KR100682711B1 - Image forming photosensitive resin composition and producing method thereof - Google Patents
Image forming photosensitive resin composition and producing method thereof Download PDFInfo
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- KR100682711B1 KR100682711B1 KR1020040022862A KR20040022862A KR100682711B1 KR 100682711 B1 KR100682711 B1 KR 100682711B1 KR 1020040022862 A KR1020040022862 A KR 1020040022862A KR 20040022862 A KR20040022862 A KR 20040022862A KR 100682711 B1 KR100682711 B1 KR 100682711B1
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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Abstract
본 발명에 의하면 1 분자중에 2개 이상의 에폭시기를 가지는 에폭시수지와 불포화일염기산을 에스테르화 촉매 존재하에 반응시켜, 이 반응으로 얻어지는 에폭시아크릴레이트중의 히드록실기에 대해 다염기산무수물을 반응시키는 것으로 얻을 수 있는 카르복실기함유 감광성수지를 포함하면서, 에스테르화 촉매로서 하기 일반식으로 표시되는 4급포스포늄염을 사용하는 화상형성용 감광성수지조성물이 제공되며, 이는 보존안정성 및 알칼리현상성이 우수하다. According to the present invention, an epoxy resin having two or more epoxy groups in one molecule is reacted with an unsaturated monobasic acid in the presence of an esterification catalyst, and the polybasic acid anhydride is reacted with a hydroxyl group in the epoxy acrylate obtained by this reaction. An image forming photosensitive resin composition using a quaternary phosphonium salt represented by the following general formula as an esterification catalyst is provided, including a carboxyl group-containing photosensitive resin, which is excellent in storage stability and alkali developability.
(식중 R1, R2, R3, R4는 서로 같거나 다르며, 치환기를 가질수도 있는, 방향환을 갖는 유기기를 나타내고, Ｘ-는 대응 아니온을 나타낸다.)
(Wherein R 1 , R 2 , R 3 , R 4 are the same or different and represent an organic group having an aromatic ring, which may have a substituent, and Ｘ − represents a corresponding anion.)
감광성수지, 화상형성, 에스테르화촉매, 4급포스포늄염Photosensitive resin, image forming, esterification catalyst, quaternary phosphonium salt
Description
본발명은 화상형성에 유용한 감광성수지조성물 및 그의 제조방법에 관한 것이다. The present invention relates to a photosensitive resin composition useful for image formation and a method of manufacturing the same.
에폭시수지와 불포화일염기산을 반응시켜서 얻은 에폭시아크릴레이트(비닐에스테르)는 열이나 광에 의해 경화되며, 경화물은 내약품성 등의 특성이 우수하여서 전자부품관련 레지스트 재료 등의 각종 용도로 사용되고 있다. 또한, 에폭시아크릴레이트가 가지고 있는 히드록실기에 다염기산무수물을 반응시켜서 카르복실기를 도입하는 것에 의해 알칼리현상가능한 감광성수지가 얻어진다는 것이 알려져 있다 (참조: 일본특개소61-243869호 공보 및 특개소63-258975호 공보).Epoxy acrylate (vinyl ester) obtained by reacting epoxy resin with unsaturated monobasic acid is cured by heat or light, and cured product has excellent characteristics such as chemical resistance and is used for various applications such as resist materials related to electronic parts. . In addition, it is known that an alkali developable photosensitive resin is obtained by reacting a hydroxyl group of an epoxy acrylate with a polybasic acid anhydride and introducing a carboxyl group (see Japanese Patent Application Laid-Open No. 61-243869 and Japanese Patent Laid-Open No. 63-). 258975).
그런데, 본원발명자들이 검토한 바에 의하면, 에폭시아크릴레이트를 합성할 때 에폭시수지와 불포화일염기산과의 에스테르화반응의 촉매로서 종래 공지의 3급아민이나 3급포스핀류 등을 사용하면 에폭시아크릴레이트를 함유하는 수지용액(수지조성물)을 보존하고 있는 동안에 그 점도가 경시적으로 증가해 버리는 문제가 발생한다. However, according to the inventors of the present invention, when synthesizing the epoxy acrylate, epoxy acrylate can be prepared by using a conventionally known tertiary amine, tertiary phosphine or the like as a catalyst for the esterification reaction between an epoxy resin and an unsaturated monobasic acid. While storing the resin solution (resin composition) to contain, the problem that the viscosity increases with time arises.
한편, 카르복실기 함유 에폭시아크릴레이트를 솔더레지스트 등의 화상형성용 감광성 수지조성물에 적용하는 경우, 노광후의 경화도막의 가교밀도를 향상시키기 위해서 에폭시수지를 배합하기도 한다. 이러한 에폭시수지를 배합한 감광성수지조성물의 도막을 노광전에 가열건조하면 알칼리현상성이 불충분하게 되는 경우가 있다. 이것은 에폭시아크릴레이트 합성 시의 3급 아민이나 3급 포스핀류 등의 에스테르화촉매가 카르복실기 함유 에폭시아크릴레이트와 에폭시수지와의 가교반응을 진행시켜서 미노광부분의 알칼리용해성을 저감시키기 때문이라고 생각된다. On the other hand, when applying a carboxyl group-containing epoxy acrylate to photosensitive resin compositions for image formation, such as a soldering resist, an epoxy resin may be mix | blended in order to improve the crosslinking density of the cured coating film after exposure. Alkali developability may become inadequate when the coating film of the photosensitive resin composition which mix | blended such an epoxy resin is heat-dried before exposure. It is considered that this is because esterification catalysts such as tertiary amines and tertiary phosphines in synthesizing epoxy acrylate proceed with crosslinking reaction between carboxyl group-containing epoxy acrylate and epoxy resin to reduce alkali solubility of unexposed portion.
수지용액의 보존중의 점도증가나 미노광부분의 현상성저감를 해결하기 위한 에스테르화촉매로서 나프텐산, 라우린산, 스테아린산, 올레인산, 옥텐산 등의 리튬, 크롬, 지르코늄, 칼륨, 나트륨염을 사용하는 기술이 개시되어 있다(예를 들면, 일본 특공평6-123233호공보). 이러한 기술은 수지용액의 보존안정성은 상당히 개량하지만 에스테르화반응 시에 불용물이 생성되기 쉽고, 이러한 불용물을 여과조작으로 완전하게 제거할 수가 없기 때문에 공업적실시라고 하는 점에서는 개량이 필요하다. 더우기, 최근에는 환경에 대한 배려에서 촉매로서 사용되는 화합물의 종류에 제한을 하고 있다.Lithium, chromium, zirconium, potassium, sodium salts such as naphthenic acid, lauric acid, stearic acid, oleic acid, octenic acid, etc. are used as esterification catalysts to solve the increase in viscosity during storage of resin solution and reduction of developability of unexposed parts. The technique to make is disclosed (for example, Unexamined-Japanese-Patent No. 6-123233). Although this technique considerably improves the storage stability of the resin solution, insoluble matters are easily generated during the esterification reaction, and such insoluble matters cannot be completely removed by a filtration operation. Moreover, in recent years, in consideration for the environment, there has been a limitation on the type of compounds used as catalysts.
게다가, 에스테르화촉매로서 종래 공지의 3급포스핀을 이용하면서 에폭시아크릴레이트 합성을 산소분위기하에서 행하고, 3급 포스핀의 촉매활성을 잃게 하는 기술도 제안되어 있다(일본 특개평14-293876호공보). 그러나 이 기술에서도 합성시의 안정성이나 미노광부분의 현상성을 확보하기 위해서는 합성공정이나 촉매실활공정에서의 온도나 시간을 엄밀하게 관리할 필요가 있다. In addition, a technique has been proposed in which an epoxy acrylate synthesis is carried out under an oxygen atmosphere while using a conventionally known tertiary phosphine as an esterification catalyst and the catalytic activity of the tertiary phosphine is lost (Japanese Patent Laid-Open No. 14-293876). . However, even in this technique, it is necessary to strictly control the temperature and time in the synthesis process or catalyst deactivation process in order to secure the stability during synthesis or developability of unexposed parts.
본발명에서는 상기 종래기술의 문제점을 감안하여 에폭시아크릴레이트의 합성을 원활하게 진행시키기 위해서 수지용액 점도의 경시변화를 일으키지 않고 미노광부분의 현상성도 양호할 뿐만아니라 환경에 부하를 주지않는 촉매를 찾아내고, 보존안정성이 우수한 화상형성용감광성수지조성물 및 그의 제조방법을 제공하는 것을 과제로 한다. In the present invention, in order to smoothly proceed with the synthesis of the epoxy acrylate in view of the problems of the prior art, to find a catalyst that does not cause a change in the viscosity of the resin solution over time, the developability of the unexposed portion is also good and does not put a load on the environment. Another object is to provide an image forming photosensitive resin composition having excellent storage stability and a method of manufacturing the same.
