KR100729171B1 - Resin composition for dry film photoresist - Google Patents

Resin composition for dry film photoresist Download PDF

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KR100729171B1
KR100729171B1 KR1020010085708A KR20010085708A KR100729171B1 KR 100729171 B1 KR100729171 B1 KR 100729171B1 KR 1020010085708 A KR1020010085708 A KR 1020010085708A KR 20010085708 A KR20010085708 A KR 20010085708A KR 100729171 B1 KR100729171 B1 KR 100729171B1
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dry film
film photoresist
methacrylate
integer
modified polysiloxane
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KR20030055664A (en
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홍창표
김정근
최준혁
한국현
김장훈
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주식회사 코오롱
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers

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  • Materials For Photolithography (AREA)
  • Graft Or Block Polymers (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

본 발명은 베이스 고분자, 광중합 개시제, 광중합 단량체 및 기타 첨가제로 구성된 드라이 필름 포토레지스트 조성물에 있어서, 다음 화학식 1로 표시되는 유기변성 폴리실록산계 유도체를 더 포함하여 제조된 드라이 필름 포토레지스트는 드라이 필름 조액시 교반공정에서 발생된 기포로 발생될 수 있는 핀홀 이나 덴트 발생을 억제하여 코팅의 균일성을 구현함으로써 품질균일화 및 안정화에 효과적임과 동시에 인쇄회로기판의 현상 및 박리공정에서의 현상액 및 박리액의 거품발생량을 감소시키는 데 효과적이다. The present invention relates to a dry film photoresist composition comprising a base polymer, a photopolymerization initiator, a photopolymerization monomer, and other additives, wherein the dry film photoresist prepared by further comprising an organic modified polysiloxane derivative represented by Formula 1 below It is effective for quality uniformity and stabilization by suppressing the generation of pinholes or dents that can be generated by bubbles generated in the stirring process, and it is effective for quality uniformity and stabilization. It is effective in reducing the amount produced.

Figure 112007003574549-pat00004
Figure 112007003574549-pat00004

상기 식에서, R은 수소, 메틸 또는 에틸기이며, R'은 폴리에테르, 탄소수 1∼10 사이의 알킬, 아크릴레이트 또는 메타크릴레이트이며, m은 1∼50 사이의 정수이며, n은 1∼10 사이의 정수이다. Wherein R is hydrogen, methyl or ethyl group, R 'is a polyether, alkyl having 1 to 10 carbon atoms, acrylate or methacrylate, m is an integer from 1 to 50, n is from 1 to 10 Is an integer.

포토레지스트*폴리실록산*핀홀*덴트*드라이필름Photoresist * Polysiloxane * Pinhole * Dent * Dry Film

Description

드라이 필름 포토레지스트 조성물{Resin composition for dry film photoresist} Resin composition for dry film photoresist

본 발명은 인쇄 회로 기판(Printed Circuited Board) 제작시 이미지 형성재료로 사용되는 드라이 필름 포토레지스트(Dry Film Photoresist) 조성물에 관한 것으로서, 상세하게는 베이스 고분자, 광중합 개시제, 광중합 단량체 및 기타 첨가제로 구성된 드라이 필름 레지스트 조성에 유기변성 폴리실로산계 유도체를 첨가한 드라이 필름 포토레지스트 조성물에 관한 것이다. The present invention relates to a dry film photoresist composition used as an image forming material when manufacturing a printed circuited board. Specifically, the present invention relates to a dry film composed of a base polymer, a photopolymerization initiator, a photopolymerization monomer, and other additives. The present invention relates to a dry film photoresist composition in which an organic modified polysilic acid derivative is added to a film resist composition.

통상적으로 인쇄회로기판에 회로를 형성하는 데에는 드라이 필름 레지스트(Dry Film Resist, 이하 DFR 이라 함)가 사용된다. Typically, a dry film resist (hereinafter referred to as DFR) is used to form a circuit on a printed circuit board.

이러한 드라이 필름은 조성에 필요한 약제를 조액한 후 일정시간 교반을 진행한 후 코팅장치를 통하여 폴리에스터 등의 필름에 도포 되어지며, 추후 건조단을 통하여 용매를 건조시킨 후 폴리에틸렌 또는 폴리에스터 보호필름을 라미네이션시켜 이루어진다. Such a dry film is prepared by preparing a drug required for the composition and then stirred for a predetermined time, and then applied to a film such as polyester through a coating apparatus.Afterwards, the solvent is dried through a drying stage, and then polyethylene or polyester protective film is applied. It is done by lamination.

