KR950012545B1 - Photosensitive resin compositions - Google Patents

Photosensitive resin compositions Download PDF

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KR950012545B1
KR950012545B1 KR1019920026326A KR920026326A KR950012545B1 KR 950012545 B1 KR950012545 B1 KR 950012545B1 KR 1019920026326 A KR1019920026326 A KR 1019920026326A KR 920026326 A KR920026326 A KR 920026326A KR 950012545 B1 KR950012545 B1 KR 950012545B1
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photosensitive resin
resin composition
glycol diacrylate
film
prepared
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KR1019920026326A
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Korean (ko)
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KR940015665A (en
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윤종진
서수형
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주식회사코오링
하기주
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Polymerisation Methods In General (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)

Abstract

The photosensitive resin composition consists of a polymeric binder, a photopolymerization initiator, a multi-functional monomer. The multi-functional monomer consists of trimethylol propane acrylate, tetra:methylene glycol diacrylate, triethylene glycol diacrylate and ethylene glycol diacrylate. The photosensitive resin composition includes 5-20 wt% of the multi-functional monomer. The composition has excellent adhesion to polyethylene terephtalate film and improved tenting property.

Description

감광성 수지 조성물Photosensitive resin composition

본 발명은 감광성수지 조성물에 관한 것으로서, 더욱 상세하게는 폴리에틸렌테레프타레이트 필름과의 밀착력이 증진되므로써 텐팅성 및 해상력이 향상된 감광성 수지 조성물에 관한 것이다.The present invention relates to a photosensitive resin composition, and more particularly, to a photosensitive resin composition having improved tenting property and resolution by enhancing adhesion with a polyethylene terephthalate film.

전자산업이 발달함에 따라 인쇄회로기판의 제작 등에 감광성수지 조성물이 널이 사용되고 있고, 따라서 이러한 감광성 수지 조성물 등에 대한 연구가 각국의 많은 연구자들에 의해 폭넓게 이루어지고 있다.As the electronic industry develops, a photosensitive resin composition is used as a substrate for manufacturing a printed circuit board, and thus, researches on such a photosensitive resin composition have been widely conducted by many researchers in each country.

예를들어 미합중국 특허 제3,448,089 및 4,783,519호에는 지지제인 결합제 고분자와 공중합 개시제 및 다관능성 단량체를 주성분으로 하여 이루어진 감광성 수지 조성물이 개시되어 있으나, 이들 감광성 수지 조성물은 노광후에 알칼리수용액으로 현상할 때에 노광된 부분까지도 팽윤(swelling)되어 해상력 및 텐팅성이 저하되는 문제점이 있다.For example, US Pat. Nos. 3,448,089 and 4,783,519 disclose photosensitive resin compositions composed mainly of a binder polymer as a support agent, a copolymerization initiator and a polyfunctional monomer, but these photosensitive resin compositions are exposed when developed with an alkaline aqueous solution after exposure. There is a problem that even the portion is swelled (swelling) is reduced resolution and tentability.

또한 미합중국 특허 제4,273,857호에는 스티릴피리디늄(SP)기 또는 스티릴 퀴놀리늄(SQ)기를 갖는 비닐 아세테이트 중합체의 수용성 사포닌화 화합물, 수분산성중합체, 에틸렌성 불포화기를 갖는 광중합 가능한 불포화 화합물 및 공중합 개시제를 함유하는 수분산액인 광감성 조성물이 개시되어 있으며, 일본국 특허공고 평2-58617호에는 트리아릴시아뉼레이트, 트리아릴이소시 아뉼레이트 및 테트라메틸롤메탄테트라아크릴레이트로 이루어지는 군에서 선택되는 적어도 1종의 폴리머를 함유하며, 광가교제로서 비스아지드 화합물을 함유하는 것을 특징으로 하는 광감성 조성물이 개시되어 있다. 그러나 이들 특허에서는 광감성 수지 조성물을 동장적층판에 적층시킨 후 PET필름에 대한 밀착력이 약하여, 후공정에서 노광 전에 PET 필름표면의 이물제거시에 PET필름이 수지 조성물로부터 탈락되는 문제가 있으며, 이는 텐팅성 및 해상력의 저하를 야기하여 인쇄회로기판 생산시 불량률이 높아지게 하는 원인이 된다.U.S. Pat. A photosensitive composition which is an aqueous dispersion containing an initiator is disclosed, and Japanese Patent Publication No. Hei 2-58617 selects from the group consisting of triarylcyanurate, triarylisocyanurate and tetramethylolmethane tetraacrylate. A photosensitive composition is disclosed which contains at least one polymer, and which contains a bisazide compound as a photocrosslinking agent. However, these patents have a weak adhesion to the PET film after laminating the photosensitive resin composition on the copper clad laminate, and there is a problem that the PET film is removed from the resin composition when the foreign material on the surface of the PET film is removed before exposure in a later step. It causes deterioration of fixability and resolution, which leads to high defect rate in printed circuit board production.