상기 과제를 해결한 본발명의 화상형성용감광성수지조성물은 1분자중에 2개이상의 에폭시기를 갖는 에폭시수지와 불포화일염기산을 에스테르화촉매 존재하에 반응시키고, 이 반응에서 얻은 에폭시아크릴레이트중의 히드록실기에 한번 더 다염기산무수물을 반응시키는 것으로 얻을 수 있는 카르복실기 함유 에폭시아크릴레이트를 포함하는 것이며, 에스테르화촉매로서 하기 화학식 1로 나타내는 4급포스포늄을 사용하는 것을 요지로 한다. An image forming photosensitive resin composition of the present invention which solves the above problems is reacted with an epoxy resin having two or more epoxy groups in one molecule and an unsaturated monobasic acid in the presence of an esterification catalyst. The carboxyl group-containing epoxy acrylate obtained by reacting a polybasic acid anhydride once again with a hydroxyl group is included, and it is a summary to use quaternary phosphonium represented by following formula (1) as an esterification catalyst.
(식중 R1, R2, R3, R4는 서로 같거나 다르며, 치환기를 가질수도 있고, 방향 환을 가지는 유기기를 나타내고, Ｘ-는 대응 아니온을 나타낸다.)(Wherein R 1 , R 2 , R 3 and R 4 are the same as or different from each other, may have a substituent, an organic group having an aromatic ring, and Ｘ − represents a corresponding anion.)
상기 R1, R2, R3, R4가 서로 같거나 다르며, 치환기를 가질 수도 있는 아릴기 또는 아랄킬기인 것이 바람직하고, 치환기를 가질 수도 있는 페닐기 또는 벤질기인 것이 보다 바람직하다.R 1 , R 2 , R 3 , and R 4 are the same as or different from each other, preferably an aryl group or an aralkyl group which may have a substituent, and more preferably a phenyl group or benzyl group which may have a substituent.
본발명은 화상형성용감광성수지조성물의 주성분인 에폭시아크릴레이트를 합성하는데 충분한 에스테르화촉매로서 방향환을 갖는 유기기를 4개 갖고 있는 4급포스포늄염을 사용하는 것에 주된 요지가 있다. 이 촉매를 이용하는 것으로 효율적으로 에스테르화반응을 실시할 수 있고, 얻어지는 감광성수지의 용액을 보존할 때 점도상승을 억제할 수가 있다. 게다가, 감광성수지조성물에 에폭시수지를 배합하는 경우에도 이 에폭시수지와 감광성수지(에폭시아크릴레이트)의 카르복실기와의 가교반응을 억제하므로 미노광부분의 알칼리현상성을 확보할 수 있게 된다. 본발명에 의하면 환경에의 부하가 염려되는 화합물을 이용하지 않고도 반응이 원활하게 진행하고 금속의 유기산염을 사용하는 종래기술과 달리 반응종료후에 간편한 여과로 불용물이 제거되므로 공업적으로 유리하다. The present invention has a main focus on using a quaternary phosphonium salt having four organic groups having an aromatic ring as an esterification catalyst sufficient for synthesizing epoxy acrylate, which is a main component of an image forming photosensitive resin composition. By using this catalyst, esterification can be performed efficiently, and the viscosity rise can be suppressed when preserving the solution of the photosensitive resin obtained. In addition, even when the epoxy resin is blended with the photosensitive resin composition, the crosslinking reaction between the epoxy resin and the photosensitive resin (epoxy acrylate) can be suppressed, thereby ensuring the alkali developability of the unexposed portion. According to the present invention, the reaction proceeds smoothly without using a compound that is concerned about the environmental load, and unlike the prior art using an organic acid salt of the metal, it is industrially advantageous because insoluble matters are removed by simple filtration after the completion of the reaction.
이하, 본발명을 상세하게 설명하기로 한다.Hereinafter, the present invention will be described in detail.
본발명의 화상형성용감광성수지조성물은 감광성수지로서 에폭시아크릴레이트를 주성분으로 포함한다. 에폭시아크릴레이트의 출발원료가 되는 에폭시수지로서는 1분자중에 2개 이상의 에폭시기를 가지는 에폭시수지이면 특별히 한정됨이 없이 이용가능하다. 구체적으로는 비스페놀형에폭시수지; 비페닐형 에폭시수지; 지환식 에폭시수지; 테트라글리시딜아미도디페닐메탄 등의 다관능성 글리시딜아민수지; 테트라글리시딜에테르에탄 등의 다관능성글리시딜에테르수지; 페놀노보락형 에폭시수지나 크레졸노보락형 에폭시수지; 페놀, ο-크레졸, m-크레졸, 나프톨 등의 페놀화합물과 페놀성 히드록실기를 가지는 방향족 알데히드와의 축합반응에 의해 얻어지는 폴리페놀화합물과 에피크롤히드린과의 반응물; 페놀화합물과 디비닐벤젠이나 디시크로펜타디엔 등의 디올레핀 화합물과의 부가반응에 의해 얻어지는 폴리페놀화합물과 에피크롤히드린과의 반응물; 4-비닐시크로헥센-1-옥사이드의 개환중합물과 과산으로 에폭시화한 것; 트리글리시딜이소시아누레이트 등의 복소환을 갖는 에폭시수지; 페놀아랄킬형 에폭시수지; 등을 들 수 있다. 또한 이러한 각 에폭시수지의 2분자 이상을 다염기산, 폴리페놀화합물, 다관능아미노화합물 혹은 다가 티올 등의 쇄연장제와의 반응에 의해 결합시켜 쇄연장한 것도 사용할 수 있다. 또한 글리시딜(메타)아크릴레이트와 같은 글리시딜기를 가지는 단량체의 단독중합체나 공중합체이어도 된다. 이것들은1종 또는 2종이상을 사용할 수도 있다. The photosensitive resin composition for image formation of the present invention contains epoxy acrylate as a main component as a photosensitive resin. As an epoxy resin which becomes a starting material of an epoxy acrylate, if it is an epoxy resin which has two or more epoxy groups in 1 molecule, it can be used without a restriction | limiting in particular. Specifically, Bisphenol-type epoxy resin; Biphenyl type epoxy resins; Alicyclic epoxy resins; Polyfunctional glycidylamine resins such as tetraglycidyl amidodiphenylmethane; Polyfunctional glycidyl ether resins such as tetraglycidyl ether ethane; Phenol novolak type epoxy resins and cresol novolak type epoxy resins; Reactant of the polyphenol compound and epicrohydrin obtained by condensation reaction of phenol compounds, such as phenol, o-cresol, m-cresol, and naphthol, with the aromatic aldehyde which has phenolic hydroxyl group; Reactant of the polyphenol compound obtained by addition reaction of a phenol compound and diolefin compounds, such as divinylbenzene and a dicyclopentadiene, with epicrohydrin; Ring-opening polymerization of 4-vinylcyclohexene-1-oxide with epoxidation; Epoxy resins having a heterocycle such as triglycidyl isocyanurate; Phenol aralkyl type epoxy resins; Etc. can be mentioned. Further, two or more molecules of each epoxy resin may be combined with a chain extender such as a polybasic acid, a polyphenol compound, a polyfunctional amino compound, or a polyvalent thiol, followed by chain extension. Moreover, the homopolymer or copolymer of the monomer which has glycidyl group like glycidyl (meth) acrylate may be sufficient. These can also use 1 type (s) or 2 or more types.
에폭시아크릴레이트를 합성할 때의 에폭시수지의 반응상대인 불포화일염기산이란 1개의 카르복실기와 1개이상의 라디칼 중합성 이중결합을 가지는 일염기산이다. 구체적인 예로서는 아크릴산, 메타크릴산, 크로톤산, 계피산, β-아크릴록시프로피온산, 1개의 히드록실기와 1개의 (메타)아크릴로일기를 가지는 히드록시알킬(메타)아크릴레이트와 이염기산 무수물과의 반응물, 1개의 히드록실기와 2개이상의 (메타)아크릴로일기를 가지는 다관능 (메타)아크릴레이트와 이염기산무수물과의 반응물이 있으나, 그중에서도 바람직한 것으로는 아크릴산, 메타크릴산 등의 (메타) 아크릴로일기를 가지는 것이다. 이것들은 1종 또는 2종이상을 사용할 수 있다.The unsaturated monobasic acid which is the reaction partner of epoxy resin at the time of synthesize | combining epoxy acrylate is monobasic acid which has one carboxyl group and one or more radically polymerizable double bond. Specific examples include reactants of acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, β-acryloxypropionic acid, hydroxyalkyl (meth) acrylate having one hydroxyl group and one (meth) acryloyl group, and a dibasic acid anhydride. And a reaction product of a polyfunctional (meth) acrylate having a hydroxyl group and two or more (meth) acryloyl groups with a dibasic acid anhydride. Among them, preferred are (meth) acrylic acids such as acrylic acid and methacrylic acid. It has a loyl group. These can use 1 type (s) or 2 or more types.