한편, 상기와 같은 드라이 필름 제조과정에서 조액시 기포발생을 억제하기 위하여 교반시간 및 교반속도를 조절하며, 교반 후 일정시간 동안 방치시켜 조액상에 남아있는 기포를 제거하는 과정을 거친다. 그러나 이러한 과정에도 불구하고, 잔존한 기포가 완전히 제거되지 않아 드라이 필름 코팅면에 핀홀(pin hole)이나 덴트(dent)가 발생하는 문제점이 있었다. On the other hand, in the dry film manufacturing process as described above to adjust the stirring time and stirring speed in order to suppress the bubble generation during the liquid preparation, the process of removing the bubbles remaining in the crude liquid by leaving for a certain time after stirring. However, despite this process, the remaining bubbles are not completely removed, there was a problem that a pin hole (dent) or a dent occurs in the dry film coating surface.

이러한 핀홀이나 덴트는 유기용매를 건조시키는 과정에서도 발생할 수 있으며, 이때는 건조속도나 건조온도의 조절을 통하여 줄여나가고 있다. Such pinholes or dents can also occur in the process of drying the organic solvent, in which case it is reduced by controlling the drying rate or drying temperature.

그러나, 조액상의 점도에 따라 상기 조건을 일정하게 할 수 없는 단점이 있으며 유기용매 건조시에 핀홀이나 덴트발생을 억제하기 위해 건조속도나 건조온도의 하향 조절이 필요하므로 생산성의 저하가 발생하는 문제점이 있었다. However, there is a disadvantage in that the above conditions cannot be made constant according to the viscosity of the crude liquid phase, and in order to suppress the generation of pinholes or dents during drying of the organic solvent, it is necessary to lower the drying speed or the drying temperature, thereby causing a decrease in productivity. There was this.

한편, 종래 인쇄회로기판 제조시에 드라이 필름 레지스트를 사용하는 경우 추후 현상 및 박리공정에서 거품발생을 억제하기 위해 소포제를 사용하여 왔다. On the other hand, in the case of using a dry film resist when manufacturing a conventional printed circuit board, a defoaming agent has been used to suppress the generation of bubbles in the later development and peeling process.

그러나, 이러한 현상 및 박리공정에서의 거품제거를 위하여 과도한 소포제의 사용으로 인한 생산비용 상승과 동시에 생산성이 떨어지는 문제점을 가지고 있으므로 현상 및 박리공정에서 거품 발생량이 적은 드라이 필름의 필요성이 증대되었다.
However, since the production cost increases due to the excessive use of the antifoaming agent for defoaming in the developing and peeling process, and the productivity is decreased, the necessity of the dry film with less foaming amount in the developing and peeling process is increased.

이에 본 발명자들은 상기와 같은 문제점을 해결하기 위하여 연구 노력하던 중, 종래의 드라이 필름 포토레지스트용 조성물에 첨가제로서 유기변성 폴리실록산계 유도체를 첨가한 결과, 드라이 필름 조액시 교반공정에서 발생된 기포로 발생할 수 있는 핀홀(Pin hole)이나 덴트(dent) 발생을 억제하여 코팅의 균일성을 구현함 으로써 드라이 필름 레지스트의 표면의 품질이 균일한 동시에 인쇄회로기판의 현상 및 박리 공정에서의 현상액 및 박리액의 거품발생량을 효과적으로 감소시킬 수 있다는 것을 알게되어 본 발명을 완성하게 되었다. Accordingly, the present inventors, while trying to solve the above problems, add the organic modified polysiloxane-based derivative as an additive to the conventional dry film photoresist composition, as a result of bubbles generated in the stirring process during dry film solution The uniformity of the surface of the dry film resist can be achieved by suppressing the occurrence of pin holes or dents that can occur, and at the same time, the development of the developer and the stripping solution in the development and peeling process of the printed circuit board. It has been found that the amount of foaming can be effectively reduced to complete the present invention.