본 발명은 상기한 바와같은 종래기술의 문제점을 해결하기 위하여 안출된 것으로서, 본 발명의 목적은 PET 필름과의 밀착력이 증진되므로써 해상력 및 텐팅성이 향상된 감광성 수지 조성물을 제공하는 데에 있다.The present invention has been made to solve the problems of the prior art as described above, an object of the present invention is to provide a photosensitive resin composition with improved resolution and tentability by improving adhesion with PET film.

상기한 바와같은 목적을 달성하기 위하여 본 발명은, 결합제 고분자, 광중합개시제 및 다관능성 단량체를 포함하여 이루어진 감광성수지 조성물에 있어서, 상기한 다관능성 단량체로서 트리메틸롤프로판트리아크릴레이트, 테트라메틸렌글리콜디아크릴레이트, 트리에틸렌글리콜디아크릴레이트 및 에틸렌글리콜디아크릴레이트를 함께 사용함을 특징으로 하는 감광성수지 조성물을 제공한다.In order to achieve the object as described above, the present invention, in the photosensitive resin composition comprising a binder polymer, a photopolymerization initiator and a polyfunctional monomer, trimethylolpropane triacrylate, tetramethylene glycol diacryl as the polyfunctional monomer It provides a photosensitive resin composition characterized by using a rate, triethylene glycol diacrylate and ethylene glycol diacrylate together.

본 발명의 감광성수지 조성물에서 결합체고분자로는 여러 종류의 아크릴단량체를 공중합하여 제조한 아크릴공중합체를 사용한다. 이러한 결합제고분자제조에 사용되는 단량체로는 예를들어 메타크릴레이트, 아크릴산, 메타크릴산, 메틸아크릴레이트, 에틸아크릴레이트, 부틸아크릴레이트, 스티렌, 페녹시에틸아크릴레이트, 말레인산 등을 들 수 있다.As the binder polymer in the photosensitive resin composition of the present invention, an acrylic copolymer prepared by copolymerizing various kinds of acrylic monomers is used. Examples of the monomer used in the preparation of the binder polymer include methacrylate, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, styrene, phenoxyethyl acrylate, maleic acid, and the like.

본 발명의 감광성 수지 조성물은 상기 다관능성 단량체로서 트리메틸롤프로판트리아크릴레이트(TMPT), 테트라메틸렌글리콜디아크릴레이트(TMGA), 트리에틸렌글리콜디아크릴레이트(TEGA) 및 에틸렌글리콜디아크릴레이트(EGD)를 함께 사용함을 특징으로 한다.The photosensitive resin composition of the present invention is trimethylolpropane triacrylate (TMPT), tetramethylene glycol diacrylate (TMGA), triethylene glycol diacrylate (TEGA) and ethylene glycol diacrylate (EGD) as the polyfunctional monomer. It is characterized by using together.

