KR20070051762A - Alkali-developable resin composition - Google Patents
Alkali-developable resin composition Download PDFInfo
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- KR20070051762A KR20070051762A KR1020067000500A KR20067000500A KR20070051762A KR 20070051762 A KR20070051762 A KR 20070051762A KR 1020067000500 A KR1020067000500 A KR 1020067000500A KR 20067000500 A KR20067000500 A KR 20067000500A KR 20070051762 A KR20070051762 A KR 20070051762A
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- 0 OC(*c1ccc(C(C2CCCCC2)(c2ccc(*C3OC3)cc2)c(cc2)ccc2-c2ccccc2)cc1)*c1ccc(C(C2CCCCC2)(c2ccc(*C3OC3)cc2)c(cc2)ccc2-c2ccccc2)cc1 Chemical compound OC(*c1ccc(C(C2CCCCC2)(c2ccc(*C3OC3)cc2)c(cc2)ccc2-c2ccccc2)cc1)*c1ccc(C(C2CCCCC2)(c2ccc(*C3OC3)cc2)c(cc2)ccc2-c2ccccc2)cc1 0.000 description 1
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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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
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Abstract
하기 일반식(I)에서 나타내는 에폭시 수지(A)에, 불포화 1염기산(B) 및 페놀 화합물, 알코올 화합물, 아민 화합물 및 카르본산에서 선택되는 화합물(C)을 부가시킨 구조를 가지는 에폭시 부가물에 대해, 다염기산무수물(D)을 에스테르화 시켜서 얻어진 반응생성물을 함유하는 알칼리 현상성 수지 조성물.An epoxy adduct having a structure in which an unsaturated monobasic acid (B) and a compound (C) selected from a phenol compound, an alcohol compound, an amine compound, and a carboxylic acid are added to the epoxy resin (A) represented by the following General Formula (I). The alkali developable resin composition containing the reaction product obtained by esterifying the polybasic acid anhydride (D).
식 중, Cy는 C3-5의 시클로알킬기, X는 H, C1-10의 알킬기 등, Y 및 Z는 C1-C10의 알킬기 등, n은 0~10, p는 0~5, r은 0~4의 수를 나타낸다.)In formula, Cy is C3-5 cycloalkyl group, X is H, C1-10 alkyl group, Y and Z are C1-C10 alkyl groups, n is 0-10, p is 0-5, r is 0- Indicates the number 4.)
알칼리, 현상성, 광중합 개시제, 감도, 해상도, 내알칼리성, 에폭시수지 Alkali, developability, photoinitiator, sensitivity, resolution, alkali resistance, epoxy resin
Description
본 발명은 에틸렌성 불포화 결합을 가지는 특정의 화합물을 알칼리 현상성 수지 조성물, 및 상기 알칼리 현상성 수지 조성물에 광중합 개시제를 함유시켜 이루어지는 알칼리 현산성 감광성 수지 조성물에 관한다.The present invention relates to an alkali developable resin composition comprising a specific compound having an ethylenically unsaturated bond in an alkali developable resin composition and the alkali developable resin composition.
알칼리 현상성 감광성 수지 조성물은 에틸렌성 불포화 결합을 가지는 화합물을 함유하는 알칼리 현상성 수지 조성물 및 광중합 개시제를 함유하는 것이며, 이 알칼리 현상성 감광성 수지 조성물에 자외선 혹은 전자선을 조사(照射)함으로서 중합 경화시킬 수 있으므로, 광경화성 잉크, 감광성 인쇄판, 프린트 배선판, 각종 포토레지스트 등에 사용되고 있다. 최근 전자기기의 경박단소화나 고기능화의 진전에 수반해 미세패턴을 정밀도 좋게 형성하는 것이 가능한 알칼리 현상성 감광성 수지 조성물이 요망되고 있다.An alkali developable photosensitive resin composition contains the alkali developable resin composition containing the compound which has an ethylenically unsaturated bond, and a photoinitiator, and makes it polymerize-cure by irradiating an ultraviolet or electron beam to this alkali developable photosensitive resin composition. Therefore, it is used for photocurable inks, photosensitive printing plates, printed wiring boards, various photoresists, and the like. BACKGROUND ART In recent years, there has been a demand for an alkali developable photosensitive resin composition capable of precisely forming a fine pattern with advances in light and thin and high functionalization of electronic devices.
이 알칼리 현상성 수지 조성물 및 알칼리 현상성 감광성 수지 조성물로서 하기 특허문헌 1에는 광중합성 불포화 화합물 및 상기 화합물을 함유하는 알칼리 현상형 감광성 수지 조성물이 제안되고 있다. 또한 하기 특허문헌 2에는 폴리카르본산 수지를 함유하는 수지 조성물 및 상기 수지 조성물을 함유하는 감광성 수지 조성물이 제안되고 있다. 또한 하기 특허문헌 3에는 알칼리 가용성 불포화 수지 및 상기 수지를 함유하는 감방사성 수지 조성물이 제안되고 있다. 그러나 이들의 공지의 알칼리 현상성 감광성 수지 조성물은 감도가 충분하지 않고, 적절한 패턴형상이나 미세패턴을 얻는 것이 곤란하였다. 그 때문에 투명성, 밀착성 및 내알칼리성에 뛰어나며, 미세패턴을 정밀도 좋게 형성할 수 있는 알칼리 현상성 감광성 수지 조성물이 요망되고 있었다.As this alkali-developable resin composition and alkali-developable photosensitive resin composition, the following patent document 1 has proposed the photopolymerizable unsaturated compound and the alkali developable photosensitive resin composition containing the said compound. Moreover, the following patent document 2 is proposed the resin composition containing polycarboxylic acid resin, and the photosensitive resin composition containing the said resin composition. Moreover, the following patent document 3 is proposed the radiation-sensitive resin composition containing alkali-soluble unsaturated resin and the said resin. However, these well-known alkali developable photosensitive resin compositions did not have sufficient sensitivity, and it was difficult to obtain an appropriate pattern shape and a fine pattern. Therefore, the alkali developable photosensitive resin composition which is excellent in transparency, adhesiveness, and alkali resistance and which can form a fine pattern with high precision was desired.
특허문헌 1: 일본 특허 제3148429호 공보Patent Document 1: Japanese Patent No. 3148429
특허문헌 2: 일본 공개특허 2003-107702호 공보Patent Document 2: Japanese Unexamined Patent Publication No. 2003-107702
특허문헌 3: 일본 공개특허 2003-89716호 공보Patent Document 3: Japanese Unexamined Patent Publication No. 2003-89716
해결하고자 하는 문제점은 상술한 바와 같이, 감도가 충분하고, 적절한 패턴형상이나 미세패턴을 얻는 것이 가능한 알칼리 현상성 수지 조성물 및 알칼리 현상성 감광성 수지 조성물이 지금까지 없었다는 것이다.The problem to be solved is that, as described above, there has been no alkali developable resin composition and alkali developable photosensitive resin composition which have sufficient sensitivity and are capable of obtaining an appropriate pattern shape or fine pattern.
따라서 본 발명의 목적은 감도, 해상도, 투명도, 밀착성, 내알칼리성 등에 뛰어나며, 미세패턴을 정밀도 좋게 형성할 수 있는 알칼리 현상성 수지 조성물 및 알칼리 현상성 감광성 수지 조성물을 제공하는 것에 있다.Accordingly, an object of the present invention is to provide an alkali developable resin composition and an alkali developable photosensitive resin composition which are excellent in sensitivity, resolution, transparency, adhesion, alkali resistance, and the like, and can form fine patterns with high accuracy.
본 발명은 하기 일반식(I)에서 나타내는 에폭시 수지(A)에, 불포화 1염기산(B) 및 페놀 화합물, 알코올 화합물, 아민 화합물 및 카르본산에서 선택되는 화합물(C)을 부가시킨 구조를 가지는 에폭시 부가물에 대해, 다염기산무수물(D)을 에스테르화시켜서 얻어진 반응생성물을 함유하는 알칼리 현상성 수지 조성물이며, 상기 에폭시 부가물은 상기 에폭시 수지(A)의 에폭시기 1개에 대해, 상기 불포화 1염기산(B)의 카르복실기가 0.1~1.0개이며, 상기 화합물(C)의 페놀성 수산기, 알코올성 수산기, 아미노기 또는 카르복실기가 0~0.9개이며, 나아가 상기 불포화 1염기산(B) 및 상기 화합물(C)의 합이 0.1~1.0개가 되는 비율로 부가시킨 구조를 가지고, 상기 에스테르화는 상기 에폭시 부가물의 수산기 1개에 대해, 상기 다염기산무수물(D)의 산무수물 구조가 0.1~1.0개가 되는 비율로 행해지는 알칼리 현상성 수지 조성물을 제공함으로써 상기 목적을 달성한 것이다.The present invention has a structure in which an unsaturated monobasic acid (B) and a compound (C) selected from a phenol compound, an alcohol compound, an amine compound and a carboxylic acid are added to an epoxy resin (A) represented by the following general formula (I). It is an alkali developable resin composition containing the reaction product obtained by esterifying a polybasic acid anhydride (D) with respect to an epoxy adduct, The said epoxy adduct is the said unsaturated monobasic with respect to one epoxy group of the said epoxy resin (A). The carboxyl group of acid (B) is 0.1-1.0, the phenolic hydroxyl group, alcoholic hydroxyl group, amino group, or carboxyl group of said compound (C) is 0-0.9, Furthermore, the said unsaturated monobasic acid (B) and said compound (C) ), And the esterification is such that the acid anhydride structure of the polybasic acid anhydride (D) is 0.1 to 1.0 with respect to one hydroxyl group of the epoxy adduct. The said objective is achieved by providing the alkali developable resin composition performed by a ratio.
(식 중, Cy는 탄소원자수 3~10의 시클로알킬기를 나타내고, X는 수소원자, 탄소원자수 1~10의 알킬기 또는 알콕시기에 의해 치환되어 있어도 좋은 페닐기 또는 탄소원자수 3~10의 시클로알킬기를 나타내고, Y 및 Z는 각각 독립해서 탄소원자수 1~10의 알킬기, 탄소원자수 1~10의 알콕시기, 탄소원자수 2~10의 알케닐기 또는 할로겐 원자를 나타내고, 상기 알킬기, 상기 알콕시기 및 상기 알케닐기는 할로겐 원자로 치환되어 있어도 좋고, n은 0~10의 수를 나타내고, p는 0~5의 수를 나타내고, r은 0~4의 수를 나타낸다.) (In the formula, Cy represents a cycloalkyl group having 3 to 10 carbon atoms, X represents a phenyl group or a cycloalkyl group having 3 to 10 carbon atoms which may be substituted by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group, Y and Z each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, and the alkyl group, the alkoxy group and the alkenyl group are halogen It may be substituted by an atom, n represents the number of 0-10, p represents the number of 0-5, r represents the number of 0-4.)
또한 본 발명은 상기 알칼리 현상성 수지 조성물 및 광중합 개시제를 함유하는 알칼리 현상성 감광성 수지 조성물을 제공함으로써 상기 목적을 달성한 것이다.Moreover, this invention achieves the said objective by providing the alkali developable photosensitive resin composition containing the said alkali developable resin composition and a photoinitiator.
이하, 본 발명의 알칼리 현상성 수지 조성물 및 알칼리 현상성 감광성 수지 조성물에 대해서 바람직한 실시형태에 기초해 상세하게 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, the alkali developable resin composition and alkali developable photosensitive resin composition of this invention are demonstrated in detail based on preferable embodiment.