따라서, 본 발명의 목적은 드라이 필름 조액시 교반공정에서 기포가 발생하지 않으며, 인쇄회로기판의 현상 및 박리 공정에서 현상액과 박리액의 거품발생을 감소시킬 수 있는 드라이 필름 포토레지스트 조성물을 제공하는 데 있다. Accordingly, an object of the present invention is to provide a dry film photoresist composition which does not generate bubbles in the stirring process during the dry film crude solution, and can reduce the foaming of the developer and the peeling solution in the development and peeling process of the printed circuit board. have.

이와같은 목적을 달성하기 위한 본 발명의 드라이 필름 포토레지스트 조성물은 베이스 고분자, 광중합 개시제, 광중합 단량체 및 기타 첨가제로 구성된 드라이 필름 포토레지스트 조성물에 있어서, 다음 화학식 1로 표시되는 유기변성 폴리실록산계 유도체를 더 포함하는 것임을 그 특징으로 한다.
The dry film photoresist composition of the present invention for achieving the above object in the dry film photoresist composition consisting of a base polymer, a photopolymerization initiator, a photopolymerization monomer and other additives, further comprising an organic modified polysiloxane derivative represented by the following formula (1) It is characterized by including.

화학식 1Formula 1

Figure 112007003574549-pat00005
Figure 112007003574549-pat00005

상기 식에서, R은 수소, 메틸 또는 에틸기이며, R'은 폴리에테르, 탄소수 1∼10 사이의 알킬, 아크릴레이트 또는 메타크릴레이트이며, m은 1∼50 사이의 정수이며, n은 1∼10 사이의 정수이다.
Wherein R is hydrogen, methyl or ethyl group, R 'is a polyether, alkyl having 1 to 10 carbon atoms, acrylate or methacrylate, m is an integer from 1 to 50, n is from 1 to 10 Is an integer.

이와같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.

본 발명은 베이스 고분자, 광중합 단량체, 광중합 개시제및 기타 첨가제를 주성분으로 하는 종래의 드라이 필름 포토레지스트 조성물에 있어서, 유기변성 폴리실록산계 유도체를 더 첨가한 드라이 필름 포토레지스트 조성물에 관한 것이다. The present invention relates to a dry film photoresist composition further comprising an organic modified polysiloxane derivative in a conventional dry film photoresist composition mainly comprising a base polymer, a photopolymerization monomer, a photopolymerization initiator, and other additives.

본 발명에서 사용하는 베이스 고분자는 통상의 DFR 조성과 같은 메타크릴계 공중합체, 아세토아세틸기를 포함하는 아크릴릭 공중합체와 같은 아크릴계 수지, 폴리에스터 수지, 폴리우레탄 수지 등이다. The base polymer used in the present invention is an acrylic resin such as a methacryl-based copolymer having a conventional DFR composition, an acrylic copolymer containing an acetoacetyl group, a polyester resin, a polyurethane resin and the like.

상기 메타크릴계 공중합체는 메틸메타크릴레이트(methylmethacrylate), 에틸메타클릴레이트, 프로필 메타크릴레이트, 부틸메타클릴레이트, 헥실 메타클릴레이트, 2-에틸헥실 메타크릴레이트, 시클로헥실 메타크릴레이트, 벤질 메타크릴레이트, 다이메틸아미노에틸 메타크릴레이트(dimethylaminoethyl methacrylate), 하이드록시에틸 메타크릴레이트(hydroxyethyl methacrylate), 하이드록시프로필 메타크릴레이트(hydroxypropyl methacrylate), 글리시딜 메타크릴레이트(glycidyl methacrylate) 등과 같은 메타크릴계 고분자 중에서 선택된 것으로 공중합시켜 사용한다.The methacryl-based copolymer is methyl methacrylate (methylmethacrylate), ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate Latex, benzyl methacrylate, dimethylaminoethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate And copolymerized with one selected from methacrylic polymers such as).