이들 다관능성 단량체는 전체수지 조성물 100중량부에 대하여 5 내지 20중량부의 양으로 사용됨이 바람직하다. 다관능성단량체의 첨가량이 5중량부 미만일 경우에는 활성광에 의한 노광시에 중합반응, 즉 가교결합의 정도가 낮아 노광부위의 강도가 약하여 현상시 노광부위가 팽윤되어 제거되는 문제점이 있고, 또한 첨가량이 20중량부를 초과하는 경우에는 중합반응, 즉 가교결합이 과잉으로 일어나, 에칭공정 후에 노광부위를 제거하는 박리공정이 어려워지는 문제점이 발생한다.These polyfunctional monomers are preferably used in an amount of 5 to 20 parts by weight based on 100 parts by weight of the total resin composition. If the amount of the polyfunctional monomer is less than 5 parts by weight, the polymerization reaction during exposure by actinic light, that is, the degree of crosslinking is low, so that the strength of the exposure site is weak, and the exposure site is swelled and removed during development, and the addition amount If it exceeds 20 parts by weight, a polymerization reaction, i.e., crosslinking occurs excessively, and a peeling process for removing the exposed portion after the etching process becomes difficult.

상기한 고분자 결합제, 다관능성 단량체 외에 본 발명의 감광성 수지 조성물 내에는 광중합개시제, 광증감제, 염료, 발색제, 양이온개시제 등의 기타 첨가제가 첨가될수 있으며, 유기용매에 용해되어 최종 감광성 수지 조성물을 형성하게 된다.In the photosensitive resin composition of the present invention, in addition to the polymer binder and the polyfunctional monomer, other additives such as a photopolymerization initiator, a photosensitizer, a dye, a coloring agent, and a cationic initiator may be added, and are dissolved in an organic solvent to form a final photosensitive resin composition. Done.

상기한 바와같은 각종 첨가제 및 유기용매로서는, 감광성 수지 조성물에 첨가되는, 소정 용도의 일반적인 화합물이 그대로 적용될수 있다.As various additives and organic solvent as mentioned above, the general compound of the predetermined use added to the photosensitive resin composition can be applied as it is.

최근에는, 이와같은 감광성 수지 조성물의 사용을 더욱 간편하게 하기 위하여, 감광성 수지 조성물을 소정 두께의 필름 형태로 제작하여 사용한다.In recent years, in order to make use of such a photosensitive resin composition simpler, the photosensitive resin composition is produced and used for the film form of predetermined thickness.

본 발명의 감광성 수지 조성물을 건식 필름으로 제작하는 방법은 다음과 같다.The method for producing the photosensitive resin composition of the present invention into a dry film is as follows.

메틸에틸케폰 또는 테트라히드로푸란 등의 휘발성 유기용매에 용해되어 있는 상태의 감광성 수지 조성물을 약 25"두께의 폴리에스테르 지지필름상에 약 40"정도의 도포량으로 도포시키고 건조시킨 다음, 감광성 수지 조성물 도포층을 보호하기 위하여, 이 도포층 상에 35"정도의 폴리에틸렌 보호 필름을 부착시킨다.The photosensitive resin composition dissolved in a volatile organic solvent such as methyl ethyl kepon or tetrahydrofuran is applied on a polyester support film having a thickness of about 25 "at a coating amount of about 40" and dried, and then the photosensitive resin composition is applied. In order to protect the layer, a 35 "polyethylene protective film is attached on this application layer.

이와같은 건식 필름 형태로 제작된 수지 조성물을 인쇄회로 기판 등의 제조에 사용할 때에는, 수지 조성물상의 보호 필름을 제거하고 수지 조성물 필름을, 구리 박막이 부착되어 있는 회로 기판상에 라미네이팅시킨다.When the resin composition produced in the form of such a dry film is used for manufacture of a printed circuit board etc., the protective film on a resin composition is removed, and a resin composition film is laminated on the circuit board with a copper thin film.

지지필름을 제거하지 않은 채로, 그 위에 네가티브형 포토마스크 회로도를 설치한 후, 활성광으로 소정시간동안 노광시킨다. 노광 완료 후 마스크 회로도를 제거하고, 또한 감광성 수지 조성물 필름상의 지지필름을 제거한 후, 탄산나트륨 등의 알칼리 수용액을 사용하여 현상한다.Without removing the supporting film, a negative photomask circuit diagram is provided thereon and then exposed to actinic light for a predetermined time. After completion of exposure, the mask circuit diagram is removed, and after the support film on the photosensitive resin composition film is removed, development is performed using an aqueous alkali solution such as sodium carbonate.