상기 에폭시수지와 불포화일염기산과의 에스테르화반응은 이미 공지되어 있는 것으로, 촉매로서 4급포스포늄염을 이용하는 것 이외에는 그대로 채용가능하다. 통상, 불포화 일염기산의 사용량으로서는 에폭시수지중의 에폭시기 1 화학당량에 대하여 0.8∼1.1몰이 적합해서, 후술하는 라디칼중합성 모노머나 용매 처럼 희석제의 존재하에 또는 비존재하에 하이드로퀴논 등의 퀴논류, 2,6-디-tert-부틸페놀 등의 알킬페놀류. 페노티아진, 4-히드록시-2,2,6,6-테트라메틸피페리진-N-옥실 등의 N-옥실류나 산소 등의 중합금지제, 반응촉매로서 4급포스포늄염의 존재하에 통상 80-130℃로 실시하는 것에 의해서 에폭시아크릴레이트가 얻어진다. The esterification reaction of the said epoxy resin and unsaturated monobasic acid is known, and it is employable as it is except using a quaternary phosphonium salt as a catalyst. In general, the amount of unsaturated monobasic acid is preferably 0.8 to 1.1 moles per 1 equivalent of the epoxy group in the epoxy resin, and quinones such as hydroquinone in the presence or absence of a diluent, such as a radically polymerizable monomer or a solvent described later, 2 Alkylphenols, such as a 6-di-tert- butylphenol. N-oxyl, such as phenothiazine and 4-hydroxy-2,2,6,6-tetramethylpiperizine-N-oxyl, polymerization inhibitor such as oxygen, and a reaction catalyst, usually 80 in the presence of a quaternary phosphonium salt. The epoxy acrylate is obtained by performing at -130 degreeC.
상기 에폭시수지와 불포화일염기산과의 반응시에는 불포화일염기산과 병용해서 장쇄알킬기, 방향환을 포함한 치환기, 알코올성 히드록실기 등을 가지는 페놀화합물이나 초산, 프로피온산, 디메틸올프로피온산 등의 라디칼 중합성을 갖지 않는 일염기산을 1종 또는 2종 이상 사용해도 된다. 이러한 종류나 사용량은 경화물 물성 등의 각 요구특성에 따라 적절히 선택하면 된다. 이것들을 불포화일염기산과 병용하여 라디칼중합성 이중결합과 히드록실기를 가지는 경화성 수지를 얻는 경우, 에폭시수지중의 에폭시기의 1 화학당량에 대하여 불포화일염기산을 0.4몰 이상, 바람직하게 0.5몰 이상으로 하는 것이 적합하고, 불포화일염기산과 페놀화합물이나 라디칼중합성을 갖지 않는 일염기산과의 합계로서는 에폭시기 1 화학당량에 대하여 0.8-1.1몰로 하는 것이 바람직하다. 불포화일염기산의 양이 적으면 에폭시아크릴레이트의 광중합성이 불충분하게 된다. 또한 그 합계량이 1.1몰을 초과하는 경우는 미반응으로 존재하는 불포화일염기산 등이 증대하고 그 결과 저분자량화합물이 경화물의 특성저하를 일으키기 때문에 바람직하지 않다. In the reaction between the epoxy resin and the unsaturated monobasic acid, in combination with the unsaturated monobasic acid, radical polymerizability such as a phenol compound having a long chain alkyl group, a substituent containing an aromatic ring, an alcoholic hydroxyl group, and the like, acetic acid, propionic acid, dimethylolpropionic acid, etc. You may use 1 type, or 2 or more types of monobasic acids which do not have. What is necessary is just to select these types and usage amounts suitably according to each required characteristic, such as hardened | cured material physical property. When using these together with an unsaturated monobasic acid to obtain a curable resin having a radically polymerizable double bond and a hydroxyl group, the unsaturated monobasic acid is 0.4 mol or more, preferably 0.5 mol or more with respect to 1 chemical equivalent of the epoxy group in the epoxy resin. It is preferable to make it, and as a sum total of unsaturated monobasic acid, a phenolic compound, and monobasic acid which does not have radical polymerization property, it is preferable to set it as 0.8-1.1 mol with respect to 1 chemical equivalent of an epoxy group. If the amount of unsaturated monobasic acids is small, the photopolymerization of the epoxy acrylate is insufficient. If the total amount exceeds 1.1 moles, the unsaturated monobasic acid or the like which is not reacted increases, and as a result, the low molecular weight compound causes deterioration of the properties of the cured product.
상기 에스테르화 반응에 있어서, 종래법에서는 촉매로서 트리에틸아민 등의 3급아민, 트리에틸벤질암모늄클로라이드 등의 4급암모늄염, 2-에틸-4-메틸이미다졸 등의 이미다졸화합물, 트리페닐포스핀 등의 3급포스핀, 금속의 유기산염 등이 사용되어 왔지만, 본 발명에서는 이러한 에스테르화 촉매 대신에 화학식 1로 나타내는 특정의 4급포스포늄을 사용한다. In the above esterification reaction, in the conventional method, as a catalyst, tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzyl ammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, and triphenyl Although tertiary phosphines, such as phosphine, organic acid salts of metals, etc. have been used, the specific quaternary phosphonium represented by General formula (1) is used instead of this esterification catalyst in this invention.
상기 4급포스포늄염은 인 원자에 결합하는 유기기 R1, R2, R3, R4 모두가 방향환을 가지고 있는 것에 특징이 있다. 후술하는 실시예로부터도 명백하게 되는 바와 같이 인 원자에 결합하는 유기기 R1, R2, R3, R4 중 1개가 방향환을 가지지 않는 알킬기인 4급포스포늄염은 수지조성물의 보존중의 점도상승을 억제하는 효과가 불충분하다. 이 때문에 본발명에서는 모든 유기기가 인원자에 직접 결합하든지, 사이에 알킬기 등의 다른 유기기를 개재하여 방향환을 가지고 있는 4급포스포늄염을 에스테르화촉매로서 사용하는 것이다. 왜, 이러한 특정의 4급포스포늄염만이 유용한가는 명확하지 않지만, 4급포스포늄염이 가지는 방향환의 영향이라고 생각된다. 다만, 상기 특정의 4급포스포늄염은 공지의 3급아민이나 3급포스핀류와 같은 에스테르화 촉매 보다 촉매활성이 높기 때문에, 에폭시아크릴레이트에 잔존하는 에폭시기가 적게 되어 감광성수지조성물을 보존하고 있는 동안에 이러한 잔존 에폭시기와 카르복실기(미반응 불포화일염기산 유래의 카르복실기 및/또는 다염기산무수물과의 반응에 의해 도입되는 카르복실기)와의 반응확률이 저감하기 때문에 점도상승이 억제되는 것이라고 생각된다. 또한 상기 특정의 4급포스포늄염은 에스테르화반응조건하에서 서서히 실활하기 때문에, 혹은 경화도막의 예비건조시의 온도조건에서는 촉매활성을 나타내지 않기 때문에 에폭시수지를 별도 배합한 경우에도 알칼리현상성의 저감이 억제되는 것이라 생각된다. The quaternary phosphonium salt is characterized in that all of the organic groups R 1 , R 2 , R 3 , and R 4 bonded to the phosphorus atom have an aromatic ring. As will be apparent from the examples described later, quaternary phosphonium salts in which one of the organic groups R 1 , R 2 , R 3 , and R 4 bonded to the phosphorus atom are alkyl groups having no aromatic ring have a viscosity during storage of the resin composition. The effect of suppressing the rise is insufficient. For this reason, in this invention, the quaternary phosphonium salt which has an aromatic ring through all organic groups couple | bonded directly with a person group, or between other organic groups, such as an alkyl group, is used as esterification catalyst. It is not clear why only this specific quaternary phosphonium salt is useful, but it is thought to be an effect of the aromatic ring possessed by the quaternary phosphonium salt. However, since the specific quaternary phosphonium salt has higher catalytic activity than known esterification catalysts such as tertiary amines and tertiary phosphines, the epoxy group remaining in the epoxy acrylate is reduced, while preserving the photosensitive resin composition. It is considered that the increase in viscosity is suppressed because the probability of reaction between the remaining epoxy group and the carboxyl group (carboxyl group introduced by reaction with unreacted unsaturated monobasic acid and / or polybasic acid anhydride) is reduced. In addition, since the specific quaternary phosphonium salt is gradually deactivated under the esterification reaction condition or does not exhibit catalytic activity under the temperature condition at the time of predrying of the cured coating film, reduction of alkali developability is suppressed even when epoxy resin is separately blended. I think it is.
화학식 1에 있어서, R1, R2, R3, R4는 아릴기 또는 아랄킬기가 바람직하고, 이것들은 치환기를 가질수도 있고, 아랄킬기의 알킬기(인원자와 방향환 사이의 탄화수소기)의 탄소수도 특별히 한정되지 않는다. 특히 바람직하기로는 R1, R2, R3 , R4가 페닐기 또는 벤질기인 4급포스포늄염이다. Ｘ-는 대응 아니온을 나타내는 것으로 할로겐화물 이온, 초산이온, 붕산이온 등을 의미한다. In formula (1), R 1 , R 2 , R 3 and R 4 are preferably an aryl group or an aralkyl group, and these may have a substituent, and may be substituted with an alkyl group (a hydrocarbon group between an atom and an aromatic ring) of the aralkyl group. Carbon number is not specifically limited, either. Especially preferably, it is a quaternary phosphonium salt whose R <1> , R <2> , R <3> , R <4> is a phenyl group or a benzyl group. Ｘ - represents a corresponding anion and means halide ions, acetate ions, borate ions, and the like.