또한, 상기 메타크릴릭 공중합체는 필요시 에틸렌 불포화 카르복실산 또는 기타 고분자와 공중합하여 사용할 수 있으며, 에틸렌 불포화 카르복실산의 구체적인 예에는 아크릴산(acrylic acid), 메타크릴산(methacrylic acid), 크로토닉산(crotonic acid)과 같은 모노아크릴산(monoacrylic acid); 말레인산(maleic acid), 푸마르산(fumaric acid), 이타콘산(itaconic acid)과 같은 디카르복실산(dicarboxylic acid); 이들의 무수물; 또는 반-에스터된 (half ester) 고분자 등도 사용될 수 있다. 이들 중 아크릴산과 메타크릴산이 특히 바람직하며, 우수한 물성을 나타낸다. 약알카리 현상형 포토레지스트 수지의 경우 에틸렌 불포화 카르복실산의 양은 15∼30 중량%로 (산가 : 100-200 mg KOH/g) 사용한다.In addition, the methacrylic copolymer may be copolymerized with an ethylenically unsaturated carboxylic acid or other polymer, if necessary, and specific examples of the ethylenically unsaturated carboxylic acid may include acrylic acid, methacrylic acid, and chromate. Monoacrylic acid, such as crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; Anhydrides thereof; Or half ester polymers may also be used. Of these, acrylic acid and methacrylic acid are particularly preferred, and exhibit excellent physical properties. In the case of weak alkali developing photoresist resin, the amount of ethylenically unsaturated carboxylic acid is 15 to 30% by weight (acid value: 100-200 mg KOH / g).

또한 기타 공중합 가능한 고분자들은 아크릴아마이드, 메타크릴아마이드, 아크릴로니트릴, 메타크릴로니트릴, 스티렌, α-메틸스티렌, 비닐아세테이트 및 알킬 비닐 에테르 등이다. Other copolymerizable polymers are acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate and alkyl vinyl ethers.

또한 본 발명에서 사용되는 광중합 단량체는 통상의 DFR 조성에서와 같이 다관능 단량체와 단관능 단량체를 사용할 수 있는 바, 다관능 단량체로는 에틸렌글리콜디메타크릴레이트, 디에틸렌글리콜디메타크릴레이트, 테트라에틸렌글리콜디메타크릴레이트, 프로필렌글리콜디메타크릴레이트, 폴리프로필렌글리콜디메타크릴레이트, 부틸렌글리콜디메타크릴레이트, 네오펜틸글리콜디메타크릴레이트, 1,6-헥산글리콜디메타크릴레이트, 트리메틸올프로판 트리메타크릴레이트(trimethyolpropane trimethacrylate), 글리세린 디메타크릴레이트, 펜타에리트리톨 디메타크릴레이트(pentaerythritol dimethacrylate), 펜타에리트리톨 트리메타크릴레이트(pentaerythritol trimethacrylate), 디펜타에리트리톨 펜타메타크릴레이트(dipentaerythritol pentamethacrylate), 2,2-비스(4-메타크릴옥시디에톡시페닐)프로판(2,2-bis(4-methacryloxydiethoxyphenyl)propane), 2-하이드록시-3-메타크릴로일옥시프로필 메타크릴레이트(2-hydroxy-3- methacryloyloxypropyl methacrylate), 에틸렌글리콜 디글리시딜에테르 디메타크릴레이트(ethylene glycol diglycidyl ether dimethacrylate), 디에틸렌글리콜 디글리시딜에테르 디메타크릴레이트(diethylene glycol diglycidyl ether dimethacrylate), 프탈산 디글리시딜에스테르 디메타크릴레이트(phthalic acid diglycidyl ester dimethacrylate), 글리세린 폴리글리시딜에테르 폴리메타크릴레이트(glycerin polyglycidyl ether polymethacrylate)등이 있다.In addition, the photopolymerizable monomer used in the present invention may use a polyfunctional monomer and a monofunctional monomer as in the conventional DFR composition, and as the polyfunctional monomer, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetra Ethylene glycol dimethacrylate, propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexane glycol dimethacrylate, trimethyl Olpropane trimethacrylate, trimethyolpropane trimethacrylate, glycerin dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentamethacrylate (pentaerythritol trimethacrylate) dipentaerythritol pentamethacrylate), 2,2-bis (4-methacryloxydiethoxy Phenyl) propane (2,2-bis (4-methacryloxydiethoxyphenyl) propane), 2-hydroxy-3-methacryloyloxypropyl methacrylate, ethylene glycol diglycidyl Ethylene glycol diglycidyl ether dimethacrylate, diethylene glycol diglycidyl ether dimethacrylate, phthalic acid diglycidyl ester dimethacrylate And glycerin polyglycidyl ether polymethacrylate.