현상이 완전히 이루어지면, 현상부위에 구리도금 및 납도금 등을 행하고, 노광된 부위를 현상하는 경우보다 훨씬 강한 수산화 나트륨 등의 알칼리수용액으로 박리시킨 다음, 적당한 에칭액을 사용하여 박리 부위의 구리를 에칭시킨 후, 앞에서 도금한 납 등을 제거하면 소망하는 인쇄 회로 기판을 얻을 수 있다.When the development is completed, copper plating and lead plating are performed on the developing part, and the exposed part is peeled with an alkaline aqueous solution such as sodium hydroxide which is much stronger than when developing, and then the copper at the peeling part is etched using a suitable etching solution. After removing the lead or the like that has been plated previously, a desired printed circuit board can be obtained.

이와같이 인쇄회로 기판을 제작하는 일련의 공정에 있어서, 첫째로는 100" 이하의 얇은 회로선이 그대로 보존되어야 하는데, 이를 위해서는 감광성 수지 조성물의 해상력이 좋아야 하며, 또한, 도금과정 중에, 호울(hole)을 막고 있는 노광된 감광성 수지 조성물 층의 부위가 제거되지 않은 채로 보존되어야 하는 바, 이를 위해서는 감광성 수지 조성물의 텐팅성이 양호하여야 한다.In such a series of processes for manufacturing a printed circuit board, first, a thin circuit line of 100 "or less must be preserved as it is. To this end, the resolution of the photosensitive resin composition should be good, and during the plating process, holes The part of the exposed photosensitive resin composition layer which is blocking the portion must be preserved without being removed. For this purpose, the tentability of the photosensitive resin composition should be good.

본 발명에서는, 상기한 다관능성 단량체로서 트리메틸롤프로판트리아크릴레이트, 테트라메틸렌글리콜디아크릴레이트, 트리에틸렌글리콜디아크릴레이트 및 에틸렌글리콜디아크릴레이트를 사용하므로써, 본 발명의 수지 조성물로 제조된 건식필름은 PET기재필름과의 밀착력이 증진되어, 자외선 노광전에 PET필름상의 이물을 제거할 때 PET필름이 수지 조성물 필름으로부터 탈락되는 것을 방지하게 되며, 이는 후공정의 불량률을 감소시키는 효과를 가져온다.In the present invention, a dry film prepared from the resin composition of the present invention by using trimethylolpropane triacrylate, tetramethylene glycol diacrylate, triethylene glycol diacrylate and ethylene glycol diacrylate as the above-mentioned multifunctional monomer. The adhesion to the PET base film is enhanced, thereby preventing the PET film from falling off from the resin composition film when removing foreign substances on the PET film before UV exposure, which has the effect of reducing the defective rate of the post process.

다음에 본 발명의 바람직한 실시예를 통하여 더욱 상세히 설명하기로 한다.Next, a preferred embodiment of the present invention will be described in more detail.

[실시예 1]Example 1

하기의 조성으로 감광성수지 조성물을 제조하였다.A photosensitive resin composition was prepared in the following composition.

성분 양(중량부)Ingredient amount (parts by weight)

(메타크릴산/아크릴산/메틸메타크릴레이트 70(Methacrylic acid / acrylic acid / methyl methacrylate 70

/2-페녹시에틸아크릴레이트)공중합체/ 2-phenoxyethyl acrylate) copolymer

(액상,고형분 50%)(Liquid, solid 50%)

트리메틸롤프로판트리아크릴레이트 2.5Trimethylolpropanetriacrylate 2.5

테트라메틸렌글리콜디아크릴레이트 2.0Tetramethylene Glycol Diacrylate 2.0

트리에틸렌글리콜디아크릴레이트 3.0Triethylene Glycol Diacrylate 3.0

에틸렌글리콜디아크릴레이트 5.0Ethylene Glycol Diacrylate 5.0

벤조페논 2.0Benzophenone 2.0

에틸 4-디메틸아미노벤조에이트 0.5Ethyl 4-dimethylaminobenzoate 0.5

다이아몬드 그린 GH(염료) 0.1Diamond green GH (dye) 0.1

P-톨루엔 술폰산·1 수화물 0.1P-toluene sulfonic acid monohydrate 0.1

메틸에틸케톤(용매) 전체 조성물이 100중량부가 되게 하는 양Methyl ethyl ketone (solvent) in an amount that makes the total composition 100 parts by weight

