KR102371057B1 - Alkali-developable resins containing unsaturated groups and resin materials for solder resists - Google Patents
Alkali-developable resins containing unsaturated groups and resin materials for solder resists Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
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- C—CHEMISTRY; METALLURGY
- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/026—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight
- C08F299/028—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight photopolymerisable compositions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
Abstract
현상성, 및 경화물에 있어서의 내열성과 유전 특성이 우수한 불포화기 함유 알칼리 현상성 수지, 이것을 함유하는 광경화형 알칼리 현상성 수지 조성물과 그 경화물, 솔더 레지스트용 수지 재료와 레지스트 부재를 제공하는 것. 폴리에폭시 화합물(A), 불포화 모노카르복시산(B), 불포화 모노카르복시산무수물(C), 및 디카르복시산무수물(D)을 필수의 원료로서 반응시켜서 얻어지는 분자 구조를 갖고, 산가가 50∼80mgKOH/g의 범위이며, 또한, 수산기가가 19mgKOH/g 이하의 범위인 불포화기 함유 알칼리 현상성 수지.To provide an unsaturated group-containing alkali developable resin excellent in developability and heat resistance and dielectric properties in a cured product, a photocurable alkali developable resin composition containing the same, a cured product thereof, a resin material for soldering resist, and a resist member . It has a molecular structure obtained by reacting a polyepoxy compound (A), an unsaturated monocarboxylic acid (B), an unsaturated monocarboxylic acid anhydride (C), and a dicarboxylic acid anhydride (D) as essential raw materials, and an acid value of 50 to 80 mgKOH/g An unsaturated group-containing alkali developable resin whose hydroxyl value is in the range of 19 mgKOH/g or less.
Description
본 발명은, 현상성, 및 경화물에 있어서의 내열성과 유전 특성이 우수한 불포화기 함유 알칼리 현상성 수지, 이것을 함유하는 광경화형 알칼리 현상성 수지 조성물과 그 경화물, 솔더 레지스트용 수지 재료와 레지스트 부재에 관한 것이다.The present invention relates to an unsaturated group-containing alkali developable resin excellent in developability and heat resistance and dielectric properties in a cured product, a photocurable alkali developable resin composition containing the same, a cured product thereof, a resin material for soldering resists, and a resist member is about
프린트 배선 기판용의 솔더 레지스트에는, 광경화형 알칼리 현상성 수지 조성물이 널리 사용되고 있고, 적은 노광량으로 경화하는 것, 알칼리 현상성이 우수한 것, 경화물에 있어서의 내열성이 높은 것, 기재 밀착성이 우수한 것, 유전 특성이 우수한 것 등, 다수의 요구 성능이 있다. 이들 요구 특성 중에서도, 근래 특히 요구 레벨이 높아져 있는 것이 유전 특성이며, 각종 전자기기에 있어서의 신호의 고속화 및 고주파수화에 수반하여, 유전율 및 유전정접이 보다 낮고, 신호의 전송 로스가 작은 수지 재료의 개발이 요구되고 있다.A photocurable alkali developable resin composition is widely used for the soldering resist for printed wiring boards, Hardening with a small exposure amount, The thing excellent in alkali developability, The thing with high heat resistance in hardened|cured material, The thing excellent in base material adhesiveness , there are a number of required performances, such as those having excellent dielectric properties. Among these required properties, dielectric properties have been of a particularly high demand in recent years, and with the speed and high frequencies of signals in various electronic devices, the dielectric constant and dielectric loss tangent are lower and the signal transmission loss is small. development is required.
종래 알려져 있는 솔더 레지스트용 수지 재료로서, 크레졸노볼락형 에폭시 수지와 아크릴산과 무수메타크릴산을 반응시켜서 얻어지는 중간체에, 추가로 테트라히드로무수프탈산을 반응시켜서 얻어지는 산펜던트형 에폭시아크릴레이트가 알려져 있다(하기 특허문헌 1 참조). 상기 산펜던트형 에폭시아크릴레이트는 광조사에 의한 경화성이 높고, 현상성도 우수한 것이지만, 경화물에 있어서의 내열성이나 유전 특성이 충분하지 않아, 근래의 요구 레벨을 충족시키는 것은 아니었다.As a conventionally known resin material for soldering resists, an acid pendant type epoxy acrylate obtained by further reacting tetrahydrophthalic anhydride with an intermediate obtained by reacting a cresol novolac type epoxy resin with acrylic acid and methacrylic anhydride is known ( See Patent Document 1 below). Although the acid pendant type epoxy acrylate has high curability by light irradiation and excellent developability, the heat resistance and dielectric properties of the cured product are not sufficient, and thus it has not been able to satisfy the level of demand in recent years.
따라서, 본 발명이 해결하려고 하는 과제는, 현상성, 및 경화물에 있어서의 내열성과 유전 특성이 우수한 불포화기 함유 알칼리 현상성 수지, 이것을 함유하는 광경화형 알칼리 현상성 수지 조성물과 그 경화물, 솔더 레지스트용 수지 재료와 레지스트 부재를 제공하는 것에 있다.Therefore, the problem to be solved by the present invention is an unsaturated group-containing alkali developable resin excellent in developability and heat resistance and dielectric properties in a cured product, a photocurable alkali developable resin composition containing the same, a cured product thereof, and a solder It is to provide a resin material for resists and a resist member.
본 발명자들은, 상기 과제를 해결하기 위하여 예의 검토를 행한 결과, 폴리에폭시 화합물, 불포화 모노카르복시산, 불포화 모노카르복시산무수물, 및 디카르복시산무수물을 필수의 원료로서 반응시켜서 얻어지는 불포화기 함유 알칼리 현상성 수지에 있어서, 어느 일정의 산가와 수산기가를 갖는 것이, 현상성, 및 경화물에 있어서의 내열성과 유전 특성이 우수한 것을 알아내어, 본 발명을 완성시키는데 이르렀다.As a result of the present inventors earnestly examining in order to solve the said subject, a polyepoxy compound, an unsaturated monocarboxylic acid, an unsaturated monocarboxylic acid anhydride, and a dicarboxylic acid anhydride are reacted as essential raw materials In the unsaturated group-containing alkali developable resin obtained by , found that those having a certain acid value and hydroxyl value are excellent in developability and heat resistance and dielectric properties in a cured product, leading to completion of the present invention.
즉, 본 발명은, 폴리에폭시 화합물(A), 불포화 모노카르복시산(B), 불포화 모노카르복시산무수물(C), 및 디카르복시산무수물(D)을 필수의 원료로서 반응시켜서 얻어지는 분자 구조를 갖고, 산가가 50∼80mgKOH/g의 범위이며, 또한, 수산기가가 19mgKOH/g 이하의 범위인 불포화기 함유 알칼리 현상성 수지에 관한 것이다.That is, the present invention has a molecular structure obtained by reacting a polyepoxy compound (A), an unsaturated monocarboxylic acid (B), an unsaturated monocarboxylic acid anhydride (C), and a dicarboxylic acid anhydride (D) as essential raw materials, and has an acid value It is the range of 50-80 mgKOH/g, and it is related with the unsaturated group containing alkali developable resin whose hydroxyl value is the range of 19 mgKOH/g or less.