또한, 단관능 단량체의 예로는 2-하이드록시에틸 메타크릴레이트, 2-하이드록시프로필 메타크릴레이트, 2-하이드록시부틸 메타크릴레이트, 2-페녹시-2-하이드록시프로필 메타크릴레이트, 2-메타크릴로일옥시-2-하이드록시프로필 프탈레이트(2-methacryloyloxy-2-hydroxypropyl phthalate), 3-클로로-2-하이드록시프로필 메타크릴레이트, 글리세린 모노메타크릴레이트, 2-메타크릴로일옥시에틸산 포스페이트, 프탈산 유도체의 메타크릴레이트, N-메틸올 메타크릴아마이드 등이 있다.In addition, examples of monofunctional monomers include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-phenoxy-2-hydroxypropyl methacrylate, 2 2-methacryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl methacrylate, glycerin monomethacrylate, 2-methacryloyloxy Ethyl phosphate, methacrylate of phthalic acid derivatives, N-methylol methacrylate, and the like.

상기 광중합 단량체의 함량은 상기 베이스 고분자 100 중량부에 대하여 10∼80 중량부로 사용할 수 있는 바, 만일 상기 함량이 10 중량부보다 적게 사용하면 레지스트의 유연성이 저하되고 현상 속도도 느려진다. 반면 상기 함량이 80 중량부를 초과할 경우 용액의 점도 및 콜드 플로우(cold flow)가 증가하고 박리 속도가 느려진다.The content of the photopolymerizable monomer may be used in an amount of 10 to 80 parts by weight based on 100 parts by weight of the base polymer. If the content is less than 10 parts by weight, the flexibility of the resist is lowered and the development speed is also slowed. On the other hand, if the content exceeds 80 parts by weight, the viscosity and cold flow of the solution increases and the peeling rate is slowed.

또한, 본 발명의 광중합 개시제로는 통상의 DFR 조성에서와 같이 벤조인 메틸 에테르, 벤조인 에틸 에테르, 벤조인 아이소프로필 에테르, 벤조인 n-부틸 에테 르, 벤조인 페닐 에테르, 벤질 디페닐 디설파이드, 벤질 디메틸 케탈, 안트라퀴논, 나프토퀴논, 3,3-디메틸-4-메톡시벤조페논(3,3-dimethyl-4-methoxybenzophenone), 벤조페논, p,p'-비스(디메틸아미노)벤조페논, p,p'-비스(디에틸아미노)벤조페논, p,p'-디에틸아미노벤조페논, 피발론 에틸에테르(pivalone ethyl ether), 1,1-디클로로 아세토페논, p-t-부틸디클로로아세토페논, 헥사아릴-이미다졸의 다이머(dimer), 2,2'-디에톡시아세토페논, 2,2'-디에톡시-2-페닐아세토페논, 2,2'-디클로로-4-페녹시아세토페논, 페닐 글리옥실레이트, α-하이드록시-이소부틸페논, 디벤조스판(dibenzospan), 1-(4-이소프로필페닐)-2-하이드록시-2-메틸-1-프로판온, 2-메틸-[4-(메틸티오)페닐]-2-모폴리노-1-프로판온(2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone), 트리-브로모페닐설폰, 트리브로모메틸페닐설폰(tribromomethylphenylsulfone) 등을 들 수 있다. In addition, the photopolymerization initiator of the present invention may be selected from the group consisting of benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, Benzyl dimethyl ketal, anthraquinone, naphthoquinone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, p, p'-bis (dimethylamino) benzophenone , p, p'-bis (diethylamino) benzophenone, p, p'-diethylaminobenzophenone, pivalone ethyl ether, 1,1-dichloro acetophenone, pt-butyldichloroacetophenone Dimers of hexaaryl-imidazole, 2,2'-diethoxyacetophenone, 2,2'-diethoxy-2-phenylacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, Phenyl glyoxylate, α-hydroxy-isobutylphenone, dibenzospan, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-prop Ropanone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone (2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone), Tri-bromophenyl sulfone, tribromomethylphenylsulfone, and the like.

한편, 상기 광개시제의 첨가량은 베이스 고분자와 광중합 단량체 100 중량부에 대하여 1∼20 중량부이다.On the other hand, the addition amount of the photoinitiator is 1 to 20 parts by weight based on 100 parts by weight of the base polymer and the photopolymerization monomer.