제조된 감광성수지 조성물을 각각 25"정도 두께의 투명한 폴리에스테르 지지필름상에 40"의 도포량으로 도포하고, 70∼75℃의 온도에서 건조하여 광중합성필름을 얻었다.Each of the prepared photosensitive resin compositions was applied at a coating amount of 40 "on a transparent polyester support film having a thickness of about 25" and dried at a temperature of 70 to 75 ° C to obtain a photopolymerizable film.

상기한 바와같이 행하여 얻어진 광중합성 필름을 직경이 각각 1, 2, 3, 4, 5mmψ인 구멍이 10개씩 형성되어 있는 구리 기판상에 라미네이팅 시킨후, 3KW의 초고압 수온 등을 이용하여 40∼50mJ/cm2정도의 노광량으로 노광시킨 다음, 1% Na2CO2수용액으로 30℃의 온도에서 60초동안 현상시켜, 이들 감광성 수지 조성물의 텐팅성을 시험하였다.The photopolymerizable film obtained as described above was laminated on a copper substrate having 10 holes each having a diameter of 1, 2, 3, 4, and 5 mmψ, and then 40 to 50 mJ / using an ultra-high pressure water temperature of 3 KW or the like. After exposing at an exposure dose of about cm 2 , the resultant was developed for 60 seconds with a 1% Na 2 CO 2 aqueous solution at a temperature of 30 ° C. to test the tentability of these photosensitive resin compositions.

상기한 바와 같은 텐팅성 시험결과와 함께, 광중합성필름을 로울형태로 권치하였을 때 액이 바깥으로 흘러나오는 현상(가장자리 융착 또는 상온유출)을 조사하여 하기 표 1에 나타내었다.In addition to the results of the tentability test as described above, when the photopolymerizable film was wound in the form of a roll, the phenomenon that the liquid flows outward (edge fusion or room temperature outflow) was investigated and shown in Table 1 below.

[실시예2]Example 2

하기의 조성으로 감광성 수지 조성물을 제조하였다.The photosensitive resin composition was manufactured with the following composition.

성분 양(중량부)Ingredient amount (parts by weight)

(메타크릴산/아크릴산/메틸메타크릴레이트 70(Methacrylic acid / acrylic acid / methyl methacrylate 70

/2-페녹시에틸아크릴레이트)공중합체/ 2-phenoxyethyl acrylate) copolymer

(액상,고형분 50%)(Liquid, solid 50%)

트리메틸롤프로판트리아크릴레이트 4.5Trimethylolpropanetriacrylate 4.5

테트라메틸렌글리콜디아크릴레이트 3.0Tetramethylene Glycol Diacrylate 3.0

트리에틸렌글리콜디아크릴레이트 2.0Triethylene Glycol Diacrylate 2.0

에틸렌글리콜디아크릴레이트 2.5Ethylene Glycol Diacrylate 2.5

벤조페논 2.0Benzophenone 2.0

에틸 4-디메틸아미노벤조에이트 0.5Ethyl 4-dimethylaminobenzoate 0.5

다이아몬드 그린 GH(염료) 0.1Diamond green GH (dye) 0.1

P-톨루엔 술폰산·1 수화물 0.1P-toluene sulfonic acid monohydrate 0.1

메틸에틸케톤(용매) 전체 조성물이 100중량부가 되게 하는 양Methyl ethyl ketone (solvent) in an amount that makes the total composition 100 parts by weight

제조된 감광성수지 조성물을 상기 실시예 1에 기재된 방법으로 광중합성필름으로 제조하고 텐팅성 및 가장자리융착(상온유출)을 조사하여 그 결과를 역시 하기 표 1에 나타내었다.The prepared photosensitive resin composition was prepared as a photopolymerizable film by the method described in Example 1, and tentative property and edge fusion (outflow at room temperature) were investigated and the results are also shown in Table 1 below.