본 발명의 알칼리 현상성 수지 조성물은 상기 일반식(I)에서 나타내는 에폭시 수지(A)에, 불포화 1염기산(B) 및 페놀 화합물, 알코올 화합물, 아민 화합물 및 카르본산에서 선택되는 화합물(C)을, 상기 에폭시 수지(A)의 에폭시기 1개에 대해, 상기 불포화 1염기산(B)의 카르복실기가 0.1~1.0개가 되는 비율로, 상기 화합물(C)의 페놀성 수산기, 알코올성 수산기, 아미노기 또는 카르복실기가 0~0.9개가 되는 비율이면서, 또한 (B)성분 및 (C)성분의 합이 0.1~1.0개가 되는 비율로 부가시킨 구조는 가지는 에폭시 부가물에 대해, 다염기산무수물(D)을 상기 에폭시 부가물의 수산기 1개 대해 산무수물 구조가 0.1~1.0개가 되는 비율로 에스테르화시켜서 얻어진 반응생성물을 함유한다.The alkali developable resin composition of the present invention is a compound (C) selected from unsaturated monobasic acids (B) and phenolic compounds, alcohol compounds, amine compounds and carboxylic acids in the epoxy resin (A) represented by the general formula (I). The phenolic hydroxyl group, alcoholic hydroxyl group, amino group, or carboxyl group of the compound (C) at a ratio such that the carboxyl group of the unsaturated monobasic acid (B) becomes 0.1 to 1.0 with respect to one epoxy group of the epoxy resin (A). The polybasic acid anhydride (D) is added to the epoxy adduct having the structure added with the ratio of 0 to 0.9, and the sum of the components (B) and (C) added at a ratio of 0.1 to 1.0. It contains the reaction product obtained by esterifying in the ratio which an acid anhydride structure becomes 0.1-1.0 with respect to one hydroxyl group.
상기 에폭시 수지(A)의 에폭시기 1개에 대하여, 상기 불포화 1염기산(B)의 카르복실기의 비율은 바람직하게는 0.4~1.0개이며, 상기 화합물(C)의 페놀성 수산기, 알코올성 수산기, 아미노기 또는 카르복실기의 비율은 바람직하게는 0~0.6개이며, (B)성분 및 (C)성분의 합은 바람직하게는 0.4~1.0개이다. 또한 상기 에폭시 부가물의 수산기 1개에 대해, 다염기산무수물(D)의 산무수물 구조의 비율은 바람직하게는 0.4~1.0개이다.The proportion of the carboxyl groups of the unsaturated monobasic acid (B) is preferably 0.4 to 1.0 with respect to one epoxy group of the epoxy resin (A), and the phenolic hydroxyl group, alcoholic hydroxyl group, amino group or the like of the compound (C) Preferably the ratio of carboxyl groups is 0-0.6 piece, and the sum of (B) component and (C) component becomes like this. Preferably it is 0.4-1.0 piece. Moreover, the ratio of the acid anhydride structure of polybasic acid anhydride (D) with respect to one hydroxyl group of the said epoxy adduct is preferably 0.4-1.0 piece.
상기 일반식(I) 중, Cy로 나타내는 탄소원자수 3~10의 시클로알킬기로서는 시클로프로필, 시클로부틸, 시클로펜틸, 시클로헥실, 메틸시틀로헥실, 시클로헵틸, 시클로옥틸, 시클로노닐, 시클로데실 등을 들 수 있고, Y 및 Z로 나타내는 탄소원 자수 1~10의 알킬기로서는 메틸, 에틸, 프로필, 이소프로필, 부틸, 이소부틸, 제2부틸, 제3부틸, 아밀, 이소아밀, 제3아밀, 헥실, 헵틸, 옥틸, 이소옥틸, 제3옥틸, 2-에틸헥실, 노닐, 이소노닐, 데실, 이소데실, 모노플루오로메틸, 디플루오로메틸, 트리플루오로메틸, 트리플루오로에틸, 퍼플루오로에틸 등을 들 수 있고, 탄소원자수 1~10의 알콕시기로서는 메톡시, 에톡시, 프로필옥시, 부틸옥시, 메톡시에틸, 에톡시에틸, 프로필옥시에틸, 메톡시에톡시에틸, 에톡시에톡시에틸, 프로필옥시에톡시에틸, 메톡시프로필 등을 들 수 있고, 탄소원자수 2~10의 알케닐기로서는 비닐, 알릴, 부테닐, 프로페닐 등을 들 수 있고, 할로겐 원자로서는 불소, 염소, 취소, 요오드소를 들 수 있다In the above general formula (I), examples of the cycloalkyl group having 3 to 10 carbon atoms represented by Cy include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and the like. Examples of the alkyl group having 1 to 10 carbon atoms represented by Y and Z include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, tertiary butyl, amyl, isoamyl, tertiary amyl and hexyl. , Heptyl, octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoro Ethyl etc. are mentioned, As an alkoxy group of 1-10 carbon atoms, methoxy, ethoxy, propyloxy, butyloxy, methoxyethyl, ethoxyethyl, Propyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, methoxypropyl, and the like. Examples of the alkenyl group having 2 to 10 carbon atoms include vinyl, allyl, butenyl, propenyl, and the like. Examples of the halogen atom include fluorine, chlorine, cancellation, and iodine.
본 발명의 알칼리 현상성 수지 조성물의 조제에 사용되는 에폭시 수지(A)는 트리아릴모노시클로알킬메탄 골격을 가짐으로써 경화물의 기재에의 밀착성, 내알칼리성, 가공성, 강도 등이 뛰어나기 때문에 비경화부를 현상 제거할 때에, 미세패턴이라도 선명한 화상을 정밀도 좋게 형성할 수 있는 것으로 생각된다. 에폭시 수지(A)로서는 상기 일반식(I)에 있어서, Cy가 시클로헥실기인 것; X가 페닐기인 것; p 및 r이 0인 것; n이 0~5, 특히 0~1인 것이 바람직하다.Since the epoxy resin (A) used for preparation of the alkali developable resin composition of this invention is excellent in adhesiveness to the base material of hardened | cured material, alkali resistance, workability, strength, etc. by having a triaryl monocycloalkylmethane skeleton, it is a non-hardened part. In removing the development, it is considered that a fine image can be formed with high precision even with a fine pattern. As an epoxy resin (A), Cy is a cyclohexyl group in the said General formula (I); X is a phenyl group; p and r are 0; It is preferable that n is 0-5, especially 0-1.
상기 일반식(I)에서 나타내는 에폭시 수지(A)의 구체예로서는 이하의 화합물 No.1~No.9의 화합물을 들 수 있다. 다만, 본 발명은 이하의 화합물에 의해 하등 제한을 받는 것은 아니다.As a specific example of the epoxy resin (A) shown by the said General formula (I), the compound of the following compounds No. 1-No. 9 is mentioned. However, this invention is not restrict | limited at all by the following compounds.
본 발명의 알칼리 현상성 수지 조성물에 함유되는, (A)성분에 (B)성분 및 필요에 따라서 (C)성분을 부가시킨 후, (D)성분을 에스테르화해 얻어지는 반응생성물은 예를 들면, 하기 [화학식 11]의 반응식에서 나타내는 방법에 의해서 제조할 수 있다.After adding (B) component and (C) component as needed to (A) component contained in the alkali developable resin composition of this invention, the reaction product obtained by esterifying (D) component is the following, for example, It can manufacture by the method shown by the reaction formula of [Formula 11].
우선, (A)성분인 에폭시 수지(1)에, (B)성분인 불포화 1염기산(2) 및 필요에 따라서 (C)성분인 페놀 화합물 등(3)을 부가시켜서, 에폭시 부가물인 화합물(4)을 포함하는 수지 조성물을 얻는다. 이어서 화합물(4)에, (D)성분인 다염기산무수물(5)을 반응시켜서 에스테르화 반응을 행하고, 목적으로 하는 반응생성물인 화합물(6)을 포함하는 수지 조성물을 얻는다. 나아가 임의로, 화합물(6)에, (E)성분인 에폭시 화합물(7)을 반응시켜서, 화합물(8)을 포함하는 수지 조성물을 얻는 것이 가능하다.First, to the epoxy resin (1) which is (A) component, unsaturated monobasic acid (2) which is (B) component, and (3) the phenolic compound etc. which are (C) component as needed, are added, and the compound which is an epoxy adduct ( The resin composition containing 4) is obtained. Subsequently, the compound (4) is made to react with the polybasic acid anhydride (5) which is (D) component, and esterification is performed, and the resin composition containing the compound (6) which is a target reaction product is obtained. Furthermore, it is possible to obtain the resin composition containing compound (8) by making compound (6) react with the epoxy compound (7) which is (E) component arbitrarily.
상기 [화학식 11]에 나타낸 에폭시 부가물인 화합물(4)을 얻는 방법은 상기의 방법에 제한되는 것은 아니고, 예를 들면, 화합물(4)에 있어서의 n이 0의 경우, 하기 [화학식 12]의 반응식에 나타내는 바와 같이 비스페놀(9)과 글리시딜메타크릴레이트(10)를 포함하는 모노에폭시 화합물을 반응시키는 방법에 의해서 화합물(4)을 얻는 것도 가능하다.The method of obtaining the compound (4) which is an epoxy adduct shown in the said [Formula 11] is not restrict | limited to the said method, For example, when n in compound (4) is 0, it is the following [formula 12] As shown in the scheme, it is also possible to obtain compound (4) by a method of reacting a monoepoxy compound containing bisphenol (9) and glycidyl methacrylate (10).
본 발명의 알칼리 현상성 수지 조성물을 얻기 위해서 사용되는 불포화 1염기산(B)으로서는 예를 들면, 아크릴산, 메타크릴산, 크로톤산(crotonic acid), 계피산, 소르빈산, 히드록시에틸메타크릴레이트·말레이트, 히드록시에틸아크릴레이트·말레이트, 히드록시프로필메타아크릴레이트·말레이트, 히드록시프로필아크릴레이트·말레이트, 디시클로펜타디엔·말레이트 등을 들 수 있다.Examples of the unsaturated monobasic acid (B) used for obtaining the alkali developable resin composition of the present invention include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, and hydroxyethyl methacrylate. And hydroxyethyl acrylate maleate, hydroxypropyl methacrylate maleate, hydroxypropyl acrylate maleate, dicyclopentadiene maleate, and the like.
본 발명의 알칼리 현상성 수지 조성물을 얻기 위해서 사용되는 화합물(C)로서 사용할 수 있는 페놀 화합물로서는 예를 들면, 페놀, 클로로페놀, 크레졸, 에틸 페놀, 프로필페놀, 큐밀페놀(cumylphenol), 제3부틸페놀, 제3아밀페놀, 헥실페놀, 옥틸페놀, 이소옥틸페놀, 제3옥틸페놀, 노닐페놀, 도데실페놀, 옥타데실페놀, 2,4-디제3부틸페놀, 2,5-디제3부틸페놀, 3,5-디제3부틸페놀, 2,4,6-트리브로모페놀, 4-(1,1,3,3-테르라메틸부틸)페놀, 2-(3,5-디메틸헵틸)페놀, 4-(3,5-디메틸헵틸)페놀, 테르펜페놀(terpene phenol), 나프톨 등을 들 수 있다.As a phenolic compound which can be used as a compound (C) used in order to obtain the alkali developable resin composition of this invention, for example, phenol, chlorophenol, cresol, ethyl phenol, propyl phenol, cumylphenol, tertiary butyl Phenol, tertiary amyl phenol, hexyl phenol, octyl phenol, isooctyl phenol, tertiary octyl phenol, nonyl phenol, dodecyl phenol, octadecyl phenol, 2,4-dize-3 butylphenol, 2,5-dize-3 butylphenol , 3,5-dije3butylphenol, 2,4,6-tribromophenol, 4- (1,1,3,3-tertamethylbutyl) phenol, 2- (3,5-dimethylheptyl) phenol , 4- (3,5-dimethylheptyl) phenol, terpene phenol, naphthol and the like.
본 발명의 알칼리 현상성 수지 조성물을 얻기 위해서 사용되는 화합물(C)로서 사용할 수 있는 알코올 화합물로서는 메탄올, 에탄올, 프로판올, 부탄올, 펜탄올, 헥산올, 헵탄올, 옥탄올, 이소프로판올, sec-부틸알코올, 2-펜틸알코올, 3-펜틸알코올, 2-헥실알코올, 3-헥실알코올, 2-헵틸알코올, 3-헵틸알코올, 4-헵틸알코올, 2-옥틸알코올, 3-옥틸알코올, 4-옥틸알코올, tert-부틸알코올, 2-메틸부틸-2-올, 2-메틸펜탄-2-올, 2-메틸헥산-2-올, 2-메틸헵탄-2-올 등을 들 수 있다.Alcohol compounds that can be used as the compound (C) used to obtain the alkali developable resin composition of the present invention include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol and sec-butyl alcohol. , 2-pentyl alcohol, 3-pentyl alcohol, 2-hexyl alcohol, 3-hexyl alcohol, 2-heptyl alcohol, 3-heptyl alcohol, 4-heptyl alcohol, 2- octyl alcohol, 3- octyl alcohol, 4- octyl alcohol , tert-butyl alcohol, 2-methylbutyl-2-ol, 2-methylpentan-2-ol, 2-methylhexan-2-ol, 2-methylheptan-2-ol, and the like.