본 발명은 또한, 상기 불포화기 함유 알칼리 현상성 수지와, 광중합개시제를 함유하는 광경화형 알칼리 현상성 수지 조성물에 관한 것이다.The present invention also relates to a photocurable alkali developable resin composition comprising the unsaturated group-containing alkali developable resin and a photopolymerization initiator.
본 발명은 또한, 상기 불포화기 함유 알칼리 현상성 수지와, 광중합개시제를 함유하는 솔더 레지스트용 수지 재료에 관한 것이다.This invention also relates to the resin material for soldering resists containing the said unsaturated group containing alkali developable resin and a photoinitiator.
본 발명은 또한, 상기 광경화형 알칼리 현상성 수지 조성물을 경화시켜서 이루어지는 경화물에 관한 것이다.The present invention further relates to a cured product obtained by curing the photocurable alkali-developable resin composition.
본 발명은 또한, 상기 솔더 레지스트용 수지 재료를 사용해서 이루어지는 레지스트 부재에 관한 것이다.This invention also relates to the resist member formed using the said resin material for soldering resists.
본 발명에 따르면, 현상성, 및 경화물에 있어서의 내열성과 유전 특성이 우수한 불포화기 함유 알칼리 현상성 수지, 이것을 함유하는 광경화형 알칼리 현상성 수지 조성물과 그 경화물, 솔더 레지스트용 수지 재료와 레지스트 부재를 제공할 수 있다.According to the present invention, an unsaturated group-containing alkali developable resin excellent in developability and heat resistance and dielectric properties in a cured product, a photocurable alkali developable resin composition containing the same, a cured product thereof, a resin material for a solder resist, and a resist Absence can be provided.
도 1은, 실시예 1에서 얻어진 불포화기 함유 알칼리 현상성 수지(1)의 GPC 차트도.
도 2는, 실시예 2에서 얻어진 불포화기 함유 알칼리 현상성 수지(2)의 GPC 차트도.
도 3은, 실시예 3에서 얻어진 불포화기 함유 알칼리 현상성 수지(3)의 GPC 차트도.
도 4는, 실시예 4에서 얻어진 불포화기 함유 알칼리 현상성 수지(4)의 GPC 차트도.
도 5는, 실시예 5에서 얻어진 불포화기 함유 알칼리 현상성 수지(5)의 GPC 차트도.BRIEF DESCRIPTION OF THE DRAWINGS It is a GPC chart figure of unsaturated group containing alkali developable resin (1) obtained in Example 1. FIG.
Fig. 2 is a GPC chart diagram of unsaturated group-containing alkali developable resin (2) obtained in Example 2.
3 is a GPC chart diagram of unsaturated group-containing alkali developable resin (3) obtained in Example 3. FIG.
Fig. 4 is a GPC chart of the unsaturated group-containing alkali developable resin (4) obtained in Example 4.
Fig. 5 is a GPC chart of the unsaturated group-containing alkali developable resin (5) obtained in Example 5;
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 불포화기 함유 알칼리 현상성 수지는, 폴리에폭시 화합물(A), 불포화 모노카르복시산(B), 불포화 모노카르복시산무수물(C), 및 디카르복시산무수물(D)을 필수의 원료로서 반응시켜서 얻어지는 분자 구조를 갖고, 산가가 50∼80mgKOH/g의 범위이며, 또한, 수산기가가 19mgKOH/g 이하의 범위인 것을 특징으로 한다.The unsaturated group-containing alkali developable resin of the present invention is a molecule obtained by reacting a polyepoxy compound (A), an unsaturated monocarboxylic acid (B), an unsaturated monocarboxylic acid anhydride (C), and a dicarboxylic acid anhydride (D) as essential raw materials. It has a structure and is characterized in that the acid value is in the range of 50 to 80 mgKOH/g, and the hydroxyl value is in the range of 19 mgKOH/g or less.
솔더 레지스트용의 불포화기 함유 알칼리 현상성 수지에 있어서는, 알칼리 용액에 의한 현상성을 높이기 위해서 수지의 산가를 80mgKOH/g을 초과하는 높은 값으로 설계하는 것이 일반적인 바, 본원 발명에서는 수지의 산가를 50∼80mgKOH/g의 비교적 낮은 값으로 하며, 또한, 수산기가를 19mgKOH/g 이하의 범위로 함에 의해, 높은 현상성을 유지한 그대로, 경화물에 있어서의 내열성이나 유전 특성도 우수한 불포화기 함유 알칼리 현상성 수지의 실현에 성공한 것이다.In an unsaturated group-containing alkali developable resin for soldering resists, in order to improve developability with an alkali solution, it is common to design the acid value of the resin to a high value exceeding 80 mgKOH/g. In the present invention, the acid value of the resin is 50 By setting the relatively low value of -80 mgKOH/g and the hydroxyl value being in the range of 19 mgKOH/g or less, high developability is maintained and unsaturated group-containing alkali development excellent in heat resistance and dielectric properties in the cured product It has succeeded in realizing the gender balance.
본 발명의 불포화기 함유 알칼리 현상성 수지의 산가는, 상술한 바와 같이 50∼80mgKOH/g의 범위이고, 경화물의 내열성과 유전 특성이 보다 우수하므로, 55∼75mgKOH/g의 범위인 것이 바람직하다.The acid value of the unsaturated group-containing alkali developable resin of the present invention is in the range of 50 to 80 mgKOH/g as described above, and since the heat resistance and dielectric properties of the cured product are more excellent, it is preferably in the range of 55 to 75 mgKOH/g.
또, 본원 발명에 있어서 불포화기 함유 알칼리 현상성 수지의 산가는 JIS K 0070(1992)의 중화 적정법으로 측정되는 값이다.In addition, in this invention, the acid value of unsaturated-group containing alkali developable resin is a value measured by the neutralization titration method of JISK0070 (1992).
또한, 본원 발명에 있어서 불포화기 함유 알칼리 현상성 수지의 수산기가는, 하기의 요령으로 측정되는 값이다.In addition, in this invention, the hydroxyl value of unsaturated-group containing alkali developable resin is a value measured in the following way.
(1) 불포화기 함유 알칼리 현상성 수지 중의 수산기를 2-클로로-4,4,5,5-테트라메틸디옥사포스포란과 반응시켜 인 원자를 도입한다. [하기 식(1) 참조](1) A hydroxyl group in the unsaturated group-containing alkali developable resin is reacted with 2-chloro-4,4,5,5-tetramethyldioxaphosphorane to introduce a phosphorus atom. [Refer to formula (1) below]
(2) 시클로헥산올의 수산기를 2-클로로-4,4,5,5-테트라메틸디옥사포스포란과 반응시켜 인 원자를 도입하고, 이것을 내부 표준으로 한다. [하기 식(1) 참조](2) The hydroxyl group of cyclohexanol is reacted with 2-chloro-4,4,5,5-tetramethyldioxaphosphorane to introduce a phosphorus atom, and this is used as an internal standard. [Refer to formula (1) below]
(3) (1)에서 얻은 샘플에 (2)에서 얻은 내부 표준을 첨가하고, 하기 조건의 31P-NMR로 스펙트럼을 측정한다.(3) The internal standard obtained in (2) is added to the sample obtained in (1), and the spectrum is measured by 31P-NMR under the following conditions.
