Miwon Specialty Chemical Co., Ltd.), 1,4-butanediol diacrylate (HDDA, 1,4 butandiol diacrylate, Korea's Miwon Specialty Chemical Co., Ltd.); And
  • Photopolymerization initiator Darocur TPO, Diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide, Ciba Special Chemicals.
  • the composition Applying the composition to a thickness of 0.5 to 5 ⁇ m on the substrate cleaned with a cleaning agent, and bonded to the polymer mold and cured for each light amount using a lamp having a 365 nm wavelength, then separating the polymer mold and coated with the composition And mold release. At this time, the surface state of the cured composition was confirmed to evaluate the degree of curing of the composition. Based on the degree of stickiness of the material after the surface condition was completely dried, the degree of curing was evaluated according to the following criteria:
  • compositions Applying the composition to a thickness of 0.5 to 5 ⁇ m on the substrate cleaned with a cleaning agent, bonded to the polymer mold and cured by using a lamp having a 365 nm wavelength, and then separated from the polymer mold to release the composition-coated substrate and release Was carried out.
  • the cured composition was subjected to adhesion evaluation based on 100 cells through the cross cut method. Substrates used were evaluated according to the following criteria using a bare glass for LCD, a Cu deposited substrate, an ITO deposited substrate, and a Mo deposited substrate on a polyimide (PI) film, and an adhesive evaluation tape was a 3M 610 tape.
  • composition-coated substrate by coating the composition to a thickness of 0.5 to 5 ⁇ m on the ITO deposited PI (Polyimide) film, bonding to the polymer mold, curing using a lamp having a 365 nm wavelength, and then separating the polymer mold. And mold release.
  • the released substrate was subjected to an etching process using an ITO etchant. After the etching process, the degree of acid resistance was evaluated based on the following degree of ITO damage:
  • the photocurable resin composition according to the present invention not only has a fast curing speed and excellent acid resistance, but also excellent adhesion to various substrates applicable to a flexible display as well as a glass substrate. .
  • the photocurable resin composition of the present invention can be applied to a printed electronics-based process by including an acrylamide monomer, thereby eliminating the need for a bake and development process used in conventional photolithography. It is possible to reduce investment cost by using UV curing machine, and it is advantageous to make flexible display based on roll process.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne une composition de résine photodurcissable et, plus particulièrement, une composition de résine photodurcissable pouvant former des micro-motifs. Cette composition peut être appliquée sur un substrat d'affichage souple puisqu'elle peut durcir à grande vitesse et présente d'excellentes propriétés de revêtement, d'adhérence, et de résistance à l'acide, du fait qu'elle contient un monomère d'acrylamide.
PCT/KR2015/005767 2014-06-11 2015-06-09 Composition de résine photodurcissable WO2015190799A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201580031176.6A CN106459316B (zh) 2014-06-11 2015-06-09 光固化性树脂组合物

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2014-0070666 2014-06-11
KR20140070666 2014-06-11
KR1020150081069A KR102381307B1 (ko) 2014-06-11 2015-06-09 광경화성 수지 조성물
KR10-2015-0081069 2015-06-09

Publications (1)

Publication Number Publication Date
WO2015190799A1 true WO2015190799A1 (fr) 2015-12-17

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PCT/KR2015/005767 WO2015190799A1 (fr) 2014-06-11 2015-06-09 Composition de résine photodurcissable

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WO (1) WO2015190799A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114561184A (zh) * 2022-02-23 2022-05-31 东莞市山盟科技有限公司 一种全固含光固化绝缘胶及其制备工艺

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09311464A (ja) * 1996-05-21 1997-12-02 Nitto Denko Corp レジスト除去用接着シ―ト類とレジスト除去方法
JP2010155889A (ja) * 2008-12-26 2010-07-15 Jsr Corp 光硬化性液状樹脂組成物およびインクジェット光造形法による支持体の製造方法
KR20100088285A (ko) * 2009-01-30 2010-08-09 주식회사 동진쎄미켐 롤 프린트 공법에 적용되는 유기절연막 형성용 잉크조성물
KR20120069565A (ko) * 2010-12-20 2012-06-28 주식회사 동진쎄미켐 프린팅 프로세스용 광경화성 수지 조성물
JP2013245229A (ja) * 2012-05-23 2013-12-09 Asahi Glass Co Ltd インプリント用光硬化性組成物および微細パターンを表面に有する成形体の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09311464A (ja) * 1996-05-21 1997-12-02 Nitto Denko Corp レジスト除去用接着シ―ト類とレジスト除去方法
JP2010155889A (ja) * 2008-12-26 2010-07-15 Jsr Corp 光硬化性液状樹脂組成物およびインクジェット光造形法による支持体の製造方法
KR20100088285A (ko) * 2009-01-30 2010-08-09 주식회사 동진쎄미켐 롤 프린트 공법에 적용되는 유기절연막 형성용 잉크조성물
KR20120069565A (ko) * 2010-12-20 2012-06-28 주식회사 동진쎄미켐 프린팅 프로세스용 광경화성 수지 조성물
JP2013245229A (ja) * 2012-05-23 2013-12-09 Asahi Glass Co Ltd インプリント用光硬化性組成物および微細パターンを表面に有する成形体の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114561184A (zh) * 2022-02-23 2022-05-31 东莞市山盟科技有限公司 一种全固含光固化绝缘胶及其制备工艺

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