한편 본 발명에서는 드라이 필름 포토레지스트 제조시의 핀홀 및 덴트 발생을 최소화하고 추후 현상 및 박리공정에서의 거품발생을 억제하기 위하여 특징적으로 상기 화학식 1로 표시되는 유기변성 폴리실록산계 유도체를 첨가하여 사용하는 바, 본 발명에서 사용되는 유기변성 폴리실록산계 유도체는 다음과 같은 특징을 가지고 있다. Meanwhile, in the present invention, in order to minimize the generation of pinholes and dents during the manufacture of a dry film photoresist and to suppress the generation of bubbles in the subsequent development and peeling process, the organic modified polysiloxane derivative represented by Chemical Formula 1 is added to the bar. , The organic modified polysiloxane derivative used in the present invention has the following characteristics.

첫째, 드라이필름 조성상 첨가된 유기변성 폴리실록산계 유도체는 교반공정에서 발생한 기포를 효과적으로 제거함으로 인하여 교반공정의 효율성을 증대시킴 과 동시에 기포제거를 위한 조액 후 방치시간을 줄일 수 있으며 기포에 의한 품질 저하를 막을 수 있다.First, the organic modified polysiloxane derivative added in the dry film composition effectively increases the efficiency of the stirring process by effectively removing the bubbles generated during the stirring process, and at the same time reduces the standing time after the preparation for removing the bubbles and reduces the quality deterioration by the bubbles. You can stop it.

둘째, 드라이필름 조성상 첨가된 유기변성 폴리실록산계 유도체는 건조공정에서 유기용매 제거시 레벨링제 역할을 수행하여 코팅면에서 생길 수 있는 핀홀이나 덴트의 양을 급격히 감소시켜 코팅표면의 평활도 및 균일한 조도를 구현할 수 있어 드라이 필름의 품질 향상에 기여할 수 있다.Secondly, the organic modified polysiloxane derivative added in the dry film composition acts as a leveling agent when removing the organic solvent in the drying process to drastically reduce the amount of pinholes or dents that may occur on the coating surface, thereby providing smoothness and uniform roughness of the coating surface. It can be implemented to contribute to the improvement of the quality of the dry film.

셋째, 인쇄 회로 기판 제조공정 중 드라이 필름의 현상 및 박리공정에서 발생할 수 있는 거품의 양을 감소시켜 소포제의 사용량을 줄일 수 있으며, 이는 생산성의 향상 및 원가 절감, 소포제 과다 사용으로 인한 수질 오염을 방지할 수 있는 장점을 가진다.
Third, the amount of defoamer used can be reduced by reducing the amount of foam that may occur in the development and peeling process of dry film during the manufacturing process of printed circuit board, which can improve productivity, reduce cost, and prevent water pollution due to excessive use of defoamer. Has the advantage to do.

본 발명에서는 상기 화학식 1 중 m=2, n=2, R이 메틸기이고, R'는 각각 폴리에테르와 메타크릴레이트인 두가지 유기변성 폴리실록산계 유도체를 사용한다. In the present invention, m = 2, n = 2, and R in the general formula (1), and R 'is used two organic modified polysiloxane derivatives of polyether and methacrylate, respectively.

한편 상기 유기변성 폴리실록산계 유도체의 함량은 레지스트 전체 조성물에 대하여 0.01∼10 중량% 이내로 사용하는 바, 만일 그 함량이 10 중량%를 초과할 경우에는 드라이 필름의 회로 구현성이 떨어지며, 현상공정에서 스컴현상이 발생하는 문제가 있다.  On the other hand, the content of the organic modified polysiloxane derivative is used within 0.01 to 10% by weight based on the total composition of the resist, if the content exceeds 10% by weight of the circuit implementation of the dry film is poor, scum in the development process There is a problem that a phenomenon occurs.

상기 조성 이외에 통상적인 DFR 조성물에 첨가할 수 있는 염료, 안정화제, 광증감제, 가소제 또는 변색방지제와 같은 첨가제를 본 발명을 손상시키지 않는 범위 내에서 첨가할 수 있다. In addition to the above composition, additives such as dyes, stabilizers, photosensitizers, plasticizers or discoloration agents that can be added to conventional DFR compositions can be added within a range not impairing the present invention.                     

이하 본 발명을 더욱 더 상세히 설명하는 바, 본 발명이 하기의 실시예에 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail, but the present invention is not limited to the following examples.