화학식 1로 나타내어 지는 4급포스포늄염의 구체적인 예로서는 벤질트리페닐포스포늄브로마이드, 벤질트리페닐포스포늄클로라이드, 벤질트리페닐포스포늄히드록사이드, 4-클로로벤질트리페닐포스포늄클로라이드, 신나밀트리페닐포스포늄클로라이드, 4-에톡시벤질트리페닐포스포늄브로마이드, 페나실트리페닐포스포늄브로마이드, 테트라페닐포스포늄브로마이드, 테트라페닐포스포늄클로라이드, 테트라페닐포스포늄요다이드, 테트라페닐포스포늄테트라페닐보레이드 등을 들수 있으며, 1종 또는 2종이상을 이용할 수가 있다. 이중에서도 벤질트리페닐포스포늄브로마이드, 벤질트리페닐포스포늄클로라이드, 4-클로로벤질트리페닐포스포늄클로라이드 등이 바람직하다. Specific examples of the quaternary phosphonium salt represented by the formula (1) include benzyl triphenyl phosphonium bromide, benzyl triphenyl phosphonium chloride, benzyl triphenyl phosphonium hydroxide, 4-chlorobenzyl triphenyl phosphonium chloride, cinnamil triphenyl phosphate Phosphorus chloride, 4-ethoxybenzyl triphenylphosphonium bromide, phenacyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium iodide, tetraphenylphosphonium tetraphenylboride, etc. And one or two or more kinds thereof may be used. Among these, benzyl triphenyl phosphonium bromide, benzyl triphenyl phosphonium chloride, 4-chlorobenzyl triphenyl phosphonium chloride, etc. are preferable.
또한, 아세토니트릴트리페닐포스포늄클로라이드, 아릴트리페닐포스포늄브로마이드, 아릴트리페닐포스포늄클로라이드, n-아밀트리페닐포스포늄브로마이드, 브로모메틸트리페닐포스포늄브로마이드, 3-브로모프로필트리페닐포스포늄브로마이드, n-부틸트리페닐포스포늄브로마이드, 4-카르복시부틸트리페닐포스포늄브로마이드, (3-카르복시프로필)트리페닐포스포늄브로마이드, 클로로메틸트리페닐포스포늄클로라이드, 시아노메틸트리-n-부틸포스포늄클로라이드, 시크로프로필트리페닐포스포늄브로마이드, 2-(1,3-디옥산-2-일)에틸트리페닐포스포늄브로마이드, 2-(1,3-디옥소란-2-일)에틸트리페닐포스포늄브로마이드, 2-(1,3-디옥소란-2-일)메틸트리페닐포스포늄브로마이드, 에톡시카보닐메틸(트리페닐)포스포늄브로마이드, 에틸트리페닐포스포늄브로마이드, (포르밀메틸)트리페닐포스포늄클로라이드, n-헵틸트리페닐포스포늄브로마이드, n-헥실트리페닐포스포늄브로마이드, 이소프로필트리페닐포스포늄요다이드, 메톡시카보닐메틸(트리페닐)포스포늄브로마이드, (메톡시메틸)트리페닐포스포늄클로라이드, 메틸트리페닐포스포늄브로마이드, 메틸트리페닐포스포늄요다이드, n-프로필트리페닐포스포늄브로마이드, 테트라-n-부틸포스포늄브로마이드, 테트라-n-부틸포스포늄클로라이드, n-테트라데실트리페닐포스포늄브로마이드, 테트라에틸포스포늄브로마이드, 테트라에틸포스포늄헥사플루오로포스페이트, 테트라에틸포스포늄테트라플루오로보레이드, 테트라키스(히드록시메틸)포스포늄클로라이드, 테트라키스(히드록시메틸)포스포늄설페이트, 테트라-n-옥틸포스포늄브로마이드, 2-(트리메틸실릴)에톡시메틸트리페닐포스포늄클로라이드, 2-(트리메틸실릴에틸)트리페닐포스포늄요다이드, (3-트리메틸실릴-2-프로피닐)트리페닐포스포늄브로마이드, 트리페닐비닐포스포늄브로마이드 등의 상기 화학식 1에는 해당하지 않는 4급포스포늄염을 상기 화학식 1로 나타내어지는 4급포스포늄염과 함께 에스테르화 촉매로 사용해도 된다. Furthermore, acetonitrile triphenyl phosphonium chloride, aryl triphenyl phosphonium bromide, aryl triphenyl phosphonium chloride, n-amyl triphenyl phosphonium bromide, bromomethyl triphenyl phosphonium bromide, 3-bromopropyl triphenyl phosphose Phosphonium bromide, n-butyltriphenylphosphonium bromide, 4-carboxybutyltriphenylphosphonium bromide, (3-carboxypropyl) triphenylphosphonium bromide, chloromethyltriphenylphosphonium chloride, cyanomethyltri-n-butyl Phosphonium chloride, cyclopropyltriphenylphosphonium bromide, 2- (1,3-dioxan-2-yl) ethyltriphenylphosphonium bromide, 2- (1,3-dioxolan-2-yl) ethyl Triphenylphosphonium bromide, 2- (1,3-dioxolan-2-yl) methyltriphenylphosphonium bromide, ethoxycarbonylmethyl (triphenyl) phosphonium bromide, ethyltriphenylphosphonium bromide De, (formylmethyl) triphenylphosphonium chloride, n-heptyltriphenylphosphonium bromide, n-hexyltriphenylphosphonium bromide, isopropyltriphenylphosphonium iodide, methoxycarbonylmethyl (triphenyl) Phosphonium bromide, (methoxymethyl) triphenylphosphonium chloride, methyltriphenylphosphonium bromide, methyltriphenylphosphonium iodide, n-propyltriphenylphosphonium bromide, tetra-n-butylphosphonium bromide, tetra- n-butylphosphonium chloride, n-tetradecyltriphenylphosphonium bromide, tetraethylphosphonium bromide, tetraethylphosphonium hexafluorophosphate, tetraethylphosphonium tetrafluoroboride, tetrakis (hydroxymethyl) phosphonium Chloride, tetrakis (hydroxymethyl) phosphonium sulfate, tetra-n-octylphosphonium bromide, 2- (trimethylsilyl) Formula (1), such as oxymethyltriphenylphosphonium chloride, 2- (trimethylsilylethyl) triphenylphosphonium iodide, (3-trimethylsilyl-2-propynyl) triphenylphosphonium bromide, triphenylvinylphosphonium bromide and the like You may use the quaternary phosphonium salt which is not applicable with the quaternary phosphonium salt represented by the said Formula (1) as an esterification catalyst.
게다가, 트리에틸아민 등의 3급아민, 트리에틸벤질암모늄클로라이드 등의 4급암모늄염, 2-에틸-4-메틸이미다졸 등의 이미다졸화합물, 트리페닐포스핀 등의 3급포스핀, 금속의 유기산 또는 무기염 혹은 킬레이트 화합물 등의, 공지의 에스테르화 촉매도 일부 병용할 수 있다. In addition, tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzyl ammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, tertiary phosphines such as triphenylphosphine and metals Some well-known esterification catalysts, such as an organic acid, an inorganic salt, or a chelate compound, can also be used together.
화학식 1로 나타내어지는 4급포스포늄염은 에폭시수지와 불포화일염기산과의 합계량에 대하여 통상 0.01-10질량%, 바람직하게 0.05-5질량% 사용한다. 사용량이 0.01질량% 보다 적으면 에폭시수지와 불포화일염기산과의 에스테르화 반응이 충분히 진행하지 않고, 10 중량%를 초과해서는 소용없게 될 뿐만아니라 수지조성물의 보존안정성이 저하해 버리는 경우가 있다. The quaternary phosphonium salt represented by the general formula (1) is usually used in an amount of 0.01-10 mass%, preferably 0.05-5 mass%, based on the total amount of the epoxy resin and the unsaturated monobasic acid. If the amount is less than 0.01% by mass, the esterification reaction between the epoxy resin and the unsaturated monobasic acid does not proceed sufficiently, and if it exceeds 10% by weight, it is not useful and the storage stability of the resin composition may be lowered.