(4) 얻어진 31-NMR 스펙트럼의 피크 높이로부터 불포화기 함유 알칼리 현상성 수지의 수산기가를 산출한다.(4) The hydroxyl value of alkali developable resin containing an unsaturated group is computed from the peak height of the obtained 31-NMR spectrum.
[31P-NMR 측정 조건][31P-NMR measurement conditions]
장치명 : 니혼덴시샤제 『JNM-ECA500』Device name: JNM-ECA500 manufactured by Nippon Electronics Co., Ltd.
측정법 : 역게이트 부착 디커플링Measurement method: Decoupling with reverse gate
적산 횟수 : 2000회Integration count: 2000 times
시료 농도 : 약 40㎎/mlSample concentration: about 40 mg/ml
본 발명에서 사용하는 폴리에폭시 화합물(A)은, 일분자 중에 둘 이상의 에폭시기를 갖는 화합물이면, 어떠한 것도 이용할 수 있다. 구체적으로는, 비스페놀형 에폭시 수지, 페닐렌에테르형 에폭시 수지, 나프틸렌에테르형 에폭시 수지, 비페닐형 에폭시 수지, 페놀노볼락형 에폭시 수지, 크레졸노볼락형 에폭시 수지, 비스페놀노볼락형 에폭시 수지, 나프톨노볼락형 에폭시 수지, 나프톨-페놀 공축 노볼락형 에폭시 수지, 나프톨-크레졸 공축 노볼락형 에폭시 수지, 페놀아랄킬형 에폭시 수지, 나프톨아랄킬형 에폭시 수지, 디시클로펜타디엔-페놀 부가 반응형 에폭시 수지 등을 들 수 있다. 폴리에폭시 화합물(A)은 각각 단독으로 사용해도 되며, 2종류 이상을 병용해도 된다. 그 중에서도, 현상성, 및 경화물에 있어서의 내열성과 유전 특성이 우수한 불포화기 함유 알칼리 현상성 수지로 되므로, 페놀노볼락형 에폭시 수지, 크레졸노볼락형 에폭시 수지, 비스페놀노볼락형 에폭시 수지, 나프톨노볼락형 에폭시 수지, 나프톨-페놀 공축 노볼락형 에폭시 수지, 나프톨-크레졸 공축 노볼락형 에폭시 수지 등의 노볼락형 에폭시 수지가 바람직하다.Any polyepoxy compound (A) used in the present invention may be used as long as it is a compound having two or more epoxy groups in one molecule. Specifically, a bisphenol type epoxy resin, a phenylene ether type epoxy resin, a naphthylene ether type epoxy resin, a biphenyl type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a bisphenol novolak type epoxy resin, Naphthol novolak type epoxy resin, naphthol-phenol coaxial novolak type epoxy resin, naphthol-cresol coaxial novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin and the like. A polyepoxy compound (A) may be used independently, respectively, and may use 2 or more types together. Among them, since it is an alkali developable resin containing an unsaturated group having excellent developability and heat resistance and dielectric properties in the cured product, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol novolak type epoxy resin, naphthol Novolac-type epoxy resins, such as a novolak-type epoxy resin, a naphthol-phenol coaxial novolak-type epoxy resin, and a naphthol-cresol coaxial novolak-type epoxy resin, are preferable.
또한, 상기 폴리에폭시 화합물(A)은, 연화점이 50∼120℃의 범위인 것이 바람직하다.Moreover, it is preferable that the said polyepoxy compound (A) has a softening point in the range of 50-120 degreeC.
본 발명에서 사용하는 불포화 모노카르복시산(B)은, 일분자 중에 (메타)아크릴로일기와 카르복시기를 갖는 화합물을 들 수 있고, 예를 들면, 아크릴산이나, 메타크릴산을 들 수 있다. 불포화 모노카르복시산(B)은 각각 단독으로 사용해도 되며, 2종류 이상을 병용해도 된다.As for the unsaturated monocarboxylic acid (B) used by this invention, the compound which has a (meth)acryloyl group and a carboxy group in one molecule is mentioned, For example, acrylic acid and methacrylic acid are mentioned. An unsaturated monocarboxylic acid (B) may be used independently, respectively, and may use 2 or more types together.
본 발명에서 사용하는 불포화 모노카르복시산무수물(C)은, 일분자 중에 (메타)아크릴로일기와 카르복시기를 갖는 화합물의 산무수물을 들 수 있고, 예를 들면, 아크릴산무수물이나, 메타크릴산무수물 등을 들 수 있다. 불포화 모노카르복시산무수물(C)은 각각 단독으로 사용해도 되며, 2종류 이상을 병용해도 된다.The unsaturated monocarboxylic acid anhydride (C) used in the present invention includes an acid anhydride of a compound having a (meth)acryloyl group and a carboxyl group in one molecule, for example, acrylic acid anhydride, methacrylic acid anhydride, etc. can be heard An unsaturated monocarboxylic acid anhydride (C) may be used independently, respectively, and may use 2 or more types together.
본 발명에서 사용하는 디카르복시산무수물(D)은, 일분자 중에 두 카르복시기를 갖는 화합물의 산무수물이면, 어떠한 것도 이용할 수 있다. 구체적으로는 옥살산, 말론산, 숙신산, 글루타르산, 아디프산, 피멜산, 수베르산, 아젤라산, 세바스산, 말레산, 푸마르산, 프탈산, 이소프탈산, 테레프탈산, 테트라히드로프탈산, 헥사히드로프탈산, 메틸헥사히드로프탈산 등의 디카르복시산화합물의 산무수물을 들 수 있다. 디카르복시산무수물(D)은 각각 단독으로 사용해도 되며, 2종류 이상을 병용해도 된다. 그 중에서도, 경화물에 있어서의 내열성이 우수한 불포화기 함유 알칼리 현상성 수지로 되므로, 프탈산, 이소프탈산, 테레프탈산, 테트라히드로프탈산, 헥사히드로프탈산, 메틸헥사히드로프탈산 등, 분자 구조 중에 환상 구조를 갖는 것의 산무수물이 바람직하다.As the dicarboxylic acid anhydride (D) used in the present invention, any one can be used as long as it is an acid anhydride of a compound having two carboxyl groups in one molecule. Specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and acid anhydrides of dicarboxylic acid compounds such as methylhexahydrophthalic acid. The dicarboxylic acid anhydride (D) may be used independently, respectively, and may use 2 or more types together. Especially, since it becomes an alkali developable resin containing an unsaturated group excellent in heat resistance in the cured product, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, etc. having a cyclic structure in the molecular structure Acid anhydrides are preferred.
본 발명의 불포화기 함유 알칼리 현상성 수지는, 상기 폴리에폭시 화합물(A), 불포화 모노카르복시산(B), 불포화 모노카르복시산무수물(C), 및 디카르복시산무수물(D)을 필수의 원료로서 반응시켜서 얻어지는 분자 구조를 갖는다.The unsaturated group-containing alkali developable resin of the present invention is obtained by reacting the polyepoxy compound (A), unsaturated monocarboxylic acid (B), unsaturated monocarboxylic acid anhydride (C), and dicarboxylic acid anhydride (D) as essential raw materials. has a molecular structure.
