KR0160459B1 - Photosensitive resin composition - Google Patents
Photosensitive resin composition Download PDFInfo
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- KR0160459B1 KR0160459B1 KR1019900022937A KR900022937A KR0160459B1 KR 0160459 B1 KR0160459 B1 KR 0160459B1 KR 1019900022937 A KR1019900022937 A KR 1019900022937A KR 900022937 A KR900022937 A KR 900022937A KR 0160459 B1 KR0160459 B1 KR 0160459B1
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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
Abstract
본 발명은 감광성 수지 적층체에 적용되는 감광성 수지 조성물에 있어서,(1)하기 일반식으로 나타낼 수 있으며, 말단 에틸렌성 불포화기를 적어도 1개 가지는 화합물의 광중합성 물질 20내지 66중량%, (2)고분자 결합체 29내지 77중량%, (3) 광개시제 0.1 내지 17중량% 및 (4)첨가제 0.4 내지 4중량%로 구성되는 감광성 수지 조성물에 관한 것으로, 미노광부 제거 속도가 빠르고, 노광가시화성 및 감도가 우수한 효과가 있다.In the photosensitive resin composition applied to the photosensitive resin laminated body, (1) 20-66 weight% of photopolymerizable materials of the compound which can be represented by following General formula and which has at least 1 terminal ethylenically unsaturated group, (2) The present invention relates to a photosensitive resin composition composed of 29 to 77% by weight of the polymer binder, (3) 0.1 to 17% by weight of the photoinitiator, and (4) 0.4 to 4% by weight of the additive. Excellent effect.
상기식에서,n은 5내지 15이다.Wherein n is 5 to 15.
Description
본 발명은 감광성 수지 조성물에 관한 것으로, 보다 상세하게는 에틸렌성 불포화기를 적어도 1개 가지는 화합물을 포함함으로써 미노광부 제거속도가 빠르고, 노광가시화성 및 감도가 우수한 감광성 수지 조성물에 관한 것이다.The present invention relates to a photosensitive resin composition, and more particularly, to a photosensitive resin composition having a high unexposed portion removal rate and excellent exposure visibility and sensitivity by including a compound having at least one ethylenically unsaturated group.
감광성 수지 조성물은 평판, 인쇄판, 수지철(凸)판, 특히 인쇄회로기판 등의 제조에 사용되고 있다. 일반적으로 인쇄회로기판은 폴리에스터 필름층, 광중합성층 및 보호필름층으로 구성된 적층체로 부터 보호필름층을 이탈시키고 동판 적층판상에 광중합성층을 적충시킨 후 자외선 조사로 화상을 형성한 다음, 현상액으로 미반응 부분을 제거시켜 내식막을 형성하고, 기판을 에칭시키고 내식막을 벗겨냄으로써 제조되며, 사용되는 광중합성층은 신속한 미노광부 제거속도, 우수한 해상도 및 감도가 요구된다.Photosensitive resin compositions are used in the manufacture of flat plates, printed boards, ferrous iron plates, in particular printed circuit boards. In general, a printed circuit board is separated from a laminate composed of a polyester film layer, a photopolymerizable layer, and a protective film layer, a photopolymerizable layer is deposited on a copper clad laminate, and an image is formed by UV irradiation. It is prepared by removing the reaction portion to form a resist, etching the substrate and peeling the resist, and the photopolymerizable layer used requires fast unexposed portion removal speed, excellent resolution and sensitivity.
상기 광중합성층의 구성물질은 광중합성 물질, 고분자 결합제, 광개시제 및 첨가제를 포함한다.The material of the photopolymerizable layer includes a photopolymerizable material, a polymer binder, a photoinitiator, and an additive.
상기 광중합성 물질로 적합한 화합물은 말단 에틸렌성 불포화기를 적어도 1개 이상 가지는 화합물 예를 들어 트리메티롤 프로판 트리아크릴레이트, 트리메티롤 프로판 디메타크릴레이트, 펜타에리트리톨 트리아크릴레이트, 디펜타에리트리톨헥사크릴레이트, 1,6-헥산디올디아크릴레이트, 2,2-비스[4-(아크릴옥사-폴리에톡시)페닐]프로판, 테트라메티롤메탄트리아크릴레이트, 테트라메티롤메탄테트라아크릴레이트, 디에틸렌글리콜디아크릴레이트, 트리프로필렌디아크릴레이트, 1,5-펜탄디올디아크릴레이트, 부틸프탈레이트, 글리세롤트리아세테이트, 트리메티롤프로판 아세테이트 등을 들 수 있다.Suitable compounds for the photopolymerizable material include compounds having at least one terminal ethylenically unsaturated group, for example, trimethol propane triacrylate, trimethol propane dimethacrylate, pentaerythritol triacrylate, dipentaerythritol Hexaacrylate, 1,6-hexanedioldiacrylate, 2,2-bis [4- (acryloxa-polyethoxy) phenyl] propane, tetrametholmethanetriacrylate, tetrametholmethane tetraacrylate, Diethylene glycol diacrylate, tripropylene diacrylate, 1,5-pentanediol diacrylate, butyl phthalate, glycerol triacetate, trimetholpropane acetate and the like.