실시예 1∼5 및 비교예 1Examples 1-5 and Comparative Example 1

다음 표 1과 같은 조성으로 DFR 조액을 실시한 후 1시간 동안 교반하여 30분 동안 방치시킨 후 코팅바를 이용하여 코팅을 실시하였다. 그 다음, 80℃ 오븐에서 60초간 건조시킨 후 20cm X 20cm 평면에서 0.5 mm이상의 덴트나 핀홀의 갯수를 측정하였다. Next, after performing the DFR crude liquid with the composition as shown in Table 1, the mixture was stirred for 1 hour and left for 30 minutes, followed by coating using a coating bar. Then, after drying for 60 seconds in an 80 ℃ oven, the number of dents or pinholes of 0.5 mm or more in the 20cm X 20cm plane was measured.

조성(단위 : g)Composition (unit: g) 실시예1Example 1 실시예2Example 2 실시예3Example 3 실시예4Example 4 실시예5Example 5 실시예6Example 6 비교예1Comparative Example 1 베이스 고분자Base polymer 아크릴레이트공중합 고분자Acrylate Copolymer 4545 4545 4545 4545 4545 4545 4545 광 개시제Photoinitiator 벤조페논Benzophenone 2.52.5 2.52.5 2.52.5 2.52.5 2.52.5 2.52.5 2.52.5 4,4'-(비스디에틸아미노)벤조페논4,4 '-(bisdiethylamino) benzophenone 1.51.5 1.51.5 1.51.5 1.51.5 1.51.5 1.51.5 1.51.5 루코 크리스탈 바이올렛Luco Crystal Violet 3.53.5 3.53.5 3.53.5 3.53.5 3.53.5 3.53.5 3.53.5 톨루엔설폰산1수화물Toluenesulfonic Acid Monohydrate 1.01.0 1.01.0 1.01.0 1.01.0 1.01.0 1.01.0 1.01.0 다이아몬드 그린 GHDiamond Green GH 1.01.0 1.01.0 1.01.0 1.01.0 1.01.0 1.01.0 1.01.0 광중합 단량체Photopolymerization monomer 9G(1) 9G (1) 10.510.5 10.510.5 10.510.5 10.510.5 10.510.5 10.510.5 10.510.5 APG-400(2) APG-400 (2) 10.510.5 10.510.5 10.510.5 10.510.5 10.510.5 10.510.5 10.510.5 BPE-500(3) BPE-500 (3) 10.510.5 10.510.5 10.510.5 10.510.5 10.510.5 10.510.5 10.510.5 용매menstruum 메틸에틸케톤Methyl ethyl ketone 13.013.0 13.013.0 13.013.0 13.013.0 13.013.0 13.013.0 13.013.0 폴리실록산계 유도체Polysiloxane derivatives R'=폴리에테르R '= polyether 0.10.1 0.50.5 1.01.0 -- -- -- -- R'=메타크릴레이트R '= methacrylate -- -- -- 0.10.1 0.50.5 1.01.0 -- (주) (1) 9G : 폴리에틸렌글리콜 다이메타크릴레이트 (2) APG-400 : 폴리에틸렌글리콜(400) 다이아크릴레이트 (3) BPE-500 : 폴리에틸렌글리콜(500) 다이아크릴레이트(1) 9G: Polyethylene glycol dimethacrylate (2) APG-400: Polyethylene glycol (400) Diacrylate (3) BPE-500: Polyethylene glycol (500) Diacrylate

또한 현상후 거품발생 정도를 비교하기 위하여 300 ml 현상액 (탄산나트륨 1중량% 수용액)에 0.5 ml 상기 조성의 드라이 필름을 녹인 후 30초간 공기 주입 후 거품의 높이를 비교하였으며, 그 결과를 다음 표 2에 나타내었다.
In addition, in order to compare the degree of foaming after development, 0.5 ml of a dry film of the composition was dissolved in a 300 ml developer (1% by weight aqueous solution of sodium carbonate), and then the height of the foam was compared after injecting air for 30 seconds, and the results are shown in Table 2 below. Indicated.