상기 폴리에폭시 화합물(A), 불포화 모노카르복시산(B), 및 불포화 모노카르복시산무수물(C)의 반응 비율은, 폴리에폭시 화합물(A) 중의 에폭시기 1몰에 대하여, 불포화 모노카르복시산(B)과 불포화 모노카르복시산무수물(C)을 합계로 0.9∼1.1몰의 범위에서 사용하는 것이 바람직하다.The reaction ratio of the polyepoxy compound (A), the unsaturated monocarboxylic acid (B), and the unsaturated monocarboxylic acid anhydride (C) is, with respect to 1 mol of the epoxy group in the polyepoxy compound (A), the unsaturated monocarboxylic acid (B) and the unsaturated monocarboxylic acid (B) It is preferable to use the carboxylic acid anhydride (C) in the range of 0.9-1.1 mol in total.
또한, 얻어지는 불포화기 함유 알칼리 현상성 수지의 현상성과, 경화물에 있어서의 내열성 및 유전 특성과의 밸런스가 우수하므로, 상기 불포화 모노카르복시산(B)과 상기 불포화 모노카르복시산무수물(C)과의 몰비[(B)/(C)]의 값이, 0.5∼1.4의 범위인 것이 보다 바람직하다.In addition, since the balance between the developability of the obtained unsaturated group-containing alkali developable resin and the heat resistance and dielectric properties in the cured product is excellent, the molar ratio of the unsaturated monocarboxylic acid (B) to the unsaturated monocarboxylic acid anhydride (C) [ (B)/(C)], it is more preferable that it is the range of 0.5-1.4.
또한, 상기 디카르복시산무수물(D)의 반응 비율은, 상기 불포화물 카르복시산(B) 1몰에 대하여, 0.9∼1.1몰의 범위에서 사용하는 것이 바람직하다.Moreover, it is preferable to use the reaction ratio of the said dicarboxylic acid anhydride (D) in 0.9-1.1 mol with respect to 1 mol of the said unsaturated carboxylic acid (B).
본 발명에 있어서, 불포화기 함유 알칼리 현상성 수지의 각 원료 성분의 반응 방법은 특히 한정되지 않지만, 예를 들면, 우선, 상기 폴리에폭시 화합물(A), 불포화 모노카르복시산(B), 및 불포화 모노카르복시산무수물(C)을 반응시켜서 중간체(M)를 얻고, 다음으로, 상기 디카르복시산무수물(D)을 반응시키는 방법을 들 수 있다.In the present invention, the reaction method of each raw material component of the unsaturated group-containing alkali developable resin is not particularly limited, but for example, first, the polyepoxy compound (A), the unsaturated monocarboxylic acid (B), and the unsaturated monocarboxylic acid A method of reacting the anhydride (C) to obtain an intermediate (M) and then reacting the dicarboxylic acid anhydride (D) is mentioned.
상기 중간체(M)를 얻는 반응은, 예를 들면, 유기 용매 중, 에스테르화 반응 촉매와, 산화방지제, 중합금지제와의 존재 하에서, 100∼150℃의 온도 범위에서 5∼12시간 정도 반응시키는 방법을 들 수 있다.The reaction to obtain the intermediate (M) is, for example, in an organic solvent, in the presence of an esterification reaction catalyst, an antioxidant, and a polymerization inhibitor, in a temperature range of 100 to 150 ° C. for about 5 to 12 hours. method can be found.
다음으로, 얻어진 중간체(M)와 상기 디카르복시산무수물(D)과의 반응은, 예를 들면, 얻어진 중간체(M)를 함유하는 반응계 중에 디카르복시산무수물(D)을 첨가하고, 90∼120℃의 온도 범위에서 1∼5시간 정도 반응시키는 방법을 들 수 있다.Next, the reaction between the obtained intermediate (M) and the dicarboxylic acid anhydride (D) is performed, for example, by adding the dicarboxylic acid anhydride (D) to a reaction system containing the obtained intermediate (M), and heating the mixture at 90 to 120°C. A method of reacting in a temperature range for about 1 to 5 hours is exemplified.
본 발명의 불포화기 함유 알칼리 현상성 수지는, 분자 구조 중에 상기 불포화물 카르복시산(B)이나 상기 불포화 모노카르복시산무수물(C) 유래의 불포화기를 가지므로, 광중합개시제를 첨가함에 의해, 광경화형 알칼리 현상성 수지 조성물로 할 수 있다.Since the unsaturated group-containing alkali developable resin of the present invention has an unsaturated group derived from the unsaturated carboxylic acid (B) or the unsaturated monocarboxylic acid anhydride (C) in its molecular structure, by adding a photopolymerization initiator, photocurable alkali developability It can be set as a resin composition.
여기에서 사용하는 광중합개시제는, 예를 들면, 1-히드록시시클로헥실페닐케톤, 2-히드록시-2-메틸-1-페닐프로판-1-온, 1-〔4-(2-히드록시에톡시)페닐〕-2-히드록시-2-메틸-1-프로판-1-온, 티오잔톤 및 티오잔톤 유도체, 2,2'-디메톡시-1,2-디페닐에탄-1-온, 2,4,6-트리메틸벤조일디페닐포스핀옥사이드, 비스(2,4,6-트리메틸벤조일)페닐포스핀옥사이드, 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노-1-프로판온, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)-부탄-1-온 등을 들 수 있다.The photoinitiator used herein is, for example, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethyl Toxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, 2 ,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino -1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and the like.
이들 광중합개시제의 시판품은, 예를 들면, 「이르가큐어184」, 「이르가큐어149」, 「이르가큐어261」, 「이르가큐어369」, 「이르가큐어500」, 「이르가큐어651」, 「이르가큐어754」, 「이르가큐어784」, 「이르가큐어819」, 「이르가큐어907」, 「이르가큐어1116」, 「이르가큐어1664」, 「이르가큐어1700」, 「이르가큐어1800」, 「이르가큐어1850」, 「이르가큐어2959」, 「이르가큐어4043」, 「다로큐어1173」(치바스페셜티케미컬즈샤제), 「루시린TPO」(비에이에스에프사제), 「카야큐어DETX」, 「카야큐어MBP」, 「카야큐어DMBI」, 「카야큐어EPA」, 「카야큐어OA」(니혼가야쿠가부시키가이샤제), 「바이큐어10」, 「바이큐어55」(스토퍼·케미컬사제), 「트리고날P1」(아크조사제), 「산도레이1000」(산도즈사제), 「디프」(업존사제), 「퀀타큐어PDO」, 「퀀타큐어ITX」, 「퀀타큐어EPD」(워드플레킨솝사제) 등을 들 수 있다.Commercially available products of these photoinitiators are, for example, "Irgacure 184", "Irgacure 149", "Irgacure 261", "Irgacure 369", "Irgacure 500", "Irgacure" 651”, “Irgacure 754”, “Irgacure 784”, “Irgacure 819”, “Irgacure 907”, “Irgacure 1116”, “Irgacure 1664”, “Irgacure 1700” ”, “Irgacure 1800”, “Irgacure 1850”, “Irgacure 2959”, “Irgacure 4043”, “Darocure 1173” (Chiba Specialty Chemicals), “Lucirin TPO” (B. (manufactured by ASF), “Kaya Cure DETX”, “Kaya Cure MBP”, “Kaya Cure DMBI”, “Kaya Cure EPA”, “Kaya Cure OA” (manufactured by Nihon Kayaku Co., Ltd.), “Vicure 10” , "Vicure 55" (Stopper Chemicals), "Trigonal P1" (Arc Jojo), "Sandorei 1000" (Sandoz), "Def" (Upzone), "Quanta Cure PDO", " Quanta Cure ITX", "Quanta Cure EPD" (manufactured by Ward Plekin Soap), and the like.