에폭시아크릴레이트합성시에 사용가능한 용제(희석제)로서는 톨루엔, 크실렌등의 탄화수소류; 셀로솔브. 부틸셀로솔브 등의 셀로솔브류; 카르비톨, 부틸카르비톨 등의 카르비톨류; 셀로솔브아세테이트, 카르비톨아세테이트, (디)프로필렌글리콜모노메틸에테르아세테이트, 프탈산(디)메틸, 호박산(디)메틸, 아디핀산(디)메틸 등의 에스테르류; 메틸이소부틸케논, 메틸에틸케톤 등의 케톤류; (디)에틸렌글리콜디메틸에테르 등의 에테르류 등을 들수 있고, 이러한 용매는 1종 또는 2종 이상을 혼합하여 사용할 수도 있다. As a solvent (diluent) which can be used at the time of epoxy acrylate synthesis, Hydrocarbons, such as toluene and xylene; Cellosolve. Cellosolves such as butyl cellosolve; Carbitols such as carbitol and butyl carbitol; Esters such as cellosolve acetate, carbitol acetate, (di) propylene glycol monomethyl ether acetate, phthalic acid (di) methyl, succinic acid (di) methyl, and adipic acid (di) methyl; Ketones such as methyl isobutyl kenone and methyl ethyl ketone; Ethers, such as (di) ethylene glycol dimethyl ether, etc. are mentioned, These solvent can also be used 1 type or in mixture of 2 or more types.
상기 에스테르화 반응에 의해서 얻어지는 에폭시아크릴레이트에는 에폭시기 의 개환반응에 의하여 히드록실기가 생성한다. 이러한 히드록실기에 다염기산무수물을 부가시키는 것으로 얻을 수 있는 에폭시아크릴레이트에는 카르복실기가 도입되기 때문에 미노광부분을 알칼리수용액에 용해시킬 수 있어, 포토리소그래피에 의해 미세가공이나 화상형성하는 경우에 알칼리현상이 가능해진다. In the epoxy acrylate obtained by the esterification reaction, a hydroxyl group is produced by the ring-opening reaction of the epoxy group. Since the carboxyl group is introduced into the epoxy acrylate obtained by adding a polybasic acid anhydride to such a hydroxyl group, the unexposed portion can be dissolved in an alkaline aqueous solution, and the alkali phenomenon occurs when microprocessing or image forming by photolithography. It becomes possible.
히드록실기에 반응하는 다염기산무수물로서는 무수프탈산, 무수호박산, 옥테닐무수호박산, 페타도데세닐무수호박산, 무수말레인산, 테트라히드로무수프탈산, 헥사히드로무수프탈산, 메틸테트라히드로무수프탈산, 3,6-엔도메틸렌테트라히드로무수프탈산, 메틸엔도메틸렌테트라히드로무수프탈산, 테트라브로모무수프탈산, 9,10-디히드로-9-옥사-10-포스파페난트렌-10-옥사이드와 무수이타콘산 혹은 무수말레인산과의 반응물 등의 이염기산무수물; 무수트리멜리트산; 비페닐테트라카본산이무수물, 나프탈렌테트라카본산이무수물, 디페닐에테르테트라카본산이무수물, 부탄테트라카본산이무수물, 시크로펜탄테트라카본산이무수물, 무수피로멜리트산, 벤조페논테트라카본산이무수물 등의 지방족 또는 방향족 사염기산 무수물 등을 들 수 있으며, 이들은 1종 또는 2종 이상을 사용할 수 있다. Examples of the polybasic acid anhydride reacting with the hydroxyl group include phthalic anhydride, amber anhydrous acid, octenyl anhydrous bakactic acid, fetadodecenyl amber anhydrous acid, maleic anhydride, tetrahydrophthalic anhydride, hexahydro phthalic anhydride, methyl tetrahydro phthalic anhydride, and 3,6-endodo. Of methylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and itaconic anhydride or maleic anhydride Dibasic acid anhydrides such as reactants; Trimellitic anhydride; Aliphatic such as biphenyltetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride and the like Aromatic tetrabasic acid anhydride etc. are mentioned, These can use 1 type (s) or 2 or more types.
에폭시아크릴레이트와 다염기산무수물과의 반응에 의해서, 카르복실기함유 에폭시아크릴레이트를 얻을 수 있지만, 이러한 카르복실기함유 에폭시아크릴레이트의 산가가 30 mgKOH/g 이상이 되도록 에폭시아크릴레이트와 다염기산무수물과의 반응율을 조정하는 것이 바람직하다. 보다 바람직하게 산가의 하한은 50 mgKOH/g이다. 또한 바람직한 상한은 120 mgKOH/g, 보다 바람직한 상한은 100 mgKOH/g 이다.이러한 산가를 만족시키려면 에폭시아크릴레이트중의 히드록실기 1화학당량에 대하 여 다염기산무수물중의 산무수물기가 0.1-1.1 몰의 범위가 되도록 반응시키는 것이 좋다. 보다 바람직하기로는 0.2-0.9몰이다. 이러한 반응은 통상 50-130℃에서 행한다. 반응시킬 때에는 앞서 언급한 용제 혹은 하이드로퀴논이나 산소 등의 중합금지제를 존재시키거나. 종종 필요에 따라 공지의 촉매를 첨가해도 된다. Although the carboxyl group-containing epoxy acrylate can be obtained by the reaction between the epoxy acrylate and the polybasic acid anhydride, the reaction rate of the epoxy acrylate and the polybasic acid anhydride is adjusted so that the acid value of such carboxyl group-containing epoxy acrylate is 30 mgKOH / g or more. It is preferable. More preferably, the lower limit of the acid value is 50 mgKOH / g. In addition, the upper limit is preferably 120 mgKOH / g, and more preferably 100 mgKOH / g. To satisfy this acid value, the acid anhydride group in the polybasic acid anhydride is 0.1-1.1 mol relative to one chemical equivalent of the hydroxyl group in the epoxy acrylate. It is good to react so that it may become in the range of. More preferably, it is 0.2-0.9 mol. This reaction is usually carried out at 50-130 ° C. When reacting, the aforementioned solvent or polymerization inhibitor such as hydroquinone or oxygen is present. Sometimes a well-known catalyst may be added as needed.
본발명의 화상형성용 감광성수지조성물은 감광성수지성분으로서 상기 카르복실기함유 에폭시아크릴레이트를 포함하는 것이지만, 이 조성물에는 공지의 라디칼중합성 화합물이 포함되어 있어도 괜찮다. 카르복실기함유 에폭시아크릴레이트와 라디칼중합성화합물의 비율은 특별히 한정되지는 않으나 100:5-500(질량비)하는 것이 바람직하다. 이러한 라디칼중합성 화합물에는 올리고머와 모노머가 있다. Although the photosensitive resin composition for image formation of this invention contains the said carboxyl group-containing epoxy acrylate as a photosensitive resin component, this composition may contain the well-known radically polymerizable compound. Although the ratio of a carboxyl group-containing epoxy acrylate and a radically polymerizable compound is not specifically limited, It is preferable that it is 100: 5-500 (mass ratio). Such radically polymerizable compounds include oligomers and monomers.
라디칼중합성 올리고머로서는 불포화폴리에스테르, 우레탄아크릴레이트, 폴리에스테르아크릴레이트 등을 사용할 수 있다. Unsaturated polyester, urethane acrylate, polyester acrylate, etc. can be used as a radically polymerizable oligomer.
라디칼중합성 모노머로서는 스티렌, α-메틸스티렌, α-클로로스티렌, 비닐톨루엔, 디비닐벤젠, 디아릴프탈레이트, 디아릴벤젠포스포네이트 등의 방향족비닐계 모노머; 초산비닐, 아디핀산비닐 등의 비닐에스테르모노머; 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, β-히드록시에틸(메타)아크릴레이트, (2-옥소-1,3-디옥소란-4-일)-메틸(메타)아크릴레이트, (디)에틸렌글리콜디(메타)아크릴레이트, 프로필렌글리콜디(메타)아크릴레이트, 트리메틸올프로판디(메타)아크릴레이트, 트리메틸올프로판트리(메타)아크릴레이트, 펜타에리스리톨테트라(메타)아크릴레이트, 디펜타에리스리톨헥사(메타)아크릴레이트, 트리스[2-(메타)아크릴로일옥시에틸]트리아진 등의 (메타)아크릴계 모노머; (메타)아크릴산2-(히드록시에톡시)에틸, (메타)아크릴산2-(티오히드록시에톡시)에틸, (메타)아크릴산2-(이소프로페녹시에톡시에톡시)에틸, (메타)아크릴산2-(이소프로페녹시에톡시에톡시에톡시)에틸, (메타)아크릴산2-(이소프로페녹시에톡시에톡시에톡시에톡시)에틸 등의 라디칼중합성이중결합을 갖는 비닐(티오)에테르화합물; 트리아릴시아누레이트 등을 들 수 있다. As a radically polymerizable monomer, Aromatic vinyl monomers, such as styrene, (alpha) -methylstyrene, (alpha)-chloro styrene, vinyltoluene, divinylbenzene, a diaryl phthalate, a diaryl benzene phosphonate; Vinyl ester monomers such as vinyl acetate and vinyl adipic acid; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, β-hydroxyethyl (meth) acrylate, (2-oxo-1,3-dioxolan-4-yl)- Methyl (meth) acrylate, (di) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol (Meth) acrylic monomers such as tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tris [2- (meth) acryloyloxyethyl] triazine; (Meth) acrylic acid 2- (hydroxyethoxy) ethyl, (meth) acrylic acid 2- (thiohydroxyethoxy) ethyl, (meth) acrylic acid 2- (isopropenoxyethoxyethoxy) ethyl, (meth) Vinyl (thio) having radically polymerizable double bonds such as 2- (isopropenoxyethoxyethoxyethoxy) ethyl acrylate and 2- (isopropenoxyethoxyethoxyethoxy) ethyl acrylate Ether compounds; Triaryl cyanurate etc. are mentioned.