본 발명의 알칼리 현상성 수지 조성물을 얻기 위해서 사용되는 화합물(C)로서 사용할 수 있는 아민 화합물로서는 예를 들면, 메틸아민, 에틸아민, 프로필아민, 부틸아민, 펜틸아민, 헥실아민, 헵틸아민, 옥틸아민, 디메틸아민, 디에틸아민, 디프로필아민, 디부틸아민, 디펜틸아민, 디헥실아민, 디헵틸아민, 디옥틸아민, 모르폴린, 피페리딘 등을 들 수 있다.Examples of the amine compound that can be used as the compound (C) used to obtain the alkali developable resin composition of the present invention include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, and octyl. Amine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, morpholine, piperidine and the like.
본 발명의 알칼리 현상성 수지 조성물을 얻기 위해서 사용되는 화합물(C)로서 사용할 수 있는 카르본산으로서는 예를 들면, 초산, 프로피온산, 2,2-디메틸올프로피온산, 젖산, 낙산(酪酸), 옥틸산, 라우린산, 리놀산, 리시놀산, 안식향산, 톨루익산(toluic acid), 계피산, 페닐초산, 시클로카르본산 등의 지방족, 방향족 또는 지환식 모노카르본산을 들 수 있다.Examples of the carboxylic acid that can be used as the compound (C) used to obtain the alkali developable resin composition of the present invention include acetic acid, propionic acid, 2,2-dimethylolpropionic acid, lactic acid, butyric acid, octylic acid, Aliphatic, aromatic or alicyclic monocarboxylic acids such as lauric acid, linoleic acid, ricinolic acid, benzoic acid, toluic acid, cinnamon acid, phenylacetic acid and cyclocarboxylic acid.
본 발명의 알칼리 현상성 수지 조성물을 얻기 위해서 사용되는 다염기산무수물(D)로서는 숙신산무수물, 말레인산무수물, 트리멜리트산무수물, 피로멜리트산 무수물, 2,2'-3,3'-벤조페논테트라카르본산무수물, 3,3'-4,4'-벤조페논테트라카르본산무수물, 에틸렌글리콜비스안히드로트리멜리테이트, 글리세롤트리스안히드로트리멜리테이트, 무수프탈산, 메틸테트라히드로무수프탈산, 테트라히드로무수프탈산, 나딘산무수물(methyl nadic anhydride), 메틸나딘산무수물(methyl nadic anhydride), 트리알킬테트라히드로무수프탈산, 헥사히드로무수프탈산, 5-(2,5-디옥소테트라히드로푸릴)-3-메틸-3-시클로헥센-1,2-디카르본산무수물, 트리알킬테트라히드로무수프탈산-무수말레인산 부가물, 도데세닐무수숙신산, 무수메틸하이믹산 등의 1무수물, 3,3',4,4'-비페닐테트라카르본산 2무수물, 3,3'4,4'-디페닐테트라설폰산 2무수물, 4,4'-옥시디프탈산 2무수물, 2,3,5-트리카르복시시클로펜틸초산 2무수물, 1,2,3,4-시클로펜탄테트라카르본산 2무수물, 메틸헥사히드로무수프탈산 등의 2무수물을 들 수 있고, 이들 중에서도 2산무수물, 또는 2산무수물과 1산무수물과의 조합이 바람직하다. Examples of the polybasic acid anhydride (D) used to obtain the alkali developable resin composition of the present invention include succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, and 2,2'-3,3'-benzophenonetetracarboxylic acid. Anhydride, 3,3'-4,4'- benzophenone tetracarboxylic anhydride, ethylene glycol bis anhydro trimellitate, glycerol tris anhydro trimellitate, phthalic anhydride, methyl tetrahydrophthalic anhydride, tetrahydro phthalic anhydride, Methyl nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3 1-anhydrides such as cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride, dodecenyl anhydrous succinic acid, and methylhydric anhydride, 3,3 ', 4,4'-ratio Phenyltetracarboxylic acid 2 Water, 3,3'4,4'-diphenyltetrasulfonic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetate dianhydride, 1,2,3, Dihydric anhydrides, such as 4-cyclopentane tetracarboxylic dianhydride and methylhexahydrophthalic anhydride, are mentioned, Among these, a combination of a diacid anhydride or a diacid anhydride and a monoacid anhydride is preferable.
본 발명에 있어서, 상기 에폭시 화합물(E)은 산가 조정을 위해서 사용되는 것으로, 본 발명의 알칼리 현상성 수지 조성물의 현상성을 개량하기 위해서 사용할 수 있다. 에폭시 화합물로서는 글리시딜메타크릴레이트, 메틸글리시딜에테르, 에틸글리시딜에테르, 프로필글리시딜에테르, 이소프로필글리시딜에테르, 부틸글리시딜에테르, 이소부틸글리시딜에테르, t-부틸글리시딜에테르, 펜틸글리시딜에테르, 헥 실글리시딜에테르, 헵틸글리시딜에테르, 옥틸글리시딜에테르, 노닐글리시딜에테르, 데실글리시딜에테르, 운데실글리시딜에테르, 도데실글리시딜에테르, 트리데실글리시딜에테르, 테트라데실글리시딜에테르, 펜타데실글리시딜에테르, 헥사데실글리시딜에테르, 2-에틸헥실글리시딜에테르, 알릴글리시딜에테르, 프로파르길(propargyl)글리시딜에테르, p-메톡시에틸글리시딜에테르, 페닐글리시딜에테르, p-메톡시글리시딜에테르, p-부틸페놀글리시딜에테르, 크레질글리시딜에테르, 2-메틸크레질글리시딜에테르, 4-노닐페닐글리시딜에테르, 벤질글리시딜, p-큐밀페닐글리시딜에테르, 트리틸글리시딜에테르, 2,3-에폭시프로필메타클릴레이트, 에폭시화 대두유, 에폭시화 아마인유(linseed oil), 글리시딜부틸레이트, 비닐시클로헥산모노옥시드, 1,2-에폭시-4-비닐시클로헥산, 스티렌옥시드, 피넨옥시드(pinene oxide), 메틸스티렌옥시드, 시클로헥센옥시드, 프로필렌옥시드, 하기 화합물 No.10, No.11 등을 들 수 있다.In this invention, the said epoxy compound (E) is used for acid value adjustment, It can be used in order to improve the developability of the alkali developable resin composition of this invention. As an epoxy compound, glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t- Butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, Dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, Propargyl glycidyl ether, p-methoxyethylglycidyl ether, phenylglycidyl ether, p-methoxyglycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl Ether, 2-methylcrezyl glycidyl ether, 4- Nylphenylglycidyl ether, benzylglycidyl, p-cumylphenylglycidyl ether, tritylglycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil ), Glycidyl butyrate, vinyl cyclohexane monooxide, 1,2-epoxy-4-vinylcyclohexane, styrene oxide, pinene oxide, methyl styrene oxide, cyclohexene oxide, propylene Oxide, following compound No. 10, No. 11, etc. are mentioned.
본 발명의 알칼리 현상성 수지 조성물은 고형분의 산가(酸價)가 60~120mgKOH/g의 범위인 것이 바람직하고, 에폭시 화합물(E) 사용량은 상기 산가를 만족시키게끔 선택하는 것이 바람직하다.It is preferable that the acid value of solid content of the alkali developable resin composition of this invention is the range of 60-120 mgKOH / g, and it is preferable to select the usage-amount of an epoxy compound (E) so that the said acid value may be satisfied.
본 발명의 알칼리 현상성 조성물은 나아가 광중합 개시제를 첨가해 알칼리 현상성 감광성 수지 조성물로 하는 것이 가능하다.The alkali developable composition of this invention can further be made into the alkali developable photosensitive resin composition by adding a photoinitiator.
본 발명의 알칼리 현상성 수지 조성물 및 알칼리 현상성 감광성 수지 조성물은 통상 필요에 따라서 상기 각 성분을 용해 또는 분해할 수 있는 용매, 예를 들면, 아세톤, 메틸에틸케톤, 메틸이소부틸케톤, 시클로헥사논, 메틸셀로솔브, 에틸셀로솔브, 프로필렌글리콜모노메틸에테르아세테이트, 클로로포름(chloroform), 염화메틸렌, 헥산, 헵탄, 옥탄, 시클로헥산, 벤젠, 톨루엔, 크실렌, 메탄올, 에탄올, 이소프로판올을 첨가한 용액상(溶液狀) 조성물로서 사용된다. 이 용액상 조성물 중, 용매의 함유량은 30~90중량%, 특히 40~70중량%가 바람직하다.The alkali developable resin composition and the alkali developable photosensitive resin composition of the present invention are usually solvents capable of dissolving or decomposing the above components, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. , Methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether acetate, chloroform, chloroform, methylene chloride, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol It is used as a phase composition. In this solution composition, the content of the solvent is preferably 30 to 90% by weight, particularly 40 to 70% by weight.
(A)성분에 (B)성분 및 필요에 따라서 (C)성분을 부가시킨 후 (D)성분을 에스테르화하고, 나아가 필요에 따라서 (E)성분을 반응시켜서 얻어진 반응생성물의 함유량은 상기 용액상 조성물 중, 1~70중량%, 특히 3~30중량%가 바람직하다.The content of the reaction product obtained by adding (B) component and (C) component as needed to (A) component, then esterifying (D) component, and reacting (E) component as needed, said content of the said solution phase 1 to 70 weight%, especially 3 to 30 weight% are preferable in a composition.
본 발명의 알칼리 현상성 감광성 수지 조성물에 사용하는 상기 광중합 개시제로서는 종래 주지의 화합물을 사용하는 것이 가능하며, 예를 들면, 벤조페논, 페닐비페닐케톤, 1-히드록시-1-벤조일시클로헥산, 벤질, 벤질디메틸케탈(benzyl-di-methylketal), 1-벤질-1-디메틸아미노-1-(4'-모르폴린벤조일)프로판, 2-모르폴릴-2-(4'-메틸메르캅토)벤조일프로판, 티옥산톤, 1-클로르-4-프로폭시티옥산톤, 이소 프로필티옥산톤, 디에틸티옥산톤, 에틸안트라퀴논, 4-벤조일-4'-메틸디페닐설피드, 벤조인부틸에테르, 2-히드록시-2-벤조일프로판, 2-히드록시-2-(4'-이소프로필)벤조일프로판, 4-부틸벤조일트리클로로메탄, 4-페녹시벤조일디클로로메탄, 벤조일개미산메틸, 1,7-비스(9'-아크리디닐(acridinyl))헵탄, 9-n-부틸-3,6-비스(2'-모르폴리노이소부틸로일)카르바졸, 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노프로판-1-온, 2-메틸-4,6-비스(트리클로로메틸)-s-트리아진, 2-페닐-4,6-비스(트리클로로메틸)-s-트리아진, 2-나프틸-4,6-비스(트리클로로메틸)-s-트리아진, 하기 화합물 No.12, No.13 등을 들 수 있다.As said photoinitiator used for the alkali developable photosensitive resin composition of this invention, it is possible to use a conventionally well-known compound, For example, benzophenone, phenyl biphenyl ketone, 1-hydroxy-1- benzoyl cyclohexane, Benzyl, benzyl-di-methylketal, 1-benzyl-1-dimethylamino-1- (4'-morpholinbenzoyl) propane, 2-morpholinyl-2- (4'-methylmercapto) benzoyl Propane, thioxanthone, 1-chloro-4-propoxycyxanthone, isopropyl thioxanthone, diethyl thioxanthone, ethyl anthraquinone, 4-benzoyl-4'-methyldiphenylsulfide, benzoinbutyl Ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4'-isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, benzoyl formate, 1 , 7-bis (9'-acridinyl) heptane, 9-n-butyl-3,6-bis (2'-morpholinoisobutyloyl) carbazole, 2-methyl-1- [ 4- (methyl tea ) Phenyl] -2-morpholinopropane-1-one, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl)- s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine, the following compound No.12, No.13, etc. are mentioned.