상기 광중합개시제의 첨가량은, 예를 들면, 상기 알칼리 현상성 수지 100질량부에 대하여, 1∼20질량부의 범위에서 사용한다.The addition amount of the said photoinitiator is used in 1-20 mass parts with respect to 100 mass parts of said alkali developable resins, for example.
본 발명의 광경화형 알칼리 현상성 수지 조성물은, 이 외에, 무기 미립자나 폴리머 미립자, 안료, 소포제, 점도조정제, 레벨링제, 난연제, 보존안정화제 등의 각종 첨가제를 함유해도 된다.The photocurable alkali-developable resin composition of the present invention may contain, in addition, various additives such as inorganic fine particles, polymer fine particles, pigments, defoamers, viscosity modifiers, leveling agents, flame retardants and storage stabilizers.
본 발명의 불포화기 함유 알칼리 현상성 수지는, 높은 현상성을 갖고, 경화물에 있어서의 내열성과 유전 특성이 우수하므로, 솔더 레지스트 용도에 호적하게 사용할 수 있다.Since the unsaturated group containing alkali developable resin of this invention has high developability and is excellent in the heat resistance and dielectric characteristic in hardened|cured material, it can be used suitably for a soldering resist use.
본 발명의 솔더 레지스트용 수지 재료는, 예를 들면, 상기 불포화기 함유 알칼리 현상성 수지, 광중합개시제 및 각종 첨가제에 더하여, 경화제, 경화촉진제, 유기 용매 등의 각 성분을 포함해서 이루어진다.The resin material for soldering resists of this invention contains each component, such as a hardening|curing agent, a hardening accelerator, and an organic solvent, in addition to the said unsaturated group containing alkali developable resin, a photoinitiator, and various additives, for example.
상기 경화제는, 상기 불포화기 함유 알칼리 현상성 수지 중의 카르복시기와 반응할 수 있는 관능기를 갖는 것이면 특히 제한되지 않으며, 예를 들면, 에폭시 수지를 들 수 있다. 여기에서 사용하는 에폭시 수지는, 예를 들면, 비스페놀형 에폭시 수지, 페닐렌에테르형 에폭시 수지, 나프틸렌에테르형 에폭시 수지, 비페닐형 에폭시 수지, 트리페닐메탄형 에폭시 수지, 페놀노볼락형 에폭시 수지, 크레졸노볼락형 에폭시 수지, 비스페놀노볼락형 에폭시 수지, 나프톨노볼락형 에폭시 수지, 나프톨-페놀 공축 노볼락형 에폭시 수지, 나프톨-크레졸 공축 노볼락형 에폭시 수지, 페놀아랄킬형 에폭시 수지, 나프톨아랄킬형 에폭시 수지, 디시클로펜타디엔-페놀 부가 반응형 에폭시 수지 등을 들 수 있다. 이들은 각각 단독으로 사용해도 되며, 2종류 이상을 병용해도 된다. 이들 에폭시 수지 중에서도, 경화물에 있어서의 내열성이 우수하므로, 페놀노볼락형 에폭시 수지, 크레졸노볼락형 에폭시 수지, 비스페놀노볼락형 에폭시 수지, 나프톨노볼락형 에폭시 수지, 나프톨-페놀 공축 노볼락형 에폭시 수지, 나프톨-크레졸 공축 노볼락형 에폭시 수지 등의 노볼락형 에폭시 수지가 바람직하고, 연화점이 50∼120℃의 범위인 것이 특히 바람직하다.The curing agent is not particularly limited as long as it has a functional group capable of reacting with a carboxyl group in the unsaturated group-containing alkali developable resin, and examples thereof include an epoxy resin. The epoxy resin used here is, for example, a bisphenol type epoxy resin, a phenylene ether type epoxy resin, a naphthylene ether type epoxy resin, a biphenyl type epoxy resin, a triphenylmethane type epoxy resin, a phenol novolak type epoxy resin , cresol novolak type epoxy resin, bisphenol novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol coaxial novolak type epoxy resin, naphthol-cresol coaxial novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin A kill type epoxy resin, a dicyclopentadiene-phenol addition reaction type epoxy resin, etc. are mentioned. These may be used independently, respectively, and may use 2 or more types together. Among these epoxy resins, since the heat resistance in the cured product is excellent, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol coaxial novolak type epoxy resin Novolac-type epoxy resins, such as an epoxy resin and a naphthol-cresol coaxial novolak-type epoxy resin, are preferable, and it is especially preferable that the softening point is the range of 50-120 degreeC.
상기 경화촉진제는, 상기 경화제의 경화 반응을 촉진하는 것이고, 상기 경화제로서 에폭시 수지를 사용하는 경우에는, 인계 화합물, 제3급아민, 이미다졸, 유기산 금속염, 루이스산, 아민 착염 등을 들 수 있다. 이들은 각각 단독으로 사용해도 되며, 2종류 이상을 병용해도 된다. 경화촉진제의 첨가량은, 예를 들면, 상기 경화제 100질량부에 대하여 1∼10질량부의 범위에서 사용한다.The curing accelerator promotes the curing reaction of the curing agent, and when an epoxy resin is used as the curing agent, a phosphorus-based compound, a tertiary amine, imidazole, an organic acid metal salt, a Lewis acid, an amine complex salt, and the like. . These may be used independently, respectively, and may use 2 or more types together. The amount of the curing accelerator to be added is, for example, used in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the curing agent.
상기 유기 용매는, 상기 불포화기 함유 알칼리 현상성 수지나 경화제 등의 각종 성분을 용해할 수 있는 것이면 특히 한정되지 않으며, 예를 들면, 메틸에틸케톤, 아세톤, 디메틸포름아미드, 메틸이소부틸케톤, 메톡시프로판올, 시클로헥산온, 메틸셀로솔브, 디에틸렌글리콜모노에틸에테르아세테이트, 프로필렌글리콜모노메틸에테르아세테이트 등을 들 수 있다.The organic solvent is not particularly limited as long as it can dissolve various components such as the unsaturated group-containing alkali-developable resin and curing agent. For example, methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, and oxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate.