[실시예 3]Example 3

하기의 조성으로 감광성수지 조성물을 제조하였다.A photosensitive resin composition was prepared in the following composition.

성분 양(중량부)Ingredient amount (parts by weight)

(메타크릴산/아크릴산/메틸메타크릴레이트 70(Methacrylic acid / acrylic acid / methyl methacrylate 70

/2-페녹시에틸아크릴레이트)공중합체/ 2-phenoxyethyl acrylate) copolymer

(액상,고형분 50%)(Liquid, solid 50%)

트리메틸롤프로판트리아크릴레이트 3.5Trimethylolpropanetriacrylate 3.5

테트라메틸렌글리콜디아크릴레이트 2.5Tetramethylene Glycol Diacrylate 2.5

트리에틸렌글리콜디아크릴레이트 2.5Triethylene Glycol Diacrylate 2.5

에틸렌글리콜디아크릴레이트 4.5Ethylene Glycol Diacrylate 4.5

벤조페논 2.0Benzophenone 2.0

에틸 4-디메틸아미노벤조에이트 0.5Ethyl 4-dimethylaminobenzoate 0.5

다이아몬드 그린 GH(염료) 0.1Diamond green GH (dye) 0.1

P-톨루엔 술폰산·1 수화물 0.1P-toluene sulfonic acid monohydrate 0.1

메틸에틸케톤(용매) 전체 조성물이 100중량부가 되게 하는 양Methyl ethyl ketone (solvent) in an amount that makes the total composition 100 parts by weight

제조된 감광성수지 조성물을 상기 실시예 1에 기재된 방법으로 광중합성필름으로 제조하고 텐팅성 및 가장자리융착(상온유출)을 조사하여 그 결과를 역시 하기 표 1에 나타내었다.The prepared photosensitive resin composition was prepared as a photopolymerizable film by the method described in Example 1, and tentative property and edge fusion (outflow at room temperature) were investigated and the results are also shown in Table 1 below.

[실시예 4]Example 4

하기의 조성으로 감광성수지 조성물을 제조하였다.A photosensitive resin composition was prepared in the following composition.

성분 양(중량부)Ingredient amount (parts by weight)

(메타크릴산/아크릴산/메틸메타크릴레이트 70(Methacrylic acid / acrylic acid / methyl methacrylate 70

/2-페녹시에틸아크릴레이트)공중합체/ 2-phenoxyethyl acrylate) copolymer

(액상,고형분 50%)(Liquid, solid 50%)

트리메틸롤프로판트리아크릴레이트 5.0Trimethylolpropanetriacrylate 5.0

테트라메틸렌글리콜디아크릴레이트 2.0Tetramethylene Glycol Diacrylate 2.0

트리에틸렌글리콜디아크릴레이트 3.0Triethylene Glycol Diacrylate 3.0

에틸렌글리콜디아크릴레이트 3.0Ethylene Glycol Diacrylate 3.0

벤조페논 2.0Benzophenone 2.0

에틸 4-디메틸아미노벤조에이트 0.5Ethyl 4-dimethylaminobenzoate 0.5

다이아몬드 그린 GH(염료) 0.1Diamond green GH (dye) 0.1

P-톨루엔 술폰산·1 수화물 0.1P-toluene sulfonic acid monohydrate 0.1

메틸에틸케톤(용매) 전체 조성물이 100중량부가 되게 하는 양Methyl ethyl ketone (solvent) in an amount that makes the total composition 100 parts by weight

제조된 감광성수지 조성물을 상기 실시예 1에 기재된 방법으로 광중합성필름으로 제조하고 텐팅성 및 가장자리융착(상온유출)을 조사하여 그 결과를 역시 하기 표 1에 나타내었다.The prepared photosensitive resin composition was prepared as a photopolymerizable film by the method described in Example 1, and tentative property and edge fusion (outflow at room temperature) were investigated and the results are also shown in Table 1 below.