상기 광중합성 물질을 지지하여 필름상을 형성하는 고분자 결합제로는 예를 들어 폴리메틸메타크릴레이트,. 폴리스티렌 등의 비닐 중합체 또는 아크릴산, 아크릴산메틸, 메틸메타크릴레이트, 아크릴산부틸, 스티렌, 메타크릴산 2-하이드록시에틸, 아크릴로니트릴, 부타디엔, 에틸아크릴레이트, 말레익안하이드라이드 등의 공중합성분을 가지는 비닐공중합체 또는 에폭시수지, 크실렌수지, 방향족 술폰 아미도 포름알테히드 수지 등을 들 수 있다.As the polymer binder for supporting the photopolymerizable material to form a film, for example, polymethyl methacrylate; Vinyl polymers such as polystyrene or copolymers such as acrylic acid, methyl acrylate, methyl methacrylate, butyl acrylate, styrene, 2-hydroxyethyl methacrylate, acrylonitrile, butadiene, ethyl acrylate and maleic hydride Vinyl copolymers or epoxy resins, xylene resins, aromatic sulfone amido formaldehyde resins, and the like.
상기 광중합 개시제로는 예를 들어 벤조페논, 클로로벤조페논, 4,4'-디메틸아미노벤조페논, 4,4'-디클로로벤조페논 등의 벤조페논류, 또는 2-에틸 안트라퀴논, 2-t-부틸안트라퀴논 등의 안트라퀴논류 또는 벤조인 에틸에테르, 벤조인이소프로필에테르, 벤질 및 이의 혼합물이 사용될 수 있다.Examples of the photopolymerization initiator include benzophenones such as benzophenone, chlorobenzophenone, 4,4'-dimethylaminobenzophenone, and 4,4'-dichlorobenzophenone, or 2-ethyl anthraquinone and 2-t-. Anthraquinones such as butyl anthraquinone or benzoin ethyl ether, benzoin isopropyl ether, benzyl and mixtures thereof can be used.
상기 첨가제로는 벤조이미다졸, 벤즈티아졸, 벤즈티옥사졸, 벤조트리아졸, 2-머캅토벤즈티아졸, 2-머캅토벤조이미다졸 등의 접착 촉진제, 감광성수지 조성물의 저장안정성 및 코팅액 건조시 또는 라미네이션시 열중합을 방지하기 위해 하이드로퀴논(p-메톡시페놀), 2-하이드록시벤조페논 등의 열중합방지제, 루이코 계통의 메틸바이올렛, 말라카이트 그린, 크리스탈바이올렛 염료 등의 첨가제를 사용하였다.The additives include adhesion promoters such as benzoimidazole, benzthiazole, benzthioxazole, benzotriazole, 2-mercaptobenzthiazole, 2-mercaptobenzoimidazole, storage stability of the photosensitive resin composition, and drying of the coating solution. In order to prevent thermal polymerization during lamination or lamination, thermal polymerization inhibitors such as hydroquinone (p-methoxyphenol) and 2-hydroxybenzophenone are used, and additives such as methyl violet, malachite green, and crystal violet dyes of leuco-based It was.
그러나 전술한 구성성분들의 감광성 수지 조성물은 현상액에 의한 미반응부분의 제거속도가 느리며, 노광 가시화성(Density of image) 및 감도 (Photosensitivity)가 낮은 경향이 있다.However, the photosensitive resin composition of the above-described components has a low removal rate of the unreacted portion by the developer, and tends to have low exposure visibility of image and sensitivity.
본 발명의 목적은 미노광부 제거 속도가 빠르고 노광가시화성 및 감도가 우수한 감광성 수지 조성물을 제공하는 것이다.An object of the present invention is to provide a photosensitive resin composition having a high unexposed portion removal rate and excellent exposure visibility and sensitivity.
본 발명의 수지 조성물은 광 조사에 의한 중합반응시 라디칼의 생성속도와 생성량이 증가되고 가교밀도가 더욱 향상된 감광성 수지 조성물이다.The resin composition of the present invention is a photosensitive resin composition in which the rate and amount of radicals are increased and the crosslinking density is further improved during polymerization by light irradiation.