본 발명의 솔더 레지스트용 수지 재료를 사용해서 레지스트 부재를 얻는 방법은, 예를 들면, 상기 솔더 레지스트용 수지 재료를 기재 상에 도포하고, 60∼100℃ 정도의 온도 범위에서 유기 용제를 휘발 건조시킨 후, 원하는 패턴이 형성된 포토 마스크를 통해서 자외선이나 전자선 등으로 노광시키고, 알칼리 수용액으로 미노광부를 현상하고, 추가로 140∼180℃ 정도의 온도 범위에서 가열 경화시키는 방법을 들 수 있다.The method of obtaining a resist member using the resin material for soldering resists of this invention, for example, apply|coats the said resin material for soldering resists on a base material, The organic solvent is volatilized and dried in the temperature range of about 60-100 degreeC Then, there is a method of exposing it to ultraviolet rays or electron beams through a photomask having a desired pattern, developing the unexposed part with an aqueous alkali solution, and further heating and curing it in a temperature range of about 140 to 180°C.
(실시예) (Example)
이하에, 실시예 및 비교예를 들어서 본 발명을 보다 상세하게 설명한다.Hereinafter, an Example and a comparative example are given and this invention is demonstrated in more detail.
또, 실시예에서 얻은 불포화기 함유 알칼리 현상성 수지의 GPC 차트는, 하기 조건의 겔 투과 크로마토그래프(GPC)로 측정했다.In addition, the GPC chart of the unsaturated group containing alkali developable resin obtained in the Example was measured with the gel permeation chromatograph (GPC) of the following conditions.
측정 장치 : 도소가부시키가이샤제 「HLC-8220 GPC」,Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation,
칼럼 : 도소가부시키가이샤제 가드칼럼 「HXL-L」Column: Guard column “HXL-L” made by Tosoh Corporation
+도소가부시키가이샤제 「TSK-GEL G5000HXL」 + "TSK-GEL G5000HXL" made by Tosoh Corporation
+도소가부시키가이샤제 「TSK-GEL G4000HXL」 + "TSK-GEL G4000HXL" made by Tosoh Corporation
+도소가부시키가이샤제 「TSK-GEL G3000HXL」 + "TSK-GEL G3000HXL" made by Tosoh Corporation
+도소가부시키가이샤제 「TSK-GEL G2000HXL」 + "TSK-GEL G2000HXL" made by Tosoh Corporation
검출기 : RI(시차굴절계) Detector: RI (Differential Refractometer)
데이터 처리 : 도소가부시키가이샤제 「GPC-8020모델II 버전4.10」 Data processing: "GPC-8020 model II version 4.10" manufactured by Tosoh Corporation
측정 조건 : 칼럼 온도 40℃ Measurement conditions: Column temperature 40℃
전개 용매 테트라히드로퓨란 Developing solvent tetrahydrofuran
유속 1.0ml/분 Flow rate 1.0ml/min
표준 : 상기 「GPC-8020모델II 버전4.10」의 측정 매뉴얼에 준거해서, 분자량이 기지의 하기의 단분산 폴리스티렌을 사용했다. Standard: According to the measurement manual of "GPC-8020 Model II Version 4.10", the following monodisperse polystyrene with known molecular weight was used.
(사용 폴리스티렌)(use polystyrene)
도소가부시키가이샤제 「A-500」 "A-500" made by Tosoh Corporation
도소가부시키가이샤제 「A-1000」 "A-1000" made by Tosoh Corporation
도소가부시키가이샤제 「A-2500」 "A-2500" made by Tosoh Corporation
도소가부시키가이샤제 「A-5000」 "A-5000" made by Tosoh Corporation
도소가부시키가이샤제 「F-1」 Tosoh Corporation "F-1"
도소가부시키가이샤제 「F-2」 "F-2" made by Tosoh Corporation
도소가부시키가이샤제 「F-4」 "F-4" made by Tosoh Corporation
도소가부시키가이샤제 「F-10」 "F-10" made by Tosoh Corporation
도소가부시키가이샤제 「F-20」 "F-20" made by Tosoh Corporation
도소가부시키가이샤제 「F-40」 Tosoh Corporation "F-40"
도소가부시키가이샤제 「F-80」 Tosoh Corporation "F-80"
도소가부시키가이샤제 「F-128」 "F-128" made by Tosoh Corporation
시료 : 수지 고형분 환산으로 1.0질량%의 테트라히드로퓨란 용액을 마이크로 필터로 여과한 것(50μl). Sample: A 1.0 mass % tetrahydrofuran solution in terms of resin solid content was filtered with a microfilter (50 μl).
본원 실시예에 있어서 불포화기 함유 알칼리 현상성 수지의 산가는 JIS K 0070(1992)의 중화 적정법으로 측정했다.The acid value of the alkali developable resin containing an unsaturated group in the Example of this application was measured by the neutralization titration method of JISK0070 (1992).
본원 실시예에 있어서 불포화기 함유 알칼리 현상성 수지의 수산기가는 하기의 요령으로 측정했다.In the Examples of the present application, the hydroxyl value of the unsaturated group-containing alkali developable resin was measured in the following manner.
(1) 불포화기 함유 알칼리 현상성 수지 중의 수산기를 2-클로로-4,4,5,5-테트라메틸디옥사포스포란과 반응시켜 인 원자를 도입한다.(1) A hydroxyl group in the unsaturated group-containing alkali developable resin is reacted with 2-chloro-4,4,5,5-tetramethyldioxaphosphorane to introduce a phosphorus atom.
(2) 내부 표준으로서 시클로헥산올의 수산기를 2-클로로-4,4,5,5-테트라메틸디옥사포스포란과 반응시켜 인 원자를 도입한 것을 준비한다.(2) As an internal standard, a phosphorus atom is prepared by reacting the hydroxyl group of cyclohexanol with 2-chloro-4,4,5,5-tetramethyldioxaphosphorane.
(3) (1)에서 얻은 샘플에 (2)에서 얻은 내부 표준을 첨가하고, 하기 조건의 31P-NMR로 스펙트럼을 측정한다.(3) The internal standard obtained in (2) is added to the sample obtained in (1), and the spectrum is measured by 31P-NMR under the following conditions.
(4) 얻어진 31-NMR 스펙트럼의 피크 높이로부터 불포화기 함유 알칼리 현상성 수지의 수산기가를 산출한다.(4) The hydroxyl value of alkali developable resin containing an unsaturated group is computed from the peak height of the obtained 31-NMR spectrum.
[31P-NMR 측정 조건][31P-NMR measurement conditions]
장치명 : 니혼덴시샤제 『JNM-ECA500』Device name: JNM-ECA500 manufactured by Nippon Electronics Co., Ltd.