본발명의 화상형성용 감광성수지조성물에는 노광후의 경화도막의 가교밀도를 향상시키기 위하여 에폭시수지를 배합할 수도 있다. 에폭시수지로서는 앞서 언급한 에폭시아크릴레이트의 출발원료로서 예시한 것이 모두 사용가능하다. 이때, 디시안디아미드, 이미다졸화합물 등의 에폭시경화제를 배합할 수도 있다. The photosensitive resin composition for image formation of the present invention may be blended with an epoxy resin in order to improve the crosslinking density of the cured coating film after exposure. As the epoxy resin, any of those exemplified as starting materials for the aforementioned epoxy acrylates can be used. At this time, epoxy hardening | curing agents, such as a dicyandiamide and an imidazole compound, can also be mix | blended.
또한, 본발명의 화상형성용 감광성수지조성물에는 필요에 따라 탈크, 클레이, 황산바륨 등의 충전재, 착색용안료, 소포제, 커플링제, 레벨링제, 증감제, 이형제, 활제, 가소제, 산화방지제, 자외선흡수제, 난연제, 중합억제제, 증점제 등의 공지의 첨가제를 첨가할 수도 있다. 또한, 옥사졸린화합물, 옥세탄화합물 등을 배합할 수도 있다. 게다가, 각종 강화섬유를 보강섬유로로 사용하여 섬유강화복합재료로 할 수가 있다. In addition, the photosensitive resin composition for forming an image of the present invention includes fillers such as talc, clay, barium sulfate, coloring pigments, antifoaming agents, coupling agents, leveling agents, sensitizers, mold release agents, lubricants, plasticizers, antioxidants, and ultraviolet rays, as necessary. Well-known additives, such as an absorbent, a flame retardant, a polymerization inhibitor, and a thickener, can also be added. Moreover, an oxazoline compound, an oxetane compound, etc. can also be mix | blended. In addition, various reinforcing fibers can be used as reinforcing fibers to form a fiber reinforced composite material.
본발명의 화상형성용 감광성수지조성물은 공지의 열중합개시제를 사용하는 것에 의해 열경화도 가능하지만, 포토리소그래피에 의한 미세가공이나 화상형성하려면 광중합개시제를 첨가하여 광경화하는 것이 바람직하다. The photosensitive resin composition for image formation of the present invention can be thermally cured by using a known thermal polymerization initiator. However, in order to finely process or form an image by photolithography, photocuring is preferably added by adding a photopolymerization initiator.
광중합개시제로서는 공지의 것을 사용할 수 있으며, 그 예로는 벤조인, 벤조인메틸에테르, 벤조인에틸에테르 등의 벤조인과 그의 알킬에테르류; 아세토페논, 2,2-디메톡시-2-페닐아세토페논, 1,1-디클로로아세토페논, 4-(1-t-부틸디옥시-1-메 틸에틸)아세토페논 등의 아세토페논류; 2-메틸안트라퀴논, 2-아밀안트라퀴논, 2-t-부틸안트라퀴논, 1-클로로안트라퀴논 등의 안트라퀴논류; 2,4-디메틸티옥산톤, 2,4-디이소프로필티옥산톤, 2-클로로티옥산톤 등의 티옥산톤류; 아세토페논디메틸케탈, 벤질디메틸케탈 등의 케탈류; 벤조페논, 4-(1-t-부틸디옥시-1-메틸에틸)벤조페논, 3,3',4,4'-테트라키스(t-부틸디옥시카보닐)벤조페논 등의 벤조페논류; 2-메틸-1-［4-(메틸티오)페닐］-2-몰호리노프로판-1-온이나 2-벤질-2-디메틸아미노-1-(4-몰호리노페닐)-부타논-1; 아실포스핀옥사이드류 및 크산톤류 등을 들 수 있다. As a photoinitiator, a well-known thing can be used, For example, benzoin, such as benzoin, benzoin methyl ether, and benzoin ethyl ether, and its alkyl ether; Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4- (1-t-butyldioxy-1-methylethyl) acetophenone; Anthraquinones such as 2-methylanthraquinone, 2-amyl anthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; Thioxanthones such as 2,4-dimethyl thioxanthone, 2,4-diisopropyl thioxanthone, and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone, 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone ; 2-methyl-1- [4- (methylthio) phenyl] -2-molhorinopropan-1-one or 2-benzyl-2-dimethylamino-1- (4-molhorinophenyl) -butanone-1; Acyl phosphine oxides, xanthones, etc. are mentioned.
이러한 광중합개시제는 1종 또는 2종이상의 혼합물로 사용되어, 화상형성용 감광성수지(카르복실기 함유 에폭시아크릴레이트와 필요에 따라 사용되는 라디칼중합성화합물의 합계) 100질량부에 대하여 0.5-30 질량부 포함되어 있는 것이 바람직하다. 광중합개시제의 양이 0.5질량부 보다 적은 경우에는 광조사시간을 늘려야만 하고, 광조사를 실시해도 중합이 어렵기도 하여 적절한 표면경도를 얻을 수 없게 된다. 또한 광중합개시제를 30중량부를 초과하여 배합하는 경우에는 다량 사용에 따른 이득이 없다.These photoinitiators are used in one kind or in a mixture of two or more kinds and contain 0.5-30 parts by mass with respect to 100 parts by mass of the photosensitive resin (the sum of the carboxyl group-containing epoxy acrylate and the radically polymerizable compound used if necessary). It is preferable that it is done. If the amount of the photopolymerization initiator is less than 0.5 parts by mass, the light irradiation time must be increased, and even if light irradiation is applied, the polymerization is difficult and proper surface hardness cannot be obtained. In addition, when the photopolymerization initiator is blended in excess of 30 parts by weight, there is no benefit of using a large amount.
화상형성용 감광성수지조성물을 기재에 도포할 때 작업성 등의 관점에서, 화상형성용 감광성수지조성물을 보존할 때는 용액상태로 보존하는 것이 바람직하다. 용매로서는 에폭시아크릴레이트 합성시에 사용할 수 있는 용매가 모두 사용가능하다. 도포작업시에는 최적점도가 되도록 희석 또는 농축할 수 있다. When applying the image forming photosensitive resin composition to a substrate, from the viewpoint of workability and the like, it is preferable to store the image forming photosensitive resin composition in a solution state. As a solvent, all the solvents which can be used at the time of epoxy acrylate synthesis can be used. During application, it may be diluted or concentrated to achieve optimum viscosity.
본발명의 화상형성용 감광성수지조성물을 광경화시켜 사용하는 경우, 미노광부분이 알칼리수용액에 용해되므로 알칼리현상을 실시할 수 있다. 사용가능한 알칼 리의 구체적인 예로서는, 예를 들어 탄산나트륨, 탄산칼륨, 수산화나트륨, 수산화칼륨 등의 알칼리금속화합물; 수산화칼슘 등의 알칼리토금속화합물; 암모니아; 모노메틸아민, 디메틸아민, 트리메틸아민, 모노에틸아민, 디에틸아민, 트리에틸아민, 모노프로필아민, 디메틸프로필아민, 모노에탄올아민, 디에탄올아민, 트리에탄올아민, 에틸렌디아민, 디에틸렌트리아민, 디메틸아미노에틸메타크릴레이트, 폴리에틸렌이민 등의 수용성 유기아민류를 들 수 있다. 이들은 1종 또는 2종 이상을 사용할 수 있다.
When the photosensitive resin composition for image formation of the present invention is used for photocuring, alkali development can be performed since the unexposed portion is dissolved in an alkaline aqueous solution. As a specific example of the alkali which can be used, For example, Alkali metal compounds, such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide; Alkaline earth metal compounds such as calcium hydroxide; ammonia; Monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, dimethyl Water-soluble organic amines, such as amino ethyl methacrylate and polyethyleneimine, are mentioned. These can use 1 type (s) or 2 or more types.
[실시예]EXAMPLE
이하, 실시예에 의해 본발명을 한층 더 상술하지만, 본발명을 제한하기 위한 것은 아니며, 앞서 설명된 또는 후술되는 범위를 일탈하지 않는 범위내에서 변경실시하는 것들 모두 본발명의 기술범위에 포함되는 것이다. 또한, 실시예중의 부 및 %는 질량기준이다.
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not intended to limit the present invention. will be. In addition, the part and% in an Example are a mass reference | standard.