[비교예 1]Comparative Example 1

하기의 조성으로 감광성수지 조성물을 제조하였다.A photosensitive resin composition was prepared in the following composition.

성분 양(중량부)Ingredient amount (parts by weight)

(메타크릴산/아크릴산/메틸메타크릴레이트 70(Methacrylic acid / acrylic acid / methyl methacrylate 70

/2-페녹시에틸아크릴레이트)공중합체/ 2-phenoxyethyl acrylate) copolymer

(액상,고형분 50%)(Liquid, solid 50%)

트리메틸롤프로판트리아크릴레이트 2.5Trimethylolpropanetriacrylate 2.5

테트라에틸렌글리콜디아크릴레이트 2.0Tetraethylene Glycol Diacrylate 2.0

트리에틸렌글리콜디아크릴레이트 3.0Triethylene Glycol Diacrylate 3.0

에틸렌글리콜디아크릴레이트 0Ethylene Glycol Diacrylate 0

벤조페논 2.0Benzophenone 2.0

에틸 4-디메틸아미노벤조에이트 0.5Ethyl 4-dimethylaminobenzoate 0.5

다이아몬드 그린 GH(염료) 0.1Diamond green GH (dye) 0.1

P-톨루엔 술폰산·1 수화물 0.1P-toluene sulfonic acid monohydrate 0.1

메틸에틸케톤(용매) 전체 조성물이 100중량부가 되게 하는 양Methyl ethyl ketone (solvent) in an amount that makes the total composition 100 parts by weight

제조된 감광성수지 조성물을 상기 실시예 1에 기재된 방법으로 광중합성필름으로 제조하고 텐팅성 및 가장자리융착(상온유출)을 조사하여 그 결과를 역시 하기 표 1에 나타내었다.The prepared photosensitive resin composition was prepared as a photopolymerizable film by the method described in Example 1, and tentative property and edge fusion (outflow at room temperature) were investigated and the results are also shown in Table 1 below.

[비교예 2]Comparative Example 2

하기의 조성으로 감광성수지 조성물을 제조하였다.A photosensitive resin composition was prepared in the following composition.

성분 양(중량부)Ingredient amount (parts by weight)

(메타크릴산/아크릴산/메틸메타크릴레이트 70(Methacrylic acid / acrylic acid / methyl methacrylate 70

/2-페녹시에틸아크릴레이트)공중합체/ 2-phenoxyethyl acrylate) copolymer

(액상,고형분 50%)(Liquid, solid 50%)

트리메틸롤프로판트리아크릴레이트 1.5Trimethylolpropanetriacrylate 1.5

테트라메틸렌글리콜디아크릴레이트 1.0Tetramethylene Glycol Diacrylate 1.0

트리에틸렌글리콜디아크릴레이트 1.0Triethylene Glycol Diacrylate 1.0

에틸렌글리콜디아크릴레이트 0.5Ethylene Glycol Diacrylate 0.5

벤조페논 2.0Benzophenone 2.0

에틸 4-디메틸아미노벤조에이트 0.5Ethyl 4-dimethylaminobenzoate 0.5

다이아몬드 그린 GH(염료) 0.1Diamond green GH (dye) 0.1

P-톨루엔 술폰산·1 수화물 0.1P-toluene sulfonic acid monohydrate 0.1

메틸에틸케톤(용매) 전체 조성물이 100중량부가 되게 하는 양Methyl ethyl ketone (solvent) in an amount that makes the total composition 100 parts by weight

제조된 감광성수지 조성물을 상기 실시예 1에 기재된 방법으로 광중합성필름으로 제조하고 텐팅성 및 가장자리융착(상호유출)을 조사하여 그 결과를 역시 하기 표 1에 나타내었다.The prepared photosensitive resin composition was prepared as a photopolymerizable film by the method described in Example 1, and tentative properties and edge fusion (interleaved leakage) were investigated. The results are also shown in Table 1 below.

[비교예3]Comparative Example 3

하기의 조성으로 감광성수지 조성물을 제조하였다.A photosensitive resin composition was prepared in the following composition.