측정법 : 역게이트 부착 디커플링Measurement method: Decoupling with reverse gate
적산 횟수 : 2000회Integration count: 2000 times
시료 농도 : 약 40㎎/mlSample concentration: about 40 mg/ml
실시예 1 불포화기 함유 알칼리 현상성 수지(1)의 제조Example 1 Preparation of unsaturated group-containing alkali developable resin (1)
온도계, 교반기, 및 환류 냉각기를 구비한 플라스크에, 디에틸렌글리콜모노에틸에테르아세테이트 114질량부를 넣고, 오르토크레졸노볼락형 에폭시 수지(DIC가부시키가이샤제 『EPICLON N-680』 에폭시 당량 214g/당량, 연화점 86℃) 428질량부를 용해시키고, 산화방지제로서 디부틸히드록시톨루엔 4.5질량부, 열중합금지제로서 메토퀴논 0.5질량부를 더한 후, 아크릴산 85질량부, 무수메타크릴산(순도 94질량%) 134질량부, 트리페닐포스핀 1.8질량부를 첨가하고, 공기를 불어넣으면서 120℃에서 10시간 반응시켰다. 다음으로, 디에틸렌글리콜모노에틸에테르아세테이트 240질량부, 테트라히드로무수프탈산 179질량부를 더하고, 110℃에서 2.5시간 반응시켜, 불포화기 함유 알칼리 현상성 수지(1) 용액(고형분 70질량%)을 얻었다. 불포화기 함유 알칼리 현상성 수지(1)의 고형분 산가는 80mgKOH/g, 수산기가는 18.5mgKOH/g이었다. 또, 아크릴산(B)과 무수메타크릴산(C)과의 몰비[(B)/(C)]는 1.36이었다.In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 114 parts by mass of diethylene glycol monoethyl ether acetate was put, After dissolving 428 parts by mass (softening point 86°C), 4.5 parts by mass of dibutylhydroxytoluene as an antioxidant, and 0.5 parts by mass of metoquinone as a thermal polymerization inhibitor, 85 parts by mass of acrylic acid and methacrylic anhydride (purity 94% by mass) 134 It was made to react at 120 degreeC for 10 hours, adding mass part and 1.8 mass parts of triphenylphosphine, and blowing in air. Next, 240 mass parts of diethylene glycol monoethyl ether acetate and 179 mass parts of tetrahydrophthalic anhydride were added, it was made to react at 110 degreeC for 2.5 hours, and the unsaturated group containing alkali developable resin (1) solution (70 mass % solid content) was obtained. . The solid content acid value of unsaturated group containing alkali developable resin (1) was 80 mgKOH/g, and the hydroxyl value was 18.5 mgKOH/g. Moreover, the molar ratio [(B)/(C)] of acrylic acid (B) and methacrylic acid anhydride (C) was 1.36.
실시예 2 불포화기 함유 알칼리 현상성 수지(2)의 제조Example 2 Preparation of unsaturated group-containing alkali developable resin (2)
온도계, 교반기, 및 환류 냉각기를 구비한 플라스크에, 디에틸렌글리콜모노에틸에테르아세테이트 106질량부를 넣고, 비스페놀F노볼락형 에폭시 수지(DIC가부시키가이샤제 『EPICLON N-570』 에폭시 당량 187g/당량, 연화점 68℃) 374질량부를 용해시키고, 산화방지제로서 디부틸히드록시톨루엔 4.2질량부, 열중합금지제로서 메토퀴논 0.4질량부를 더한 후, 아크릴산 79질량부, 무수메타크릴산(순도 94질량%) 148질량부, 트리페닐포스핀 1.6질량부를 첨가하고, 공기를 불어넣으면서 120℃에서 10시간 반응시켰다. 다음으로, 디에틸렌글리콜모노에틸에테르아세테이트 223질량부, 테트라히드로무수프탈산 167질량부를 더하고, 110℃에서 2.5시간 반응시켜, 불포화기 함유 알칼리 현상성 수지(2) 용액(고형분 70질량%)을 얻었다. 불포화기 함유 알칼리 현상성 수지(2)의 고형분 산가는 80mgKOH/g, 수산기가는 16.3mgKOH/g이었다. 또, 아크릴산(B)과 무수메타크릴산(C)과의 몰비[(B)/(C)]는 1.14였다.In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 106 parts by mass of diethylene glycol monoethyl ether acetate was put, and bisphenol F novolac type epoxy resin (“EPICLON N-570” manufactured by DIC Corporation, epoxy equivalent 187 g/equivalent, After dissolving 374 parts by mass (softening point 68°C) and adding 4.2 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of metoquinone as a thermal polymerization inhibitor, 79 parts by mass of acrylic acid and methacrylic anhydride (purity 94% by mass) 148 It was made to react at 120 degreeC for 10 hours, adding mass part and 1.6 mass parts of triphenylphosphine, and blowing in air. Next, 223 mass parts of diethylene glycol monoethyl ether acetate and 167 mass parts of tetrahydrophthalic anhydride were added, it was made to react at 110 degreeC for 2.5 hours, and the unsaturated group containing alkali developable resin (2) solution (solid content 70 mass %) was obtained. . The solid content acid value of unsaturated group containing alkali developable resin (2) was 80 mgKOH/g, and the hydroxyl value was 16.3 mgKOH/g. Moreover, the molar ratio [(B)/(C)] of acrylic acid (B) and methacrylic acid anhydride (C) was 1.14.
실시예 3 불포화기 함유 알칼리 현상성 수지(3)의 제조Example 3 Preparation of unsaturated group-containing alkali developable resin (3)
온도계, 교반기, 및 환류 냉각기를 구비한 플라스크에, 디에틸렌글리콜모노에틸에테르아세테이트 162질량부를 넣고, 오르토크레졸노볼락형 에폭시 수지(DIC가부시키가이샤제 『EPICLON N-695』 에폭시 당량 215g/당량, 연화점 97℃) 430질량부를 용해시키고, 산화방지제로서 디부틸히드록시톨루엔 1.6질량부, 열중합금지제로서 하이드로퀴논 0.3질량부를 더한 후, 아크릴산 85질량부, 무수메타크릴산(순도 94질량%) 134질량부, 트리페닐포스핀 3.2질량부를 첨가하고, 공기를 불어넣으면서 120℃에서 8시간 반응시켰다. 다음으로, 디에틸렌글리콜모노에틸에테르아세테이트 284질량부, 테트라히드로무수프탈산 179질량부를 더하고, 110℃에서 2.5시간 반응시켜 불포화기 함유 알칼리 현상성 수지(3) 용액(고형분 65질량%)을 얻었다. 불포화기 함유 알칼리 현상성 수지(3)의 고형분 산가는 80mgKOH/g, 수산기가는 12.3mgKOH/g이었다. 또, 아크릴산(B)과 무수메타크릴산(C)과의 몰비[(B)/(C)]는 1.36이었다.In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 162 parts by mass of diethylene glycol monoethyl ether acetate was put, and an orthocresol novolak type epoxy resin ("EPICLON N-695" manufactured by DIC Corporation, epoxy equivalent 215 g/equivalent, softening point 97°C) 430 parts by mass were dissolved, and after adding 1.6 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.3 parts by mass of hydroquinone as a thermal polymerization inhibitor, 85 parts by mass of acrylic acid and methacrylic anhydride (purity 94% by mass) 134 It was made to react at 120 degreeC for 8 hours, adding mass part and 3.2 mass parts of triphenylphosphine, and blowing in air. Next, 284 mass parts of diethylene glycol monoethyl ether acetate and 179 mass parts of tetrahydrophthalic anhydride were added, it was made to react at 110 degreeC for 2.5 hours, and the unsaturated group containing alkali developable resin (3) solution (65 mass % solid content) was obtained. The solid content acid value of unsaturated group containing alkali developable resin (3) was 80 mgKOH/g, and the hydroxyl value was 12.3 mgKOH/g. Moreover, the molar ratio [(B)/(C)] of acrylic acid (B) and methacrylic acid anhydride (C) was 1.36.