합성예 1Synthesis Example 1
크레졸노보락형에폭시수지 ESCN195 XHH (스미토모화학제품, 에폭시당량 200) 400부에 , 아크릴산145부, 에틸카르비톨아세테이트 293부, 벤질트리페닐포스포늄브로마이드 2.2부 및 메틸하이드로퀴논 0.5부를 가하고, 115℃에서 10시간 반응시키고, 반응물의 산가가 1.7이 되었을 때 반응을 종료하였다. 에폭시아크릴레이트를 65% 포함한 에틸카르비톨아세테이트 용액을 얻었다. To 400 parts of cresol novolak-type epoxy resin ESCN195 XHH (Sumitomo Chemical, Epoxy Equivalent 200), 145 parts of acrylic acid, 293 parts of ethylcarbitol acetate, 2.2 parts of benzyltriphenylphosphonium bromide and 0.5 parts of methylhydroquinone were added at 115 ° C. The reaction was carried out for 10 hours, and the reaction was terminated when the acid value of the reactant became 1.7. An ethyl carbitol acetate solution containing 65% of epoxy acrylate was obtained.
다음, 이 용액 200부에 테트라히드로무수프탈산 43부와 에틸카르비톨아세테이트 23부를 가하고, 100℃에서 6시간 반응시켰다. 산가 94의 카르복실기 함유 에폭시아크릴레이트를 65% 포함하는 에틸카르비톨아세테이트 용액 Ａ-1을 얻었다.
Next, 43 parts of tetrahydrophthalic anhydride and 23 parts of ethyl carbitol acetate were added to 200 parts of this solution, and the mixture was reacted at 100 ° C for 6 hours. Ethyl carbitol acetate solution A-1 containing 65% of carboxyl group-containing epoxy acrylate of acid value 94 was obtained.
합성예 2Synthesis Example 2
합성예 1에서 사용한 벤질트리페닐포스포늄브로마이드 2.2부를 테트라페닐포스포늄브로마이드 2.2부로 변경한 것 이외에는 합성예 1과 동일하게 하여 115℃에서 10시간 반응시키고, 반응물의 산가가 2.5가 되었을 때 반응을 종료하였다. 에폭시아크릴레이트를 65% 포함하는 에틸카르비톨아세테이트 용액을 얻었다. Except for changing 2.2 parts of benzyltriphenylphosphonium bromide used in Synthesis Example 1 to 2.2 parts of tetraphenylphosphonium bromide, the reaction was carried out at 115 ° C. for 10 hours in the same manner as in Synthesis Example 1, and the reaction was terminated when the acid value of the reaction product reached 2.5. It was. An ethyl carbitol acetate solution containing 65% of epoxy acrylate was obtained.
다음, 이 용액 200부에 테트라히드로무수프탈산 43부와 에틸카르비톨아세테이트 23부를 가하고 100℃에서 6시간 반응시켜 산가 96의 카르복실기함유에폭시아크릴레이트를 65% 포함하는 에틸카르비톨아세테이트 용액 Ａ-2를 얻었다.
Then, 43 parts of tetrahydrophthalic anhydride and 23 parts of ethyl carbitol acetate were added to 200 parts of the solution, and the mixture was reacted at 100 ° C for 6 hours to prepare an ethyl carbitol acetate solution A-2 containing 65% of an carboxyl group-containing epoxy acrylate having an acid value of 96. Got it.
합성예 3Synthesis Example 3
합성예 1에서 사용한 것과 동일한 크레졸노보락형에폭시수지 ESCN195 XHH 400부에 ｐ-히드록시페닐-2-에탄올 83부, 에틸카르비톨아세테이트 315부, 테트라-n-부틸암모늄클로라이드 0.6부를 가하고, 120℃에서 4시간 반응시킨 후, 아크릴산 102부, 벤질트리페닐포스포늄클로라이드 2.3부 및 메틸하이드로퀴논 0.6부를 가하고, 한번 더 115℃에서 10시간 반응시키고, 반응물의 산가가 1.5가 되었을 때 반응을 종료하였다. 에폭시아크릴레이트를 65% 포함하는 에틸카르비톨아세테이트용액을 얻었다. 83 parts of k-hydroxyphenyl-2-ethanol, 315 parts of ethylcarbitol acetate, and 0.6 parts of tetra-n-butylammonium chloride were added to 400 parts of cresol novolak-type epoxy resins ESCN195XHH same as what was used in the synthesis example 1, and it is 120 degreeC After reacting for 4 hours, 102 parts of acrylic acid, 2.3 parts of benzyltriphenylphosphonium chloride and 0.6 parts of methylhydroquinone were added, and the reaction was further performed at 115 ° C for 10 hours, and the reaction was terminated when the acid value of the reaction product reached 1.5. An ethyl carbitol acetate solution containing 65% of epoxy acrylate was obtained.
다음, 이 용액 200부에 테트라히드로무수프탈산 34부와 에틸카르비톨아세테이트 18부를 가하고, 100℃에서 6시간 반응시켜 산가 79의 카르복실기함유 에폭시아크릴레이트를 65% 함유하는 에틸카르비톨아세테이트용액 Ａ-3을 얻었다.
Then, 34 parts of tetrahydrophthalic anhydride and 18 parts of ethyl carbitol acetate were added to 200 parts of the solution, and the resultant was reacted at 100 ° C for 6 hours to make an ethyl carbitol acetate solution containing 65% of the carboxyl group-containing epoxy acrylate having an acid value of 79%. Got.
비교합성예1Comparative Synthesis Example 1
합성예 1에서 사용한 벤질트리페닐포스포늄브로마이드 2.2부를 트리페닐포스핀 2.2부로 변경한 것 이외에는 합성예 1과 동일하게 하여 115℃에서 10시간반응시키고, 반응물의 산가가 6.6이 되었을 때 반응을 종료하였다. 에폭시아크릴레이트를 65% 함유하는 에틸카르비톨아세테이트용액을 얻었다. The reaction was repeated at 115 DEG C for 10 hours in the same manner as in Synthesis Example 1, except that 2.2 parts of benzyltriphenylphosphonium bromide used in Synthesis Example 1 was changed to 2.2 parts of triphenylphosphine, and the reaction was terminated when the acid value of the reaction product reached 6.6. . An ethyl carbitol acetate solution containing 65% of epoxy acrylate was obtained.
다음, 이 용액 200부에 테트라히드로무수프탈산 43부와 에틸카르비톨아세테이트 23부를 가하고, 100℃에서 6시간 반응시켰다. 산가 100의 비교용의 카르복실기함유 에폭시아크릴레이트를 65% 함유하는 에틸카르비톨아세테이트용액 Ｂ-1을 얻었다.
Next, 43 parts of tetrahydrophthalic anhydride and 23 parts of ethyl carbitol acetate were added to 200 parts of this solution, and the mixture was reacted at 100 ° C for 6 hours. Ethyl carbitol acetate solution VIII-1 containing 65% of carboxyl group-containing epoxy acrylate for comparison with acid value 100 was obtained.
비교합성예2Comparative Synthesis Example 2
합성예 1에서 사용한 벤질트리페닐포스포늄브로마이드 2.2부를 테트라-n-부틸암모늄브로마이드2.2부로 변경한 것 이외에는 합성예 1과 동일하게 하여 115℃에서 10시간반응시키고, 반응물의 산가가 4.0가 되었을 때 반응을 종료하였다. 에폭시아크릴레이트를 65% 함유하는 에틸카르비톨아세테이트용액을 얻었다. The reaction was carried out at 115 ° C. for 10 hours in the same manner as in Synthesis Example 1, except that 2.2 parts of benzyltriphenylphosphonium bromide used in Synthesis Example 1 was changed to 2.2 parts of tetra-n-butylammonium bromide, and the acid value of the reaction product was 4.0. Terminated. An ethyl carbitol acetate solution containing 65% of epoxy acrylate was obtained.
다음, 이 용액 200부에 테트라히드로무수프탈산 43부와 에틸카르비톨아세테이트 23부를 가하고, 100℃에서 6시간 반응시켰다. 산가 99의 비교용의 카르복실기함유 에폭시아크릴레이트를 65%함유하는 에틸카르비톨아세테이트용액 Ｂ-2를 얻었다. Next, 43 parts of tetrahydrophthalic anhydride and 23 parts of ethyl carbitol acetate were added to 200 parts of this solution, and the mixture was reacted at 100 ° C for 6 hours. Ethyl carbitol acetate solution # -2 containing 65% of carboxyl group-containing epoxy acrylate for comparison of acid value 99 was obtained.
비교합성예3Comparative Synthesis Example 3
합성예 에서 사용한 벤질트리페닐포스포늄브로마이드 2.2부를 에틸트리페닐포스포늄브로마이드 2.2부로 변경한 것 이외에 합성예 1과 동일하게 하여 115℃에서 10시간 반응시키고, 반응물의 산가가 3.9가 되었을 때 반응을 종료하였다. 에폭시아크릴레이트를 65% 함유하는 에틸카르비톨아세테이트용액을 얻었다. 2.2 parts of benzyltriphenylphosphonium bromide used in the synthesis example was changed to 2.2 parts of ethyltriphenylphosphonium bromide, except that the reaction was carried out at 115 ° C. for 10 hours in the same manner as in Synthesis example 1, and the reaction was terminated when the acid value of the reaction product reached 3.9. It was. An ethyl carbitol acetate solution containing 65% of epoxy acrylate was obtained.