본 발명의 수지 조성물은 (1)말단 에틸렌성 불포화기를 적어도 1개 가지는 화합물의 광중합성 물질 20 내지 66중량%, (2)고분자 결합제 29내지 77중량%, (3) 광개시제 0.1 내지 17중량% 및 (4)첨가제 0.4내지 4중량%를 포함하는 감광성 수지 조성물에 있어서, 상기 광중합물질로 하기 일반식으로 표시되는 다가알콕시레이티드트리메티롤프로판트리아크릴레이트(Highly Alkoxylated Trimetylol Propane Triacrylate: HATPTA)를 포함하는 감광성 수지 조성물이다.The resin composition of the present invention comprises (1) 20 to 66% by weight of the photopolymerizable material of the compound having at least one terminal ethylenically unsaturated group, (2) 29 to 77% by weight of the polymer binder, (3) 0.1 to 17% by weight of the photoinitiator, and (4) A photosensitive resin composition comprising 0.4 to 4% by weight of an additive, comprising a polyalkoxylated trimethtylol propane triacrylate represented by the following general formula as the photopolymer: It is a photosensitive resin composition.
상기식에서,n은 5내지 15이다.Wherein n is 5 to 15.
말단 에틸렌성 불포화기를 적어도 1개 가지는 화합물의 광중합성 물질인 다가알콕시레이티드트리메티롤프로판트리아크릴레이트(Highly Alkoxylated Trimetylol Propane Triacrylate)기능은 상술한 일반식내의 알콕시드기(Alkoxide)에 의해 알칼리 수용액에 대한 용해성을 향상시켜 현상시 미노광부 제거시 속도를 빠르게 하며 알콕시드기의 산소원자 주위에 비공유 전자쌍에 의해 안정된 광개시제 라디칼(Radical)생성이 가능하여 감도를 증진시키는 역할을 한다.The function of Highly Alkoxylated Trimetylol Propane Triacrylate, which is a photopolymerizable material of a compound having at least one terminal ethylenically unsaturated group, is applied to the aqueous alkali solution by the alkoxide group in the general formula described above. It improves the solubility and increases the speed when removing unexposed part during development, and it is possible to generate stable photoinitiator radical (radical) by unshared electron pair around oxygen atom of alkoxide group.
본 발명에 따른 감광성 수지 조성물 및 그 적층체는 우수한 감도 및 현상속도 때문에 인쇄회로기판 제조시 노광시간 단축으로 인한 생산성의 향상을 기대할 수 있으며, 또한 상기 우수한 현상성 때문에 잔존물(Scum)이 발생하지 않으며, 경시적으로 안정하기 때문에 드라이필름 포토레지스트와 감관성인쇄판, 칼라프루우프(Color Proof)등의 감관성을 부여한 감광재료로 이용하는 경우 저장 수명이 양호해진다.The photosensitive resin composition and the laminate thereof according to the present invention can be expected to improve productivity due to shortening the exposure time when manufacturing a printed circuit board due to the excellent sensitivity and development speed, and also because of the excellent developability, no residue (Scum) occurs. As a result, the shelf life is good when used as a photosensitive material that provides sensitivity such as dry film photoresist, capillary printing plate, and color proof.
이하 실시예를 들어 본 발명을 더욱 상세히 설명하고자 하나 본 발명이 하기 실시예에 의하여 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited by the following examples.
[실시예 1]Example 1
폴리메틸메타크릴레이트/히드록시에틸아크릴레이트/메탈메타크릴레이트Polymethyl methacrylate / hydroxyethyl acrylate / metal methacrylate
삼원공중합체 48.0gTerpolymer 48.0g
테카에톡시레이티드트리메티롤프로판트리아크릴레이트 23.0gTecaethoxylated trimetholpropane triacrylate 23.0 g
트리에틸렌그리콜디아세테이트 7.0gTriethylene glycol diacetate 7.0 g
벤조페논 2.2gBenzophenone 2.2g
크리스탈바이올렛 0.1gCrystal Violet 0.1g
메틸에틸하이드로퀴논 0.3g0.3 g of methyl ethyl hydroquinone
메틸에틸케톤 100.0gMethyl ethyl ketone 100.0 g
상기 조성물을 교반기를 이용하여 교반하여 충분히 혼합한 후 25㎛두께의 폴리에틸렌테레프탈레이트(PET)필름 위에 도포하고 80내지 130℃의 열풍대류식 건조기로 5분간 건조하여 용제를 모두 휘발시켜 30㎛ 두께의 감광층을 형성시키고, 이 감광층위에 보호층으로 폴리에틸렌 필름 또는 폴리프로필렌필름(25㎛)을 적층시켜 1 내지 2일간 상온에서 숙성시킨다.The composition was stirred and mixed well using a stirrer, and then coated on a 25 μm-thick polyethylene terephthalate (PET) film, and dried in a hot air convection dryer at 80 to 130 ° C. for 5 minutes to volatilize all solvents to obtain a thickness of 30 μm. A photosensitive layer is formed, and a polyethylene film or polypropylene film (25 µm) is laminated on the photosensitive layer as a protective layer and aged at room temperature for 1 to 2 days.