(식 중, X1는 할로겐원자 또는 알킬기를 나타내고, R1는 R OR, COR, SR, CONRR', 또는 CN를 나타내고, R2는 R OR, COR, SR 또는 NRR'을 나타내고, r은 R, OR, COR, SR 또는 NRR'을 나타내고, R 및 R'은 알킬기, 아릴기, 아랄킬기 또는 복소환기를 나타내고, 이들은 할로겐원자 및/또는 복소환기로 치환되어 있어도 좋고, 이들 중 알킬기 및 아랄킬기의 알킬렌 부분은 불포화 결합, 에테르 결합, 티오에테르 결합 및 에스테르 결합에서 선택되는 1종 이상에 의해 중단되어 있어도 좋고, 또한 R 및 R'은 함께 고리를 형성하고 있어도 좋고, n은 0~5이다.)Wherein X 1 represents a halogen atom or an alkyl group, R 1 represents R OR, COR, SR, CONRR ', or CN, R 2 represents R OR, COR, SR or NRR', and r represents R , OR, COR, SR or NRR ', and R and R' represent an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, which may be substituted with a halogen atom and / or a heterocyclic group, of which an alkyl group and an aralkyl group The alkylene moiety of may be interrupted by one or more selected from unsaturated bonds, ether bonds, thioether bonds and ester bonds, and R and R 'may together form a ring, and n is 0 to 5 .)
(식 중, X1, R1, R2, R3, R 및 R'은 상기 화합물 No.12와 동일하며, X1'은 할로겐 또는 알킬기를 나타내고, Z는 산소원자 또는 유황원자를 나타내고, m 및 n은 각각 1~4의 수를 나타내고, R1', R, OR, COR, SR, CONRR' 또는 CN을 나타내고, R2'은 R, OR, COR, SR 또는 NRR'을 나타내고, R3'은 각각 R, OR, COR, SR 또는 NRR'을 나타내고, R4는 디올 잔기 또는 디티올 잔기를 나타낸다.)(Wherein X 1 , R 1 , R 2 , R 3 , R and R ′ are the same as in compound No. 12, X 1 ′ represents a halogen or an alkyl group, Z represents an oxygen atom or a sulfur atom, m and n each represent a number from 1 to 4, R 1 ′, R, OR, COR, SR, CONRR 'or CN, R 2 ′ represents R, OR, COR, SR or NRR', and R 3 'represents R, OR, COR, SR or NRR', respectively, and R 4 represents a diol residue or dithiol residue.)
본 발명의 알칼리 현상성 감광성 수지 조성물에 있어서, 상기 광중합 개시제의 함유량은 본 발명의 알칼리 현상성 수지 조성물에 용매를 첨가한 상기 용액상 조성물에 대해서, 0~30중량%, 특히 0.5~5중량%가 바람직하다.In the alkali developable photosensitive resin composition of the present invention, the content of the photopolymerization initiator is from 0 to 30% by weight, in particular from 0.5 to 5% by weight, based on the solution composition wherein a solvent is added to the alkali developable resin composition of the present invention. Is preferred.
본 발명의 알칼리 현상성 수지 조성물 및 알칼리 현상성 감광성 수지 조성물에는 더욱 불포화 결합을 가지는 모노머, 연쇄이동제, 계면활성제 등을 병용할 수 있다.The alkali developable resin composition and alkali developable photosensitive resin composition of this invention can use together the monomer which has an unsaturated bond, a chain transfer agent, surfactant, etc. together.
상기 불포화 결합을 가지는 모노머로서는 아크릴산-2-히드록시에틸, 아크릴산-2-히드록시프로필, 아크릴산이소부틸, 아크릴산 N-옥틸, 아크릴산이소옥틸, 아크릴산이소노닐, 아크릴산스테알릴, 아크릴산메톡시에틸, 아크릴산디메틸아미노에 틸, 아크릴산아연, 1,6-헥산디올디아크릴레이트, 트리메틸올프로판트리아크릴레이트, 메타크릴산-2-히드록시에틸, 메타크릴산-2-히드록시프로필, 메타크릴산부틸, 메타크릴산터셔리부틸, 메타크릴산시클로헥실, 트리메틸올프로판트리메타크릴레이트, 디펜타에스리톨펜타아크릴레이트, 디펜타에리스리톨헥사아크릴레이트, 펜타에리스리톨테트라아크릴레이트, 펜타에리스리톨트리아크릴레이트 등을 들 수 있다.As a monomer which has the said unsaturated bond, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, N-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, methoxyethyl acrylate, Dimethylamino ethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropanetriacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate Butyl methacrylate, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and the like. Can be.
상기 연쇄이동제로서는 티오글리콜산, 티오사과산, 티오살리실산, 2-메르캅토프로피온산, 3-메르캅토프로피온산, 3-메르캅토낙산, N-(2-메르캅토프로피오닐)글리신, 2-메르캅토니코틴산, 3-[N-(2-메르캅토에틸)카르바모일]프로피온산, 3-[N-(2-메르캅토에틸)아미노]프로피온산, N-(3-메르캅토프로피오닐)알라닌, 2-메르캅토에탄설폰산, 3-메르캅토프로판설폰산, 4-메르캅토부탄설폰산, 도데실(4-메틸티오)페닐에테르, 2-메르캅토에탄올, 3-메르캅토-1,2-프로판디올, 1-메르캅토-2-프로판올, 3-메르캅토-2-부탄올, 메르캅토페놀, 2-메르캅토에틸아민, 2-메르캅토이미다졸, 2-메르캅토-3-피리디놀, 2-메르캅토벤조티아졸, 메르캅토초산, 트리메틸올프로판트리스(3-메르캅토프로피오네이트), 펜타에리스리톨테트라키스(3-메르캅토프로피오네이트) 등의 메르캅토 화합물, 이 메르캅토 화합물을 산화해 얻어지는 디설피드 화합물, 요오드초산, 요오드프로피온산, 2-요오드에탄올, 2-요오도에탄설폰산, 3-요오드프로판설폰산 등의 요오드화 알킬 화합물 등을 들 수 있다.Examples of the chain transfer agent include thioglycolic acid, thio apple acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptonaric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercapto Ethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenylether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1 Mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, 2-mercapto Mercapto compounds such as benzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and And iodide alkyl compounds such as disulfide compounds obtained by oxidizing the mercapto compound, iodine acetic acid, iodine propionic acid, 2-iodineethanol, 2-iodoethanesulfonic acid, and 3-iodine propanesulfonic acid.
상기 계면활성제로서는 퍼플루오로알킬인산에스테르, 퍼플루오로알킬카르본산염 등의 불소 계면활성제, 고급지방산 알칼리염, 알킬설폰산염, 알킬황산염 등의 음이온계 계면활성제, 고급 아민할로겐산염, 제4급 암모늄염 등의 양이온계 계면활 성제, 폴리에틸렌글리콜알킬에테르, 폴리에틸렌글리콜지방산에스테르, 소르비탄지방산에스테르, 지방산모노글리세리드 등의 비이온계면활성제, 양성계면활성제, 실리콘계 계면활성제 등의 계면활성제를 사용하는 것이 가능하며, 이들은 조합시켜 사용해도 좋다.Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphate esters and perfluoroalkyl carbonates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, higher amine halogenates, and quaternary Nonionic surfactants such as cationic surfactants such as ammonium salts, polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, and surfactants such as amphoteric surfactants and silicone surfactants can be used. These may be used in combination.
본 발명의 알칼리 현상성 수지 조성물 및 알칼리 현상성 감광성 수지 조성물에는 또 열가소성 유기중합체를 사용함으로써 경화물의 특성을 개선할 수 있다. 상기 열가소성 유기 중합체로서는 예를 들면, 폴리스티렌, 폴리메틸메타크릴레이트, 메틸메타크릴레이트-에틸아크릴레이트 공중합체, 폴리(메타)아크릴산, 스티렌-(메타)아크릴산 공중합체, (메타)아크릴산-메틸메타크릴레이트 공중합체, 폴리비닐부틸랄, 셀룰로오스에스테르, 폴리아크릴아미드, 포화 폴리에스테르 등을 들 수 있다.The characteristics of hardened | cured material can be improved by using a thermoplastic organic polymer for the alkali developable resin composition and alkali developable photosensitive resin composition of this invention. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, and (meth) acrylic acid-methylmetha. Acrylate copolymers, polyvinyl butyral, cellulose esters, polyacrylamides, saturated polyesters and the like.
또한 본 발명의 알칼리 현상성 수지 조성물 및 알칼리 현상성 감광성 수지 조성물에는 필요에 따라서 아니솔(anisole), 하이드로퀴논(hydroquinone), 필로카테콜(pyrocatechol), 제3부틸카테콜, 페노티아진(phenothiazine) 등의 열중합 억제제; 가소제; 접착촉진제; 충전제; 소포제; 레벨링제 등의 관용의 첨가물을 첨가할 수 있다.In addition, the alkali developable resin composition and the alkali developable photosensitive resin composition of the present invention may be anisole, hydroquinone, pyrocatechol, tert-butylcatechol, phenothiazine, and the like, as necessary. Thermal polymerization inhibitors, such as); Plasticizers; Adhesion promoters; Fillers; Antifoam; General additives, such as a leveling agent, can be added.
본 발명의 알칼리 현상성 감광성 수지 조성물은 롤코터, 커텐코터, 각종의 인쇄, 침지 등의 공지의 수단으로 금속, 종이, 플라스틱 등의 지지기체 상에 적용할 수 있다. 또한 일단 필름 등의 지지기체 상에 시행한 후, 다른 지지기체 상에 전사하는 것도 가능하고, 그 적용방법에 제한은 없다.The alkali developable photosensitive resin composition of the present invention can be applied to supporting substrates such as metal, paper, and plastic by known means such as a roll coater, a curtain coater, various printing, and immersion. In addition, it is also possible to transfer onto another support gas once it has been carried out on a support gas such as a film, and the application method is not limited.
본 발명의 알칼리 현상성 감광성 수지 조성물은 광경화성 도료, 광경화성 접착제, 인쇄판, 인쇄 배선판용 포토레지스트 등의 각종의 용도로 사용할 수 있고, 그 용도에 특히 제한은 없다.The alkali developable photosensitive resin composition of this invention can be used for various uses, such as a photocurable coating material, a photocurable adhesive agent, a printing board, and photoresist for a printed wiring board, There is no restriction | limiting in particular in the use.
또한 본 발명의 알칼리 현상성 감광성 수지 조성물을 경화시킬 때에 사용되는 활성광의 광원으로서는 파장 300~450nm의 광(光)을 발광하는 것을 사용할 수 있으며, 예를 들어, 초고압수은, 수은증기 아크, 카본 아크(carbon arc), 크세논 아크(xenon arc) 등을 사용할 수 있다.Moreover, as a light source of the active light used when hardening the alkali developable photosensitive resin composition of this invention, what emits light of wavelength 300-450 nm can be used, For example, ultra-high pressure mercury, a mercury vapor arc, a carbon arc carbon arc, xenon arc, or the like.
<실시예><Example>
이하, 실시예 등을 들어서 본 발명을 더욱 상세하게 설명하는데, 본 발명은 이들의 실시예에 제한되는 것은 아니다.Hereinafter, although an Example etc. are given and this invention is demonstrated in more detail, this invention is not restrict | limited to these Examples.
[실시예 1] 알칼리 현상성 수지 조성물 No.1의 제조Example 1 Preparation of Alkaline Developable Resin Composition No. 1
<스텝 1> 1,1-비스(4'-히드록시페닐)-1-(1''-비페닐)-1-시클로헥실메탄의 제조<Step 1> Preparation of 1,1-bis (4'-hydroxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexylmethane
비페닐시클로헥실케톤 70.5g, 페놀 200.7g 및 티오초산 10.15g을 넣고, 트리플루오로메탄설폰산 40.0g을 18도에서 20분에 걸쳐 적하하였다. 17~19도에서 18시간 반응 후, 물 500g을 첨가해 반응을 정지시키고, 톨루엔 500g을 첨가하고, 유기층을 pH3~4가 될 때까지 물로 씻어 유기층을 분리하였다. 톨루엔, 물 및 과잉의 페놀을 제거하였다. 잔여물(residue)에 톨루엔을 첨가해 석출한 고체를 여과 분리하고, 톨루엔으로 분산 세정해 염황색 결정 59.2g(수율 51%)을 얻었다. 상기 염황색 결정의 융점은 239.5도이며, 상기 염황색 결정은 목적물임을 확인하였다.70.5 g of biphenylcyclohexyl ketone, 200.7 g of phenol and 10.15 g of thioacetic acid were added thereto, and 40.0 g of trifluoromethanesulfonic acid was added dropwise at 18 degrees over 20 minutes. After 18 hours of reaction at 17-19 ° C, 500 g of water was added to stop the reaction, 500 g of toluene was added, and the organic layer was washed with water until the pH was 3 to 4 to separate the organic layer. Toluene, water and excess phenol were removed. Toluene was added to the residue, and the precipitated solid was separated by filtration and dispersed and washed with toluene to obtain 59.2 g (yield 51%) of yellow-yellow crystals. It was confirmed that the melting yellow crystal had a melting point of 239.5 degrees, and the yellow crystal was a target product.