다음, 이 용액 200부에 테트라히드로무수프탈산 43부와 에틸카르비톨아세테이트 23부를 가하고, 100℃에서 6시간 반응시켰다. 산가 97의 비교용의 카르복실기함유 에폭시아크릴레이트를 65% 함유하는 에틸카르비톨아세테이트용액 Ｂ-3를 얻었다.
Next, 43 parts of tetrahydrophthalic anhydride and 23 parts of ethyl carbitol acetate were added to 200 parts of this solution, and the mixture was reacted at 100 ° C for 6 hours. Ethyl carbitol acetate solution # -3 containing 65% of carboxyl group-containing epoxy acrylate for comparison with acid value 97 was obtained.
실시예 1∼3 및 비교예 1∼3Examples 1-3 and Comparative Examples 1-3
[보존안정성］[Storage stability]
합성예 1∼3 및 비교합성예 1∼3에서 얻은 수지용액에 대해 보존안정성을 평가하고 그 결과를 표1 에 나타내었다. 또한 보존안정성은 각 수지용액을 지름 18mm의 파이렉스제 시험관에 넣고 80℃의 오일배스중에 유지하고, Ｅ형점도계를 사용하여 점도를 경시적으로 측정하고, 초기점도(=1.0)에 대한 증점도(배율)을 평가 하였다. 수지용액의 보존안정성 평가결과(초기점도에 대한 증점율)는 표 1에 제시된다.
The storage stability was evaluated for the resin solutions obtained in Synthesis Examples 1-3 and Comparative Synthesis Examples 1-3, and the results are shown in Table 1. In addition, the storage stability of each resin solution is placed in a Pyrex test tube of 18 mm in diameter and kept in an oil bath at 80 ° C., the viscosity is measured over time using an E-type viscosity meter, and the viscosity of the initial viscosity (= 1.0) Magnification) was evaluated. The results of evaluating the storage stability of the resin solution (thickening rate with respect to the initial viscosity) are shown in Table 1.
표 1로부터 본발명의 실시예는 점도의 경시적인 상승이 억제되어 보존안정성이 뛰어난 것을 알수 있다. 비교예는 점도상승이 현저하였다.
From Table 1, it turns out that the Example of this invention is suppressed with time, and excellent in storage stability. In the comparative example, the viscosity increase was remarkable.
실시예 4∼6 및 비교예 4∼6Examples 4-6 and Comparative Examples 4-6
합성예 1∼3 및 비교합성예 1∼3에서 얻은 수지용액을 사용하여, 표 2에 나타낸 배합(표 2에서 숫자는 부수이다.)의 감광성수지조성물을 조제하고, 다음의 방법으로 알칼리현상과 광경화성을 평가하였다. 평가결과는 표 3에 제시된다.
Using the resin solutions obtained in Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 to 3, a photosensitive resin composition of the formulation shown in Table 2 (the numbers in the Table 2 are incidental) was prepared. Photocurability was evaluated. The evaluation results are presented in Table 3.
[알칼리현상성］[Alkali developability]
각 감광성수지조성물을 탈지세정한 두께 1.6mm의 동장적층판(銅張積層板) 위에 20∼30㎛의 두께로 도포하고, 열풍순환식 건조로 속에서 80℃로 건조하여 도막을 얻고나서, 1% Na2CO3 수용액을 사용하여 30℃에서 각각 2.1 ㎏/㎠의 압력하에서 60초간 현상을 행하여 도막의 잔존 유무를 육안으로 평가하였다.
Each photosensitive resin composition was coated with a thickness of 20 to 30 μm on a 1.6 mm thick copper clad laminate plate degreased, and dried at 80 ° C. in a hot air circulation drying furnace to obtain a coating film. Using Na 2 CO 3 aqueous solution, development was carried out at 30 ° C. under a pressure of 2.1 kg / cm 2 for 60 seconds to visually evaluate the presence or absence of the coating.
[광경화성］[Photocurability]
각 감광성수지조성물을 탈지세정한 두께 1.6mm의 동장적층판 위에 20∼30㎛의 두께로 도포하고, 열풍순환식 건조로 속에서 80℃로 30분 건조하여 도막을 얻었다. 다음, 자외선노광장치를 사용하여 500mJ/㎠ 노광한후, 1% Na2CO3 수용액을 사용하여 30℃에서 각각 2.1 ㎏/㎠의 압력하에서 60초간 현상을 행하여 도막의 잔존 유무를 육안으로 평가하였다.
Each photosensitive resin composition was coated with a thickness of 20 to 30 µm on a copper strip laminated sheet of 1.6 mm thickness degreased, and dried at 80 ° C. for 30 minutes in a hot air circulation drying furnace to obtain a coating film. Next, after exposure to 500mJ / ㎠ using an ultraviolet exposure apparatus, using a 1% Na 2 CO 3 aqueous solution was developed for 60 seconds at 30 ℃ under a pressure of 2.1 kg / ㎠ each to visually evaluate the presence of the coating film. .
1)치바·스페셜티·케미칼사제의 광중합개시제1) Photopolymerization initiator made by Chiba, Specialty Chemical
2)동도화성사제의 페놀노보락형 에폭시수지 2) Phenol Novolac Epoxy Resin
표 3으로부터 본발명의 실시예는 알칼리현상성이 우수하여 건조시간을 길게 해도 현상성이 유지되는 것을 알 수 있다. 비교예는 건조시간을 연장하면 현상성 저하가 현저하였다. 또한 광경화성은 모두 양호하였다.
It can be seen from Table 3 that the examples of the present invention are excellent in alkali developability and maintainability even when the drying time is extended. In the comparative example, developability was remarkable when the drying time was extended. Moreover, all photocurability was favorable.
본발명의 화상형성용감광성수지조성물 및 그의 제조방법은 특정 촉매를 사용하여 합성된 에폭시아크릴레이트를 주성분으로 하고 있으므로, 수지조성물의 보존중에 증점거동을 보이지 않고 우수한 보존안정성을 보인다. 또한 노광전의 도막건조시에 건조시간을 길게해도 약알칼리수용액에서의 현상성이 양호하다. 본발명의 화상형성용 감광성수지조성물은 다양한 용도에 이용할 수 있다. 예를 들어 FRP의 매트릭스수지, 도료, 접착제 등에도 이용할 수 있고, 미세가공이나 화상형성이 가능하여서 인쇄판이나 각종레지스트 재료에 사용할 수 있다. The image forming photosensitive resin composition of the present invention and a method for producing the same are mainly composed of epoxy acrylate synthesized using a specific catalyst, and thus exhibit excellent storage stability without showing thickening behavior during storage of the resin composition. Moreover, developability in a weak alkali aqueous solution is favorable even if drying time is extended at the time of drying a coating film before exposure. The photosensitive resin composition for image formation of the present invention can be used for various applications. For example, it can be used for matrix resins, paints, adhesives and the like of FRP, and can be used for printing plates and various resist materials because of fine processing and image formation.
Claims (6)
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| CN103045015B (en) * | 2013-01-25 | 2016-05-11 | 深圳市万佳原丝印器材有限公司 | Anti-anodic oxidation ink of liquid photosensitive imaging and developing with alkali and preparation method thereof |
| JP6075772B2 (en) * | 2013-04-18 | 2017-02-08 | 日本化薬株式会社 | Resin composition and cured product thereof |
| TWI506085B (en) | 2014-12-31 | 2015-11-01 | Ind Tech Res Inst | Resin composition and coating material using the same |
| CN106886128B (en) * | 2017-03-28 | 2021-02-19 | 深圳市道尔顿电子材料有限公司 | Negative photoresist |
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|---|---|---|---|---|
| US4175973A (en) | 1974-05-02 | 1979-11-27 | General Electric Company | Curable compositions |
| US4632891A (en) | 1984-10-04 | 1986-12-30 | Ciba-Geigy Corporation | Process for the production of images |
| JPH06135869A (en) * | 1992-10-28 | 1994-05-17 | Sagami Chem Res Center | Production of compound having perfluoroalkyl group |
| JP2002293876A (en) * | 2001-03-30 | 2002-10-09 | Dainippon Ink & Chem Inc | Production method for active-energy ray curing resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4175973A (en) | 1974-05-02 | 1979-11-27 | General Electric Company | Curable compositions |
| US4632891A (en) | 1984-10-04 | 1986-12-30 | Ciba-Geigy Corporation | Process for the production of images |
| JPH06135869A (en) * | 1992-10-28 | 1994-05-17 | Sagami Chem Res Center | Production of compound having perfluoroalkyl group |
| JP2002293876A (en) * | 2001-03-30 | 2002-10-09 | Dainippon Ink & Chem Inc | Production method for active-energy ray curing resin |
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| US20220127453A1 (en) * | 2020-10-26 | 2022-04-28 | Nan Ya Plastics Corporation | Unsaturated polyester resin composition and molded article thereof |
| US11834576B2 (en) * | 2020-10-26 | 2023-12-05 | Nan Ya Plastics Corporation | Unsaturated polyester resin composition and molded article thereof |
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| CN1278184C (en) | 2006-10-04 |
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