실시예1Example 1 실시예2Example 2 실시예3Example 3 실시예4Example 4 실시예5Example 5 실시예6Example 6 비교예1Comparative Example 1 덴트갯수Number of dents 2525 1414 99 2525 2020 1313 3030 거품높이(mm)Foam height (mm) 134134 120120 9696 170170 147147 118118 200200

상기 표 2의 결과로부터 유기변성 폴리실록산계 유도체를 첨가함에 따라 덴트와 핀홀을 갯수가 감소하여 표면물성이 우수할 뿐만 아니라 거품발생이 적음을 알 수 있다.
From the results of Table 2, it can be seen that as the number of dents and pinholes is reduced by adding the organo-modified polysiloxane derivatives, the surface properties are excellent and foaming is less.

이상에서 상세히 설명한 바와 같이, 베이스 고분자, 광중합 단량체, 광중합 개시제 및 기타 첨가제로 구성된 드라이 필름 포토레지스트 조성물에 유기변성 폴리실록산계 유도체를 첨가한 본 발명의 드라이 필름 포토레지스트는, 드라이 필름 조액시 교반공정에서 발생된 기포로 발생할 수 있는 핀홀이나 덴트 발생을 억제하여 코팅의 균일성을 구현함으로써 품질균일화 및 안정화에 효과적임과 동시에 인쇄회로기판의 현상 및 박리공정에서의 현상액 및 박리액의 거품발생량을 감소시키는 데 효과적이다. As described in detail above, the dry film photoresist of the present invention, in which an organic-modified polysiloxane derivative is added to a dry film photoresist composition composed of a base polymer, a photopolymerization monomer, a photopolymerization initiator, and other additives, is used in a stirring process during dry film preparation. It is effective in quality uniformity and stabilization by reducing pinholes or dents that can be generated by generated bubbles, and reducing the amount of foaming of developer and peeling liquid in developing and peeling process of printed circuit board. Is effective.

Claims (2)

베이스 고분자, 광중합 개시제, 광중합 단량체 및 기타 첨가제로 구성된 드라이 필름 포토레지스트 조성물에 있어서, In a dry film photoresist composition composed of a base polymer, a photopolymerization initiator, a photopolymerization monomer and other additives, 다음 화학식 1로 표시되는 유기변성 폴리실록산계 유도체를 더 포함하는 것임을 특징으로 하는 드라이 필름 포토레지스트 조성물. A dry film photoresist composition characterized in that it further comprises an organic modified polysiloxane derivative represented by the following formula (1). 화학식 1Formula 1
Figure 112007003574549-pat00006
Figure 112007003574549-pat00006
 상기 식에서, R은 수소, 메틸 또는 에틸기이며, R'은 폴리에테르, 탄소수 1∼10 사이의 알킬, 아크릴레이트 또는 메타크릴레이트이며, m은 1∼50 사이의 정수이며, n은 1∼10 사이의 정수이다. Wherein R is hydrogen, methyl or ethyl group, R 'is a polyether, alkyl having 1 to 10 carbon atoms, acrylate or methacrylate, m is an integer from 1 to 50, n is from 1 to 10 Is an integer. 제 1항에 있어서, 상기 화학식 1로 표시되는 유기변성 폴리실록산계 유도체는 전체 조성 중 0.01∼10 중량%로 포함되는 것임을 특징으로 하는 드라이 필름 포토레지스트 조성물. The dry film photoresist composition of claim 1, wherein the organo-modified polysiloxane derivative represented by Chemical Formula 1 is contained in an amount of 0.01 to 10 wt% based on the total composition.
KR1020010085708A 2001-12-27 2001-12-27 Resin composition for dry film photoresist KR100729171B1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10319594A (en) * 1997-05-21 1998-12-04 Fuji Photo Film Co Ltd Positive photoresist composition for far ultraviolet ray exposure
JPH111602A (en) * 1997-06-12 1999-01-06 Jsr Corp Photosensitive resin composition and photosensitive dry film using the same
JP2002156752A (en) * 2000-11-16 2002-05-31 Fuji Photo Film Co Ltd Photosensitive transfer material and image forming method using the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10319594A (en) * 1997-05-21 1998-12-04 Fuji Photo Film Co Ltd Positive photoresist composition for far ultraviolet ray exposure
JPH111602A (en) * 1997-06-12 1999-01-06 Jsr Corp Photosensitive resin composition and photosensitive dry film using the same
JP2002156752A (en) * 2000-11-16 2002-05-31 Fuji Photo Film Co Ltd Photosensitive transfer material and image forming method using the same

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