<스텝 2> 1,1-비스(4'-에폭시프로필옥시페닐)-1-(1''-비페닐)-1-시클로헥실메탄의 제조<Step 2> Preparation of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexylmethane
스텝 1에서 얻어진 1,1-비스(4'-히드록시페닐)-1-(1''-비페닐)-1-시클로헥실메탄 57.5g 및 에피클로로히드린(epichlorohydrin) 195.8g을 넣고, 벤질트리에틸암모늄클로리드 0.602g을 첨가해 64도에서 18시간 교반하였다. 계속해서 54도까지 승온하고, 24중량% 수산화나트륨 수용액 43.0g을 적하해 30분 교반하였다. 에피클로로히드린 및 물을 제거하고, 메틸이소부틸케톤 216g을 첨가해서 물로 씻은 후, 24중량% 수산화나트륨 2.2g을 적하하였다. 80도에서 2시간 교반 후, 실온까지 냉각하고, 3중량% 모노인산나트륨 수용액으로 중화해 물로 씻어냈다. 용매를 제거해 황색고체를 57g(수율 79%)을 얻었다. (융점 64.2도, 에폭시 당량 282, n=0.04). 상기 황색결정은 목적물임을 확인하였다.57.5 g of 1,1-bis (4'-hydroxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexylmethane and 195.8 g of epichlorohydrin obtained in Step 1 were added thereto, and benzyl 0.602 g of triethylammonium chloride was added and the mixture was stirred at 64 degrees for 18 hours. Then, it heated up to 54 degreeC, 43.0 g of 24weight% sodium hydroxide aqueous solution was dripped, and it stirred for 30 minutes. Epichlorohydrin and water were removed, 216 g of methyl isobutyl ketone was added, the mixture was washed with water, and then 2.2 g of 24% by weight sodium hydroxide was added dropwise. After stirring at 80 ° C for 2 hours, the mixture was cooled to room temperature, neutralized with 3% by weight aqueous sodium monophosphate solution, and washed with water. The solvent was removed to obtain 57 g (yield 79%) of a yellow solid. (Melting point 64.2 degrees, epoxy equivalent 282, n = 0.04). It was confirmed that the yellow crystal was the target product.
<스텝 3> 알칼리 현상성 수지 조성물 No.1의 제조<Step 3> Production of alkali developable resin composition No. 1
스텝 2에서 얻어진 1,1-비스(4'-에폭시프로필옥시페닐)-1-(1''-비페닐)-1-시클로헥실메탄(이하, 화합물(a)이라고도 함) 43g, 아크릴산(이하, 화합물(b)이라고도 함) 11g, 2,6-디-tert-부틸-p-크레졸 0.05g, 테트라부틸암모늄아세테이트 0.11g 및 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 23g을 넣고, 120도에서 16시간 교반하였다. 실온까지 냉각하고, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 35g 및 비페닐테트라카르본산 2무수물(이하, 화합물(d-1)이라고도 함) 9.4g을 첨가해 120도에서 8시간 교반하였다. 나아가 테트라히드로무수프탈산(이하, 화합물(d-1)이라고도 함) 6.0g을 첨가해 120도에서 4시간, 100도에서 3시간, 80도에서 4시 간, 60도에서 6시간, 40도에서 11시간 교반 후, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 29g을 첨가해 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 용액으로 해서 목적물인 알칼리 현상성 수지 조성물 No.1을 얻었다(Mw=4000, Mn=2100, 산가(고형분) 85mgKOH/g).43 g of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexylmethane (hereinafter also referred to as compound (a)) obtained in step 2, acrylic acid (hereinafter 11 g, 2,6-di-tert-butyl-p-cresol, 0.11 g of tetrabutylammonium acetate, and 23 g of propylene glycol-1-monomethyl ether-2-acetate were added thereto. It stirred for 16 hours. After cooling to room temperature, 35 g of propylene glycol-1-monomethyl ether-2-acetate and 9.4 g of biphenyltetracarboxylic dianhydride (hereinafter also referred to as compound (d-1)) were added, followed by stirring at 120 ° C for 8 hours. . Furthermore, 6.0 g of tetrahydrophthalic anhydride (hereinafter also referred to as compound (d-1)) was added to the mixture at 120 degrees for 4 hours, 100 degrees for 3 hours, 80 degrees for 4 hours, 60 degrees for 6 hours, and 40 degrees. After stirring for 11 hours, 29 g of propylene glycol-1-monomethyl ether-2-acetate was added to give a propylene glycol-1-monomethyl ether-2-acetate solution to obtain an alkali developable resin composition No. 1 as a target product (Mw = 4000, Mn = 2100, acid value (solid content) 85 mgKOH / g).
아울러 알칼리 현상성 수지 조성물 No.1을 함유하는 반응생성물은 (A)성분인 화합물(a)에 (B)성분인 화합물(b)을 부가시킨 구조를 가지는 에폭시 부가물의 수산기 1개에 대해, (D)성분인 화합물(d-1) 및 화합물(d-2)의 산무수물 구조가 0.68개의 비율로 에폭시 부가물과 화합물(d-1) 및 화합물(d-2)을 에스테르화 반응시켜서 얻어진 것이다. 또한 상기 에폭시 부가물은 화합물(a)의 에폭시기 1개에 대해, 화합물(b)의 카르복실기가 1.0개의 비율로 부가시킨 구조를 가지는 것이다.In addition, the reaction product containing alkali-developable resin composition No. 1 has one hydroxyl group of the epoxy adduct which has a structure which added compound (b) which is (B) component to compound (a) which is (A) component, ( The acid anhydride structure of the compound (d-1) and the compound (d-2) which are D) component is obtained by esterifying an epoxy adduct, a compound (d-1), and a compound (d-2) by 0.68 ratio. . In addition, the said epoxy adduct has a structure which the carboxyl group of compound (b) added in 1.0 ratio with respect to one epoxy group of compound (a).
[실시예 2] 알칼리 현상성 수지 조성물 No.2의 제조Example 2 Preparation of Alkaline Developable Resin Composition No. 2
1,1-비스(4'-에폭시프로필옥시페닐)-1-(1''-비페닐)-1-시클로헥실메탄(화합물(a)) 43g, 아크릴산(화합물(b)) 11g, 2,6-디-tert-부틸-p-크레졸 0.05g, 테트라부틸암모늄아세테이트 0.11g 및 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 23g을 넣고, 120도에서 16시간 교반하였다. 실온까지 냉각하고, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 35g 및 비페닐테트라카르본산 2무수물(화합물(d-1)) 16g을 첨가하고 120도에서 8시간 교반하였다. 나아가 테트라히드로무수프탈산(화합물(d-2)) 0.7g을 첨가해 120도에서 4시간, 100도에서 3시간, 80도에서 4시간, 60도에서 6시간, 40도에서 11시간 교반 후, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 29g을 첨가하고, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 용액으로 해 서 목적물인 알칼리 현상성 수지 조성물 No.2를 얻었다(Mw=8100, Mn=2900, 산가(고형분) 89mgKOH/g).43 g of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexylmethane (compound (a)), 11 g of acrylic acid (compound (b)), 2, 0.05 g of 6-di-tert-butyl-p-cresol, 0.11 g of tetrabutylammonium acetate, and 23 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 120 ° C. for 16 hours. After cooling to room temperature, 35 g of propylene glycol-1-monomethyl ether-2-acetate and 16 g of biphenyltetracarboxylic dianhydride (compound (d-1)) were added, and the mixture was stirred at 120 degrees for 8 hours. Furthermore, after adding 0.7 g of tetrahydrophthalic anhydride (compound (d-2)) and stirring for 4 hours at 120 degrees, 3 hours at 100 degrees, 4 hours at 80 degrees, 6 hours at 60 degrees, and 11 hours at 40 degrees, 29 g of propylene glycol-1-monomethyl ether-2-acetate was added to give a solution of propylene glycol-1-monomethyl ether-2-acetate to obtain alkali developable resin composition No. 2 as a target product (Mw = 8100, Mn = 2900, acid value (solid content) 89 mg KOH / g).
아울러 알칼리 현상성 수지 조성물 No.2가 함유하는 반응생성물은 (A)성분인 화합물(a)에 (B)성분인 화합물(b)을 부가시킨 구조를 가지는 에폭시 부가물의 수산기 1개에 대해, (D)성분인 화합물(d-1) 및 화합물(d-2)의 산무수물 구조가 0.74개의 비율로 에폭시 부가물과 화합물(d-1) 및 화합물(d-2)을 에스테르화 반응시켜서 얻어지는 것이다. 또한 상기 에폭시 부가물은 화합물(a)의 에폭시기 1개에 대해, 화합물(b)의 카르복실기가 1.0개의 비율로 부가시킨 구조를 가지는 것이다.In addition, the reaction product contained in alkali-developable resin composition No. 2 is one hydroxyl group of the epoxy adduct which has a structure which added compound (b) which is (B) component to compound (a) which is (A) component, ( The acid anhydride structures of the compound (d-1) and the compound (d-2) as the component D) are obtained by esterifying an epoxy adduct with the compound (d-1) and the compound (d-2) at a ratio of 0.74. . In addition, the said epoxy adduct has a structure which the carboxyl group of compound (b) added in 1.0 ratio with respect to one epoxy group of compound (a).
[실시예 3] 알칼리 현상성 수지 조성물 No.3의 제조Example 3 Preparation of Alkaline Developable Resin Composition No. 3
1,1-비스(4'-에폭시프로필옥시페닐)-1-(1''-비페닐)-1-시클로헥실메탄(화합물(a)) 43g, 아크릴산(화합물(b)) 11g, 2,6-디-tert-부틸-p-크레졸 0.05g, 테트라부틸암모늄아세테이트 0.11g 및 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 23g을 넣고, 120에서 16시간 교반하였다. 실온까지 냉각하고, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 35g, 비페닐테트라카르본산 2무수물(화합물(d-1)) 16g 및 테트라-n-부틸암모늄브로미드 39mg을 첨가해 120도에서 4시간, 100도에서 3시간, 80도에서 4시간, 60도에서 6시간, 40도에서 11시간 교반 후, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 29g을 첨가하고, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 용액으로 해서 목적물인 알칼리 현상성 수지 조성물 No.3을 얻었다(Mw=8600, Mn=3000, 산가(고형분) 87mgKOH/g).43 g of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexylmethane (compound (a)), 11 g of acrylic acid (compound (b)), 2, 0.05 g of 6-di-tert-butyl-p-cresol, 0.11 g of tetrabutylammonium acetate, and 23 g of propylene glycol-1-monomethyl ether-2-acetate were added thereto, followed by stirring at 120 for 16 hours. Cool to room temperature, add 35 g of propylene glycol-1-monomethyl ether-2-acetate, 16 g of biphenyltetracarboxylic dianhydride (compound (d-1)), and 39 mg of tetra-n-butylammonium bromide, and add 120 degrees. After stirring for 4 hours at 100 degrees, 3 hours at 100 degrees, 4 hours at 80 degrees, 6 hours at 60 degrees, and 11 hours at 40 degrees, 29 g of propylene glycol-1-monomethyl ether-2-acetate was added, and propylene glycol As a 1-monomethyl ether-2-acetate solution, the alkali developing resin composition No. 3 which is a target object was obtained (Mw = 8600, Mn = 3000, acid value (solid content) 87 mgKOH / g).