성분 양(중량부)Ingredient amount (parts by weight)

(메타크릴산/아크릴산/메틸메타크릴레이트 70(Methacrylic acid / acrylic acid / methyl methacrylate 70

/2-페녹시에틸아크릴레이트)공중합체/ 2-phenoxyethyl acrylate) copolymer

(액상,고형분 50%)(Liquid, solid 50%)

트리메틸롤프로판트리아크릴레이트 5.5Trimethylolpropanetriacrylate 5.5

테트라메틸렌글리콜디아크릴레이트 4.5Tetramethylene Glycol Diacrylate 4.5

트리에틸렌글리콜디아크릴레이트 4.5Triethylene Glycol Diacrylate 4.5

에틸렌글리콜디아크릴레이트 6.5Ethylene Glycol Diacrylate 6.5

벤조페논 2.0Benzophenone 2.0

에틸 4-디메틸아미노벤조에이트 0.5Ethyl 4-dimethylaminobenzoate 0.5

다이아몬드 그린 GH(염료) 0.1Diamond green GH (dye) 0.1

P-톨루엔 술폰산·1 수화물 0.1P-toluene sulfonic acid monohydrate 0.1

메틸에틸케톤(용매) 전체 조성물이 100중량부가 되게 하는 양Methyl ethyl ketone (solvent) in an amount that makes the total composition 100 parts by weight

제조된 감광성수지 조성물을 상기 실시예 1에 기재된 방법으로 광중합성필름으로 제조하고 텐팅성 및 가장자리융착(상온유출)을 조사하여 그 결과를 역시 하기 표 1에 나타내었다.The prepared photosensitive resin composition was prepared as a photopolymerizable film by the method described in Example 1, and tentative property and edge fusion (outflow at room temperature) were investigated and the results are also shown in Table 1 below.

[표 1] 평가 결과Table 1 Evaluation Results

상기 표 1의 결과로부터, 본 발명에 따르는 감광성수지 조성물로 제조된 광중합성필름의 4종류의 다관능성아크릴단량체, 리콜디아크릴레이트, 즉 트리메틸콜프로판트리아크릴레이트, 테트라메틸렌글리롤디아크릴레이트, 트리에틸렌글리콜디아크릴레이트, 에틸렌글리콜디아크릴레이트를 모두 함유하지 않거나 5 내지 20중량부를 벗어나는 양으로 함유하는 비교예의 조성물에 비해 텐팅성이 현저히 우수하며 가장자리융착(상온유출)현상도 훨씬 적게 발생함을 알 수 있다.From the results in Table 1, four types of polyfunctional acrylic monomers, recall diacrylates, that is, trimethyl cholpropane triacrylate, tetramethylene glycol diacrylate, and tri-polymer of the photopolymerizable film prepared by the photosensitive resin composition according to the present invention Compared to the composition of the comparative example containing neither ethylene glycol diacrylate nor ethylene glycol diacrylate or in an amount exceeding 5 to 20 parts by weight, the tentability is remarkably excellent, and the edge fusion (at room temperature) phenomenon is much less likely to occur. Able to know.

Claims (1)

결합제 고분자, 광중합 개시제, 및 다관능성 단량체를 포함하여 이루어지는 감광성 수지 조성물에 있어서, 상기한 다관능성 단량체를 트리메틸롤프로판트리아크릴레이트, 테트라메틸렌그릴롤디아크릴레이트, 트리에틸렌글리콜디아크릴레이트 및 에틸렌글리콜디아크릴레이트의 4성분으로 구성하여 수지 조성물의 전체에 대하여 5 내지 20중량% 포함시킴을 특징으로 하는, 감광성 수지 조성물.In the photosensitive resin composition which consists of a binder polymer, a photoinitiator, and a polyfunctional monomer, the said polyfunctional monomer is trimethylolpropane triacrylate, tetramethylene grillol acrylate, triethylene glycol diacrylate, and ethylene glycol di. A photosensitive resin composition comprising four components of an acrylate and containing 5 to 20% by weight based on the entirety of the resin composition.
KR1019920026326A 1992-12-30 1992-12-30 Photosensitive resin compositions KR950012545B1 (en)

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