이렇게 제조된 3층 적층체 필름에 보호층 필름을 벗겨내고 라미네이터(Laminator)를 사용하여 감광층을 동판 적층판위에 라미네이션 시킨다(이 경우 라미네이터의 가열온도는 90 내지 120℃이다)The protective layer film is peeled off the three-layer laminate film thus prepared, and the photosensitive layer is laminated on the copper laminate using a laminator (in this case, the heating temperature of the laminator is 90 to 120 ° C).
라미네이션된 감광층 위에 스토우퍼 스탭표(Stouffer Step Tablet)를 놓고 초고압 수은등을 사용하여 광조사를 행한 후 폴리에틸렌테레프탈레이트 필름지지체를 벗겨낸 다음 1중량부의 탄산나트륨 수용액으로 현상하면서 화상이 드러나는 시간을 초시계(Stop Watch)를 사용하여 측정한다.Place the Stopper Step Tablet on the laminated photosensitive layer, perform light irradiation using an ultra-high pressure mercury lamp, peel off the polyethylene terephthalate film support, and develop with 1 part by weight aqueous sodium carbonate solution. Measure using Stop Watch.
이렇게 얻어진 스탭(Step)의 화상으로부터 첫 번째 클리어 단수를 취하여 이를 감도의 값으로 한다. 그 결과는 하기 표1과 같다.The first clear stage is taken from the image of the step obtained in this way, and this value is set as the sensitivity value. The results are shown in Table 1 below.
[실시예 2]Example 2
폴리메틸메타크릴레이트/에틸아크릴레이트/아크릴산의 삼원공중합체 20.0g20.0 g of terpolymer of polymethyl methacrylate / ethyl acrylate / acrylic acid
스티렌/무수말레인산 공중합체의 변성체 25.0gModified 25.0g of styrene / maleic anhydride copolymer
데커에톡시레이티드 트리메티롤 프로판 트리아크릴레이트 23.0gDeckerethoxylated Trimethol Propane Triacrylate 23.0g
트리에틸렌그리콜디아세테이트 7.0gTriethylene glycol diacetate 7.0 g
벤조페논 2.2gBenzophenone 2.2g
크리스탈바이올렛 0.1gCrystal Violet 0.1g
메틸에틸하이드로퀴논 0.3g0.3 g of methyl ethyl hydroquinone
메틸에틸케톤 100.0gMethyl ethyl ketone 100.0 g
상기 조성물로 실시예1과 같은 3층 적층체 필름을 제조하고 마찬가지 방법으로 현상속도 및 스토우퍼 스탭에 의한 감도를 측정한다. 그 결과는 하기표1과 같다.The three-layer laminated film as in Example 1 was prepared from the composition, and the development speed and the sensitivity by the stopper staff were measured in the same manner. The results are shown in Table 1 below.
[비교예 1]Comparative Example 1
상기 조성물 성분중에서 말단 에틸렌성 불포화기를 적어도 1개 가지는 광중합성 물질을 트리메티롤 프로판 트리아크릴레이트를 사용하여 실시예1과 마찬가지 방법에 의해 현상속도 및 스토우퍼 스탭에 의한 감도를 측정하여 실시예1 및 실시예2와 비교하였으며 그 결과를 하기표 1에 나타내었다.The photopolymerizable material having at least one terminal ethylenically unsaturated group in the composition component was measured by the development method and the sensitivity of the stopper staff by the same method as in Example 1 using trimetholol propane triacrylate. And Example 2 and the results are shown in Table 1 below.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019900022937A KR0160459B1 (en) | 1990-12-31 | 1990-12-31 | Photosensitive resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019900022937A KR0160459B1 (en) | 1990-12-31 | 1990-12-31 | Photosensitive resin composition |
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| Publication Number | Publication Date |
|---|---|
| KR920013034A KR920013034A (en) | 1992-07-28 |
| KR0160459B1 true KR0160459B1 (en) | 1999-02-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019900022937A KR0160459B1 (en) | 1990-12-31 | 1990-12-31 | Photosensitive resin composition |
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| Country | Link |
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| KR (1) | KR0160459B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100718922B1 (en) * | 2001-12-20 | 2007-05-16 | 주식회사 코오롱 | Dry film photoresist composition |
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1990
- 1990-12-31 KR KR1019900022937A patent/KR0160459B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100718922B1 (en) * | 2001-12-20 | 2007-05-16 | 주식회사 코오롱 | Dry film photoresist composition |
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| Publication number | Publication date |
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| KR920013034A (en) | 1992-07-28 |
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