아울러 알칼리 현상성 수지 조성물 No.3이 함유하는 반응생성물은 (A)성분인 화합물(a)에 (B)성분인 화합물(d-1)의 산무수물 구조가 0.71개의 비율로 에폭시 부가물과 화합물(d-1)을 에스테르화 반응시켜서 얻어진 것이다. 또한 상기 에폭시 부가물은 화합물(a)의 에폭시기 1개에 대해, 화합물(b)의 카르복실기가 1.0개의 비율로 부가시킨 구조를 가지는 것이다.In addition, the reaction product which alkali-developable resin composition No. 3 contains is an epoxy adduct and a compound in 0.71 ratio of the acid anhydride structure of the compound (a) which is (A) component, and the compound (d-1) which is (B) component It is obtained by esterifying (d-1). In addition, the said epoxy adduct has a structure which the carboxyl group of compound (b) added in 1.0 ratio with respect to one epoxy group of compound (a).
[실시예 4] 알칼리 현상성 수지 조성물 No.4의 제조Example 4 Preparation of Alkaline Developable Resin Composition No. 4
1,1-비스(4'-에폭시프로필옥시페닐)-1-(1''-비페닐)-1-시클로헥실메탄(화합물(a)) 43g, 아크릴산(화합물(b)) 11g, 2.6-디-tert-부틸-p-크레졸 0.05g, 테트라부틸암모늄아세테이트 0.11g 및 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 23g을 넣고, 120에서 16시간 교반하였다. 실온까지 냉각하고, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 35g, 비페닐테트라카르본산 2무수물(화합물(d-1)) 10g을 첨가해 120도에서 8시간 교반하였다. 나아가 테트라히드로무수프탈산(화합물(d-2)) 6g을 첨가해 120도에서 4시간, 100도에서 3시간, 80도에서 4시간, 60도에서 6시간, 40도에서 11시간 교반 후, 크레질글리시딜에테르(화합물(e)) 6.3g을 첨가해 120도에서 10시간 교반하였다. 50도까지 냉각하고, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 29g을 첨가하고, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 용액으로 해서 목적물인 알칼리 현상성 수지 조성물 No.4를 얻었다(Mw=4700, Mn=2500, 산가(고형분) 45mgKOH/g).43 g of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexylmethane (compound (a)), 11 g of acrylic acid (compound (b)), 2.6- 0.05 g of di-tert-butyl-p-cresol, 0.11 g of tetrabutylammonium acetate, and 23 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 120 to 16 hours. After cooling to room temperature, 35 g of propylene glycol-1-monomethyl ether-2-acetate and 10 g of biphenyltetracarboxylic dianhydride (compound (d-1)) were added, followed by stirring at 120 degrees for 8 hours. Furthermore, 6 g of tetrahydrophthalic anhydride (compound (d-2)) was added, and after stirring for 4 hours at 120 degrees, 3 hours at 100 degrees, 4 hours at 80 degrees, 6 hours at 60 degrees, and 11 hours at 40 degrees, 6.3 g of gillycidyl ether (compound (e)) was added and the mixture was stirred at 120 ° C for 10 hours. It cooled to 50 degree | times, 29 g of propylene glycol-1-monomethyl ether-2-acetates were added, and it was set as the propylene glycol-1-monomethyl ether-2-acetate solution, and obtained alkali developing resin composition No. 4 which is a target object. (Mw = 4700, Mn = 2500, acid value (solid content) 45 mgKOH / g).
아울러 알칼리 현상성 수지 조성물 No.4가 함유하는 반응생성물은 (A)성분인 화합물(a)에 (B)성분인 화합물(b)을 부가시킨 구조를 가지는 에폭시 부가물의 수산기 1개에 대해, (D)성분인 화합물(d-1) 및 화합물(d-2)의 산무수물 구조가 0.7개의 비율로, 에폭시 부가물과 화합물(d-1) 및 화합물(d-1)을 에스테르화 반응시켜서 얻어진 것에, 나아가 산무수물 구조에 유래하는 카르복실기의 0.36개를 (E)성분인 화합물(e)로 에스테르화한 구조이다. 또한 상기 에폭시 부가물은 화합물(a)의 에폭시기 1개에 대해서 화합물(b)의 카르복실기가 1개의 비율로 부가시킨 구조를 가지는 것이다.In addition, the reaction product which alkali-developable resin composition No. 4 contains per one hydroxyl group of the epoxy adduct of the structure which added the compound (b) which is (B) component to the compound (a) which is (A) component, ( The acid anhydride structure of the compound (d-1) and the compound (d-2) which are D) component was obtained by esterifying an epoxy adduct, a compound (d-1), and a compound (d-1) in 0.7 ratio. Furthermore, it is a structure which esterified 0.36 of the carboxyl groups derived from an acid anhydride structure by the compound (e) which is (E) component. In addition, the said epoxy adduct has a structure which the carboxyl group of compound (b) added in one ratio with respect to one epoxy group of compound (a).
[실시예 5] 알칼리 현상성 수지 조성물 No.5의 제조Example 5 Preparation of Alkaline Developable Resin Composition No. 5
1,1-비스(4'-에폭시프로필옥시페닐)-1-(1''-비페닐)-1-시클로헥실메탄(화합물(a)) 43g, 페놀(이하, 화합물(c)이라고도 함) 5.7g 및 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 25g을 첨가해 115도까지 가열하였다. 트리페닐포스핀 0.2g를 첨가해 120도에서 4시간 교반하고, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 50g을 첨가해 50도까지 냉각하였다. 2.6-디-tert-부틸-p-크레졸 48mg, 벤질트리에틸암모늄브로미드 0.49g 및 아크릴산(화합물) 6.6g을 첨가해 120에서 5시간 교반하고, 50도까지 냉각하였다. 비페닐테트라카르본산 2무수물(화합물(d-1)) 10.27g을 첨가해 120도에서 8시간 교반하였다. 나아가 테트라히드로무수프탈산(화합물(d-2)) 6.23g을 첨가해 120도에서 4시간, 100도에서 3시간, 80도에서 4시간, 60도에서 6시간, 40도에서 11시간 교반하였다. 50도까지 냉각하고, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 58.3g을 첨가하고, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 용액으로 해서 목적물인 알칼리 현상성 수지 조성물 No.5를 얻었다(Mw=4300, Mn=2200, 산가(고형분) 87mgKOH/g).43 g of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexylmethane (compound (a)), phenol (hereinafter also referred to as compound (c)) 5.7 g and 25 g of propylene glycol-1-monomethyl ether-2-acetate were added and heated to 115 degrees. 0.2 g of triphenylphosphine was added, and it stirred at 120 degree | times for 4 hours, 50 g of propylene glycol-1-monomethyl ether- 2-acetate was added, and it cooled to 50 degree | times. 48 mg of 2.6-di-tert-butyl-p-cresol, 0.49 g of benzyltriethylammonium bromide and 6.6 g of acrylic acid (compound) were added, stirred at 120 for 5 hours, and cooled to 50 degrees. 10.27 g of biphenyl tetracarboxylic dianhydride (compound (d-1)) were added, and it stirred at 120 degree | times for 8 hours. Furthermore, 6.23 g of tetrahydrophthalic anhydride (compound (d-2)) was added, and it stirred for 4 hours at 120 degree | times, 3 hours at 100 degree | times, 4 hours at 80 degree | times, 6 hours at 60 degree | times, and 11 hours at 40 degree | times. It cools to 50 degree | times, adds 58.3 g of propylene glycol-1-monomethyl ether- 2-acetates, and prepares the alkali developable resin composition No. 5 which is a target object as a propylene glycol-1-monomethyl ether- 2-acetate solution. Obtained (Mw = 4300, Mn = 2200, acid value (solid content) 87 mgKOH / g).
또한 알칼리 현상성 수지 조성물 No.5가 함유하는 반응생성물은 (A)성분인 화합물(a)에 (B)성분인 화합물(b) 및 (C)성분인 화합물(c)을 부가시킨 구조를 가지는 에폭시 부가물의 수산기 1개에 대해, (D)성분인 화합물(d-1) 및 화합물(d-2)의 산무수물 구조가 0.73개의 비율로, 에폭시 부가물과 화합물(d-1) 및 화합물(d-1)을 에스테르화 반응시켜서 얻어진 것이다. 또한 상기 에폭시 부가물은 화합물(a)의 에폭시기 1개에 대해, 화합물(b)의 카르복실기가 0.5개, 화합물(c)의 페놀성 수산기가 0.4개, 화합물(b) 및 화합물(c)의 합이 1.0개의 비율로 부가시킨 구조를 가지는 것이다.In addition, the reaction product contained in alkali developable resin composition No. 5 has a structure in which compound (a) which is (A) component is added compound (b) and compound (c) which are (C) component. With respect to one hydroxyl group of an epoxy adduct, the acid anhydride structure of compound (d-1) and compound (d-2) which are (D) component is 0.73 ratio, and an epoxy adduct, a compound (d-1), and a compound ( It is obtained by esterifying d-1). In addition, the said epoxy adduct has the sum of 0.5 carboxyl groups of compound (b), 0.4 phenolic hydroxyl groups of compound (c), and compound (b) and compound (c) with respect to one epoxy group of compound (a). It has a structure added at 1.0 ratio.
[실시예 6] 알칼리 현상성 수지 조성물 No.6의 제조Example 6 Preparation of Alkaline Developable Resin Composition No. 6
1,1-비스(4'-에폭시프로필옥시페닐)-1-(1''-비페닐)-1-시클로헥실메탄(화합물(a)) 43g, 페놀(화합물(c)) 7.1g 및 프로필렌글리콜-1-모노에틸에테르-2-아세테이트 25g을 첨가해 115도까지 가열하였다. 트리페닐포스핀 0.2g를 첨가하고 120도에서 4시간 교반하고, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 50g을 첨가해 50도까지 냉각하였다. 2,6-디-tert-부틸-p-크레졸 48mg, 벤질트리에틸암모늄브로미드 0.49g 및 아크릴산(화합물) 5.5g을 부가하고, 120에서 5시간 교반하고, 50도까지 냉각하였다. 비페닐테트라카르본산 2무수물(화합물(d-1)) 10.27g을 첨가해 120도에서 8시간 교반하였다. 나아가 테트라히드로무수프탈산(화합물(d-2)) 6.23g을 첨가해 120도에서 4시간, 100도에서 3시간, 80도에서 4시간, 60도에서 6시간, 40도에서 11시간 교반하였다. 50도까지 냉각하고, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 58.3g을 첨가하고, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 용액으로 해서 목적물인 알칼리 현상성 수지 조성물 No.6을 얻었다(Mw=4400, Mn=2230, 산가(고형분) 87mgKOH/g).43 g of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexylmethane (compound (a)), 7.1 g of phenol (compound (c)) and propylene 25 g of glycol-1-monoethyl ether-2-acetate were added and heated to 115 degrees. 0.2 g of triphenylphosphine was added, and it stirred at 120 degree | times for 4 hours, 50 g of propylene glycol-1-monomethyl ether- 2-acetate was added, and it cooled to 50 degree | times. 48 mg of 2,6-di-tert-butyl-p-cresol, 0.49 g of benzyltriethylammonium bromide and 5.5 g of acrylic acid (compound) were added, stirred at 120 for 5 hours, and cooled to 50 degrees. 10.27 g of biphenyl tetracarboxylic dianhydride (compound (d-1)) were added, and it stirred at 120 degree | times for 8 hours. Furthermore, 6.23 g of tetrahydrophthalic anhydride (compound (d-2)) was added, and it stirred for 4 hours at 120 degree | times, 3 hours at 100 degree | times, 4 hours at 80 degree | times, 6 hours at 60 degree | times, and 11 hours at 40 degree | times. It cools to 50 degree | times, adds 58.3 g of propylene glycol-1-monomethyl ether- 2-acetates, and prepares the alkali developable resin composition No. 6 which is a target object as a propylene glycol-1-monomethyl ether- 2-acetate solution. Obtained (Mw = 4400, Mn = 2230, acid value (solid content) 87 mgKOH / g).
또한 알칼리 현상성 수지 조성물 No.6이 함유하는 반응생성물은 (A)성분인 화합물(a)에 (B)성분인 화합물(b) 및 (C)성분인 화합물(c)을 부가시킨 구조를 가지는 에폭시 부가물의 수산기 1개에 대해, (D)성분인 화합물(d-1) 및 화합물(d-2)의 산무수물 구조가 0.7개의 비율로, 에폭시 부가물과 화합물(d-1) 및 화합물(d-1)을 에스테르화 반응시켜서 얻어진 것이다. 또한 상기 에폭시 부가물은 화합물(a)의 에폭시기 1개에 대해, 화합물(b)의 카르복실기가 0.5개, 화합물(c)의 페놀성 수산기가 0.5개, 화합물(b) 및 화합물(c)의 합이 1.0개의 비율로 부가시킨 구조를 가지는 것이다.In addition, the reaction product contained in alkali-developable resin composition No. 6 has a structure in which compound (a) which is (A) component is added compound (b) and compound (c) which are (C) component. With respect to one hydroxyl group of an epoxy adduct, the acid anhydride structure of compound (d-1) and compound (d-2) which are (D) component is 0.7 ratio, and an epoxy adduct, a compound (d-1), and a compound ( It is obtained by esterifying d-1). In addition, the said epoxy adduct has the sum of 0.5 carboxyl group of compound (b), 0.5 phenolic hydroxyl group of compound (c), compound (b), and compound (c) with respect to one epoxy group of compound (a). It has a structure added at 1.0 ratio.
[실시예 7] 알칼리성 현상성 감광성 수지 조성물 No.1의 제조Example 7 Preparation of alkaline developable photosensitive resin composition No. 1
실시예 1에서 얻어진 알칼리 현상성 수지 조성물 No.1의 14g에 대해, 트리메틸올 프로판트리아크릴레이트 5.9g, 벤조페논 2.1g 및 에틸셀로솔브 78g을 첨가해 잘 교반하고, 알칼리 현상성 감광성 수지 조성물을 No.1을 얻었다.To 14 g of alkali developable resin composition No. 1 obtained in Example 1, 5.9 g of trimethylol propane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition was stirred. No. 1 was obtained.
[실시예 8] 알칼리성 현상성 감광성 수지 조성물 No.2의 제조Example 8 Preparation of alkaline developable photosensitive resin composition No. 2
실시예 2에서 얻어진 알칼리 현상성 수지 조성물 No.2의 14g에 대해, 트리메틸올 프로판트리아크릴레이트 5.9g, 벤조페논 2.1g 및 에틸셀로솔브 78g을 첨가해 잘 교반하고, 알칼리 현상성 감광성 수지 조성물을 No.2를 얻었다.To 14 g of alkali developable resin composition No. 2 obtained in Example 2, 5.9 g of trimethylol propane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition was stirred. No. 2 was obtained.
[실시예 9] 알칼리성 현상성 감광성 수지 조성물 No.3의 제조Example 9 Preparation of alkaline developable photosensitive resin composition No. 3
실시예 1에서 얻어진 알칼리 현상성 수지 조성물 No.1의 12g에 대해, 디펜타에리스리톨헥사아크릴레이트 8.1g, 벤조페논 1.9g 및 에틸셀로솔브 47g 및 시클로 헥사논 31g을 첨가해 잘 교반하고, 알칼리 현상성 감광성 수지 조성물을 No.3을 얻었다.To 12 g of alkali developable resin composition No. 1 obtained in Example 1, 8.1 g of dipentaerythritol hexaacrylate, 1.9 g of benzophenone, 47 g of ethyl cellosolve, and 31 g of cyclohexanone were added and stirred well, and alkali No. 3 was obtained for the developable photosensitive resin composition.
[실시예 10] 알칼리성 현상성 감광성 수지 조성물 No.4의 제조Example 10 Preparation of alkaline developable photosensitive resin composition No. 4
실시예 1에서 얻어진 알칼리 현상성 수지 조성물 No.1의 7.2g에 대해, 트리메틸올프로판트리아크릴레이트 4.3g, 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노프로판-1-온 1.5g 및 에틸셀로솔브 87g을 첨가해 잘 교반하고, 알칼리 현상성 감광성 수지 조성물을 No.4을 얻었다.To 7.2 g of alkali developable resin composition No. 1 obtained in Example 1, 4.3 g of trimethylolpropane triacrylate and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane 1.5 g of -1-one and 87 g of ethyl cellosolve were added and stirred well to obtain No. 4 for an alkali developable photosensitive resin composition.
[실시예 11] 알칼리성 현상성 감광성 수지 조성물 No.5의 제조Example 11 Preparation of alkaline developable photosensitive resin composition No. 5
실시예 1에서 얻어진 알칼리 현상성 수지 조성물 No.1의 20g에 대해, 트리메틸올프로판트리아크릴레이트 8.7g, 아크릴계 공중합체 4.6g, 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노프로판-1-온 1.7g 및 에틸셀로솔브 65g을 첨가해 잘 교반하고, 알칼리 현상성 감광성 수지 조성물을 No.5을 얻었다.To 20 g of alkali developable resin composition No. 1 obtained in Example 1, 8.7 g of trimethylolpropane triacrylate, 4.6 g of an acrylic copolymer, and 2-methyl-1- [4- (methylthio) phenyl] -2 1.7 g of morpholino propane-1-one and 65 g of ethyl cellosolve were added and stirred well to obtain No. 5 as the alkali developable photosensitive resin composition.
아울러 상기 아크릴계 공중합체는 메타크릴산 20중량부, 히드록시에틸메타크릴레이트 15중량부, 메틸메타크릴레이트 10중량부 및 부틸메틸메타크릴레이트 55중량부를 에틸셀로솔브 300중량부에 용해하고, 질소분위기하에서 아조비스이소부틸니트릴 0.75중량부를 첨가해 70도에서 5시간 반응시킴으로써 얻어진 것이다.In addition, the acrylic copolymer is dissolved 20 parts by weight of methacrylic acid, 15 parts by weight of hydroxyethyl methacrylate, 10 parts by weight of methyl methacrylate and 55 parts by weight of butyl methyl methacrylate in 300 parts by weight of ethyl cellosolve, It was obtained by adding 0.75 parts by weight of azobisisobutylnitrile in a nitrogen atmosphere and reacting at 70 degrees for 5 hours.
[비교예 1] 알칼리 현상성 수지 조성물 No.7의 제조Comparative Example 1 Production of alkali developable resin composition No. 7
비스페놀플루오렌형 에폭시 수지(에폭시 당량 231) 184g, 아크릴산 58g, 2,6-디-tert-부틸-p-크레졸 0.26g, 테트라부틸암모늄아세테이트 0.11g 및 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 23g을 넣고, 120도에서 16시간 교반하였다. 실온까지 냉각하고, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 35g 비프탈산무수물 59g 및 테트라-n-부틸암모늄브로미드 0.24g을 첨가해 120도에서 4시간 교반하였다. 나아가 테트라히드로무수프탈산 20g을 첨가하고, 120도에서 4시간, 100도에서 3시간, 80도에서 4시간, 60도에서 6시간, 40도에서 11시간 교반 후, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 90g을 첨가하고, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 용액으로 해서 목적물의 알칼리 현상성 수지 조성물 No.7을 얻었다(Mw=5000, Mn=2100, 산가(고형분) 92.7mgKOH/g).184 g of bisphenol fluorene type epoxy resin (epoxy equivalent 231), 58 g of acrylic acid, 0.26 g of 2,6-di-tert-butyl-p-cresol, 0.11 g of tetrabutylammonium acetate, and propylene glycol-1-monomethyl ether-2- 23 g of acetate was added and stirred for 16 hours at 120 degrees. After cooling to room temperature, 59 g of propylene glycol-1-monomethyl ether-2-acetate 35 g nonphthalic anhydride and 0.24 g of tetra-n-butylammonium bromide were added, and the mixture was stirred at 120 degrees for 4 hours. Furthermore, 20 g of tetrahydrophthalic anhydride was added and after stirring for 4 hours at 120 degrees, 3 hours at 100 degrees, 4 hours at 80 degrees, 6 hours at 60 degrees, and 11 hours at 40 degrees, propylene glycol-1-monomethyl ether 90 g of -2-acetate was added and alkali developing resin composition No. 7 of the target object was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution (Mw = 5000, Mn = 2100, acid value (solid content) 92.7). mgKOH / g).
[비교예 2] 알칼리 현상성 수지 조성물 No.8의 제조[Comparative Example 2] Preparation of alkali developable resin composition No. 8
비스페놀A형 에폭시 수지(에폭시 당량 190) 154g, 아크릴산 59g, 2,6-디-tert-부틸-p-크레졸 0.26g, 테트라부틸암모늄아세테이트 0.11g 및 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 23g을 넣고, 120도에서 16시간 교반하였다. 실온까지 냉각하고, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 365g, 비프탈산무수물 67g 및 테트라-n-부틸암모늄브로미드 0.24g을 첨가해 120도에서 4시간, 100도에서 3시간, 80도에서 4시간, 60도에서 6시간, 40도에서 11시간 교반 후, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 90g을 첨가하고, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 용액으로 해서 목적물의 알칼리 현상성 수지 조성물 No.8을 얻었다(Mw=7500, Mn=2100, 산가(고형분) 91mgKOH/g).154 g of bisphenol-A epoxy resin (epoxy equivalent 190), 59 g of acrylic acid, 0.26 g of 2,6-di-tert-butyl-p-cresol, 0.11 g of tetrabutylammonium acetate, and propylene glycol-1-monomethyl ether-2-acetate 23 g was added and stirred for 16 hours at 120 degrees. After cooling to room temperature, 365 g of propylene glycol-1-monomethyl ether-2-acetate, 67 g of non-phthalic anhydride, and 0.24 g of tetra-n-butylammonium bromide were added, and 4 hours at 120 ° C and 3 hours at 100 ° C After stirring for 4 hours at 60, 6 hours at 60 degrees, and 11 hours at 40 degrees, 90 g of propylene glycol-1-monomethyl ether-2-acetate was added thereto, followed by propylene glycol-1-monomethyl ether-2-acetate solution. Thus, the alkali developable resin composition No. 8 of the target object was obtained (Mw = 7500, Mn = 2100, acid value (solid content) 91 mgKOH / g).
[비교예 3] 알칼리 현상성 수지 조성물 No.9의 제조[Comparative Example 3] Preparation of alkali developable resin composition No. 9
<스텝 1> 1,1-비스(4'-히드록시페닐)-1-(1''-비페닐)에탄의 제조<Step 1> Preparation of 1,1-bis (4'-hydroxyphenyl) -1- (1 ''-biphenyl) ethane
페논 75g 및 4-아세틸비페닐 50g을 60도에서 가열 용해시키고, 3-메르캅토프 로피온산 5g을 첨가해 교반하면서 염화수소가스를 24시간 불어넣고, 그 후, 72시간 반응시켰다. 70도의 온수에서 세정한 다음, 감압하에서 180도까지 가열해 증발물을 제거하였다. 잔사(殘渣)에 크실렌을 첨가해 냉각하고, 석출한 결정을 여과 분리해, 감압 건조해 염황색 결정 65g(수율 68%)을 얻었다. 상기 염황색 결정의 융점은 184도이며, 상기 염황색 경정은 목적물임을 확인하였다.75 g of phenone and 50 g of 4-acetylbiphenyl were dissolved by heating at 60 degrees, and hydrogen chloride gas was blown in for 24 hours while stirring and adding 5 g of 3-mercaptoproic acid, followed by reacting for 72 hours. It was washed in hot water at 70 degrees and then heated to 180 degrees under reduced pressure to remove evaporates. Xylene was added to the residue, the mixture was cooled, the precipitated crystals were separated by filtration, and dried under reduced pressure to obtain 65 g of a yellowish yellow crystal (yield 68%). The melting point of the yellowish-yellow crystals was 184 degrees, and it was confirmed that the yellow-yellow crystals were the target product.
<스텝 2> 1,1-비스(4'-에폭시프로필옥시페닐)-1-(1''-비페닐)에탄의 제조 <Step 2> Preparation of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) ethane
스텝 1에서 얻어진 1,1-비스(4'-히드록시페닐)-1-(1''-비페닐)에탄 37g 및 에피클로로히드린 149.5g을 넣고, 벤질트리에틸암모늄클로리드 0.45g을 첨가해 64도에서 18시간 교반하였다. 계속해서 54도까지 승온하고, 24중량% 수산화나트륨 수용액 32.6g을 적하해 30분 교반하였다. 에피클로로히드린 및 물을 제거하고, 메틸이소부틸케톤 140g을 첨가해 물로 씻는 다음, 24중량% 수산화나트름 1.7g을 적하하였다. 80도에서 2시간 교반 후, 실온까지 냉각하고, 3중량% 모노인산나트륨 수용액으로 중화해 물로 씻어냈다. 용매를 제거하고, 황색 점성 액체 38.7g(수율 80%)을 얻었다(에폭시 당량 248, n=0.04). 상기 황색 점성 액체는 목적물임을 확인하였다.37 g of 1,1-bis (4'-hydroxyphenyl) -1- (1 ''-biphenyl) ethane and 149.5 g of epichlorohydrin obtained in Step 1 were added, and 0.45 g of benzyltriethylammonium chloride was added. It stirred for 18 hours at 64 degree. Then, it heated up to 54 degreeC, 32.6 g of 24weight% sodium hydroxide aqueous solution was dripped, and it stirred for 30 minutes. Epichlorohydrin and water were removed, and 140 g of methyl isobutyl ketone was added and washed with water, followed by dropwise addition of 1.7 g of 24 wt% sodium hydroxide. After stirring at 80 ° C for 2 hours, the mixture was cooled to room temperature, neutralized with 3% by weight aqueous sodium monophosphate solution, and washed with water. The solvent was removed and 38.7 g (yield 80%) of yellow viscous liquid was obtained (epoxy equivalent 248, n = 0.04). It was confirmed that the yellow viscous liquid was the target product.
<스텝 3> 알칼리 현상성 수지 조성물 No.9의 제조<Step 3> Alkali-developable resin composition No. 9 production
1,1-비스(4'-에폭시프로필옥시페닐)-1-(1''-비페닐)에탄 49.6g, 아크릴산 14.4g, 2,6-디-tert-부틸-p-크레졸 0.05g, 테트라부틸암모늄아세테이트 0.14g 및 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 27.4g을 넣고, 120도에서 16시간 교반하였다. 실온까지 냉각하고, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 41.5g 및 비페닐테트라카르본산 2무수물 12.4g을 첨가해 120도에서 8시간 교반하였 다. 나아가 테트라히드로무수프탈산 7.9g을 첨가해 120도에서 4시간, 100도에서 3시간, 80도에서 4시간, 60도에서 6시간, 40도에서 11시간 교반 후, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 34g을 첨가하고, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트 용액으로 해서 목적물의 알칼리 현상성 수지 조성물 No.9를 얻었다(Mw=3700, Mn=1900, 산가(고형분) 93mgKOH/g).49.6 g of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) ethane, 14.4 g of acrylic acid, 2,6-di-tert-butyl-p-cresol, 0.05 g, tetra 0.14 g of butylammonium acetate and 27.4 g of propylene glycol-1-monomethyl ether-2-acetate were added thereto, and the mixture was stirred at 120 degrees for 16 hours. After cooling to room temperature, 41.5 g of propylene glycol-1-monomethyl ether-2-acetate and 12.4 g of biphenyltetracarboxylic dianhydride were added, followed by stirring at 120 ° C for 8 hours. Furthermore, 7.9 g of tetrahydrophthalic anhydride was added and after stirring for 4 hours at 120 degrees, 3 hours at 100 degrees, 4 hours at 80 degrees, 6 hours at 60 degrees, and 11 hours at 40 degrees, propylene glycol-1-monomethyl ether -2-acetate 34g was added and alkali developing resin composition No. 9 of the target object was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution (Mw = 3700, Mn = 1900, acid value (solid content) 93mgKOH) / g).
[비교예 4] 알칼리 현상성 감광성 수지 조성물 No.6의 제조[Comparative Example 4] Production of alkali developable photosensitive resin composition No. 6
비교예 1에서 얻어진 알칼리 현상성 수지 조성물 No.7의 14g에 대해, 트리메틸올프로판트리아크릴레이트 5.9g, 벤조페논 2.1g 및 에틸셀로솔브 78g을 첨가해 잘 교반하고, 알칼리 현상성 감광성 수지 조성물 No.6을 얻었다.To 14 g of alkali developable resin composition No. 7 obtained in Comparative Example 1, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition was stirred. No.6 was obtained.
[비교예 5] 알칼리 현상성 감광성 수지 조성물 No.7의 제조[Comparative Example 5] Production of alkali developable photosensitive resin composition No. 7
비교예 2에서 얻어진 알칼리 현상성 수지 조성물 No.8의 14g에 대해, 트리메틸올프로판트리아크릴레이트 5.9g, 벤조페논 2.1g 및 에틸셀로솔브 78g을 첨가해 잘 교반하고, 알칼리 현상성 감광성 수지 조성물 No.7을 얻었다.To 14 g of alkali developable resin composition No. 8 obtained in Comparative Example 2, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition was stirred. No. 7 was obtained.
[비교예 6] 알칼리 현상성 감광성 수지 조성물 No.8의 제조[Comparative Example 6] Production of alkali developable photosensitive resin composition No. 8
비교예 3에서 얻어진 알칼리 현상성 수지 조성물 No.9의 14g에 대해, 트리메틸올프로판트리아크릴레이트 5.9g, 벤조페논 2.1g 및 에틸셀로솔브 78g을 첨가해 잘 교반하고, 알칼리 현상성 감광성 수지 조성물 No.8을 얻었다.To 14 g of alkali developable resin composition No. 9 obtained in Comparative Example 3, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition was stirred. No.8 was obtained.
얻어진 알칼리 현상성 감광성 수지 조성물 No.1~8의 평가를 이하와 같이 행하였다.Evaluation of obtained alkali developable photosensitive resin composition No. 1-8 was performed as follows.
즉 기판상에 r-글리시독시프로필메틸에톡시실란을 스핀코트해 잘 스핀 건조 시킨 후, 상기 알칼리 현상성 감광성 수지 조성물 No.1~7을 스핀코트(1300r.p.m, 50초간)해 건조시켰다. 70도에서 20분간 프리베이크를 행한 후, 폴리비닐알코올 5중량% 용액을 코트해 산소 차단막으로 하였다. 70도에서 20분간의 건조 후, 소정의 마스크를 사용해, 광원으로서 초고압 수은 램프를 사용해 노광 후, 2.5중량% 탄산나트륨 용액에 25도로 30초간 침지해 현상하고, 잘 물로 씻었다. 수세(水洗) 건조 후, 230도에서 1시간 베이크해 패턴을 정착시켰다. 얻어진 패턴에 대해서 이하의 평가를 행하였다. 결과를 표 1에 나타낸다.That is, after spin-coating r-glycidoxy propylmethylethoxysilane on a board | substrate and spin-drying well, the said alkali developable photosensitive resin composition Nos. 1-7 were spin-coated (1300 r.pm, 50 second), and dried. . After prebaking at 70 degrees for 20 minutes, a 5% by weight solution of polyvinyl alcohol was coated to form an oxygen barrier film. After 20 minutes of drying at 70 degrees, a predetermined mask was used, and after exposure using an ultrahigh pressure mercury lamp as a light source, the solution was immersed in a 2.5 wt% sodium carbonate solution for 25 seconds for 30 seconds, and washed well with water. After washing with water, baking was carried out at 230 degrees for 1 hour to fix the pattern. The following evaluation was performed about the obtained pattern. The results are shown in Table 1.
<감도><Sensitivity>
노광 시에 노광량이 100mJ/cm2로 충분했던 것을 a, 100mJ/cm2로 불충분하고, 200mJ/cm2로 노광한 것을 b로 하였다.The exposure amount at the time of exposure that is sufficient to 100mJ / cm 2 in a, 100mJ / cm 2 is insufficient, and that were exposed to 200mJ / cm 2 by b.
<해상도><Resolution>
노광현상 시에, 선폭 10㎛ 이하에서도 양호하게 패턴 형성할 수 있었던 것을 A, 선촉 10~30㎛이면 양호하게 패턴 형성할 수 있었던 것을 B, 선폭 30㎛ 이상의 것이 아니면 양호한 패턴 형성을 할 수 없었던 것을 C로 평가하였다.At the time of exposure development, A was able to form a pattern satisfactorily even at a line width of 10 µm or less, A was able to form a pattern satisfactorily if it was 10-30 µm, and B was not able to form a good pattern unless it was 30 µm or more. It was evaluated by C.
<밀착성><Adhesiveness>
JIS D 0202의 시험방법에 따라, 도막에 그리드형상으로 크로스컷을 넣은 다음 셀로판 테이프에 의해서 필링 테스트를 행하고, 그리드의 박리의 상태를 눈으로 평가하였다. 전혀 박리가 인정되지 않았던 것을 ○, 박리가 인정된 것을 ×로 하였다.In accordance with the test method of JIS D 0202, a crosscut was put in the grid shape to the coating film, the peeling test was done with the cellophane tape, and the peeling state of the grid was visually evaluated. (Circle) and the thing in which peeling was recognized were made into what was not recognized at all.
<내알칼리성><Alkali resistance>
가열처리 후의 도막 a) 5중량% NaOHaq. 중 24시간, b)4중량% KOHaq. 중 50도에서 10분간, c)1중량% NaOHaq. 중 80도에서 5분간의 조건에서 침지하고, 침지 후의 외관을 눈으로 평가하였다. 외관 변화도 없고 레지스트의 박리도 전혀 없었던 것을 ○, 레지스트의 뜸이 보이거나 레지스트의 박리가 인정된 것을 ×로 하였다.Coating film after heat treatment a) 5% by weight NaOHaq. 24 h, b) 4 wt% KOHaq. 10 minutes at 50 ° C., c) 1 wt.% NaOHaq. It was immersed in the conditions of 5 minutes at 80 degreeC, and the appearance after immersion was visually evaluated. (Circle) and the thing in which the moxibustion of the resist was seen or the peeling of the resist was recognized as x that there was no external appearance change and there was no peeling of the resist at all.
실시예 7~11의 알칼리 현상성 감광성 수지 조성물은 고감도이면서 해상도에 뛰어난 것이며, 또한 얻어진 도막은 가판과의 밀착성, 내알칼리성에 뛰어난 것이였다.Alkali-developable photosensitive resin compositions of Examples 7 to 11 were highly sensitive and excellent in resolution, and the obtained coating film was excellent in adhesiveness with the substrate and alkali resistance.
그것에 비해서, 비교예 4~6의 알칼리 현상성 감광성 수지 조성물은 감도가 낮은 때문에 노광량을 많게 할 수가 없고, 해상도가 저하하고, 선폭 30㎛ 이상이지 않으면 형성할 수 없고, 또한 얻어진 도막의 기판과의 밀착성, 내알칼리성도 바람직하지 않았다.On the other hand, since the alkali developable photosensitive resin composition of Comparative Examples 4-6 is low in sensitivity, it is not possible to increase the exposure dose, the resolution is lowered, and it cannot be formed unless the line width is 30 µm or more, and the obtained coating film with the substrate Adhesiveness and alkali resistance were also undesirable.
본 발명의 알칼리 현상성 감광성 수지 조성물은 투명성, 밀착성, 내알칼리성 등에 뛰어나며, 미세패턴을 정밀도 좋게 형성할 수 있다.The alkali developable photosensitive resin composition of this invention is excellent in transparency, adhesiveness, alkali resistance, etc., and can form a fine pattern with high precision.
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| WO2016129195A1 (en) * | 2015-02-10 | 2016-08-18 | Jsr株式会社 | Photosensitive resin composition and resin composition, patterned resin film and method for manufacturing same, and cell culture device |
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- 2004-09-17 JP JP2004271688A patent/JP4198101B2/en active Active
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2005
- 2005-08-30 KR KR1020067000500A patent/KR101168438B1/en active IP Right Grant
- 2005-08-30 WO PCT/JP2005/015719 patent/WO2006030630A1/en active Application Filing
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI375863B (en) | 2012-11-01 |
| WO2006030630A1 (en) | 2006-03-23 |
| TW200625005A (en) | 2006-07-16 |
| CN100580555C (en) | 2010-01-13 |
| JP2006084985A (en) | 2006-03-30 |
| CN1860415A (en) | 2006-11-08 |
| JP4198101B2 (en) | 2008-12-17 |
| KR101168438B1 (en) | 2012-07-25 |
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