실시예 4 불포화기 함유 알칼리 현상성 수지(4)의 제조Example 4 Preparation of unsaturated group-containing alkali developable resin (4)
온도계, 교반기, 및 환류 냉각기를 구비한 플라스크에, 디에틸렌글리콜모노에틸에테르아세테이트 168질량부를 넣고, 오르토크레졸노볼락형 에폭시 수지(DIC가부시키가이샤제 『EPICLON N-695』 에폭시 당량 215g/당량, 연화점 97℃) 430질량부를 용해시키고, 산화방지제로서 디부틸히드록시톨루엔 1.7질량부, 열중합금지제로서 하이드로퀴논 0.3질량부를 더한 후, 아크릴산 68질량부, 무수메타크릴산(순도 94질량%) 174질량부, 트리페닐포스핀 3.4질량부를 첨가하고, 공기를 불어넣으면서 120℃에서 8시간 반응시켰다. 다음으로, 디에틸렌글리콜모노에틸에테르아세테이트 271질량부, 테트라히드로무수프탈산 143질량부를 더하고, 110℃에서 2.5시간 반응시켜, 불포화기 함유 알칼리 현상성 수지(4) 용액(고형분 65질량%)을 얻었다. 불포화기 함유 알칼리 현상성 수지(4)의 고형분 산가는 65mgKOH/g, 수산기가는 14.0mgKOH/g이었다. 또, 아크릴산(B)과 무수메타크릴산(C)과의 몰비[(B)/(C)]는 0.84였다.In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 168 parts by mass of diethylene glycol monoethyl ether acetate was put, softening point 97°C) 430 parts by mass was dissolved, and 1.7 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.3 parts by mass of hydroquinone as a thermal polymerization inhibitor were added, followed by 68 parts by mass of acrylic acid and methacrylic anhydride (purity 94% by mass) 174 It was made to react at 120 degreeC for 8 hours, adding mass part and 3.4 mass parts of triphenylphosphine, and blowing in air. Next, 271 mass parts of diethylene glycol monoethyl ether acetate and 143 mass parts of tetrahydrophthalic anhydride were added, and it was made to react at 110 degreeC for 2.5 hours, and the unsaturated group containing alkali developable resin (4) solution (65 mass % of solid content) was obtained. . The solid content acid value of unsaturated group containing alkali developable resin (4) was 65 mgKOH/g, and the hydroxyl value was 14.0 mgKOH/g. Moreover, the molar ratio [(B)/(C)] of acrylic acid (B) and methacrylic acid anhydride (C) was 0.84.
실시예 5 불포화기 함유 알칼리 현상성 수지(5)의 제조Example 5 Preparation of unsaturated group-containing alkali developable resin (5)
온도계, 교반기, 및 환류 냉각기를 구비한 플라스크에, 디에틸렌글리콜모노에틸에테르아세테이트 173질량부를 넣고, 오르토크레졸노볼락형 에폭시 수지(DIC가부시키가이샤 『EPICLON N-695』 에폭시 당량 215g/당량, 연화점 97℃) 430질량부를 용해시키고, 산화방지제로서 디부틸히드록시톨루엔 1.7질량부, 열중합금지제로서 하이드로퀴논 0.3질량부를 더한 후, 아크릴산 52질량부, 무수메타크릴산(순도 94질량%) 210질량부, 트리페닐포스핀 3.5질량부를 첨가하고, 공기를 불어넣으면서 120℃에서 8시간 반응시켰다. 다음으로, 디에틸렌글리콜모노에틸에테르아세테이트 258질량부, 테트라히드로무수프탈산 109질량부를 더하고, 110℃에서 2.5시간 반응시켜, 불포화기 함유 알칼리 현상성 수지(5) 용액(고형분 65질량%)을 얻었다. 불포화기 함유 알칼리 현상성 수지(5)의 고형분 산가는 50mgKOH/g, 수산기가는 14.0mgKOH/g이었다. 또, 아크릴산(B)과 무수메타크릴산(C)과의 몰비[(B)/(C)]는 0.53이었다.In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 173 parts by mass of diethylene glycol monoethyl ether acetate was put, and an orthocresol novolak type epoxy resin (DIC Corporation "EPICLON N-695" epoxy equivalent 215 g/equivalent, softening point) 97°C) 430 parts by mass was dissolved, and 1.7 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.3 parts by mass of hydroquinone as a thermal polymerization inhibitor were added, followed by 52 parts by mass of acrylic acid and 210 parts by mass of methacrylic anhydride (purity 94% by mass). Part and 3.5 mass parts of triphenylphosphine were added, and it was made to react at 120 degreeC for 8 hours, blowing in air. Next, 258 mass parts of diethylene glycol monoethyl ether acetate and 109 mass parts of tetrahydrophthalic anhydride were added, and it was made to react at 110 degreeC for 2.5 hours, and the unsaturated group containing alkali developable resin (5) solution (65 mass % of solid content) was obtained. . The solid content acid value of unsaturated group containing alkali developable resin (5) was 50 mgKOH/g, and the hydroxyl value was 14.0 mgKOH/g. Moreover, the molar ratio [(B)/(C)] of acrylic acid (B) and methacrylic acid anhydride (C) was 0.53.
비교제조예 1 불포화기 함유 알칼리 현상성 수지(1')의 제조Comparative Preparation Example 1 Preparation of unsaturated group-containing alkali developable resin (1')
온도계, 교반기, 및 환류 냉각기를 구비한 플라스크에, 디에틸렌글리콜모노에틸에테르아세테이트 101질량부를 넣고, 오르토크레졸노볼락형 에폭시 수지(DIC가부시키가이샤제 『EPICLON N-680』 에폭시 당량 214g/당량) 428질량부를 용해시키고, 산화방지제로서 디부틸히드록시톨루엔 4질량부, 열중합금지제로서 메토퀴논 0.4질량부를 더한 후, 아크릴산 144질량부, 트리페닐포스핀 1.6질량부를 첨가하고, 공기를 불어넣으면서 120℃에서 10시간 반응시켰다. 다음으로, 디에틸렌글리콜모노에틸에테르아세테이트 311질량부, 테트라히드로무수프탈산 160질량부를 더하고 110℃에서 2.5시간 반응시켜, 불포화기 함유 알칼리 현상성 수지(1') 용액(고형분 64질량%)을 얻었다. 불포화기 함유 알칼리 현상성 수지(1')의 고형분 산가는 85mgKOH/g이었다.In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 101 parts by mass of diethylene glycol monoethyl ether acetate was put, and an orthocresol novolak-type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation, epoxy equivalent 214 g/equivalent) After dissolving 428 parts by mass and adding 4 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of metoquinone as a thermal polymerization inhibitor, 144 parts by mass of acrylic acid and 1.6 parts by mass of triphenylphosphine are added, while blowing air 120 It was reacted at ℃ for 10 hours. Next, 311 mass parts of diethylene glycol monoethyl ether acetate and 160 mass parts of tetrahydrophthalic anhydride were added, it was made to react at 110 degreeC for 2.5 hours, and the unsaturated group containing alkali developable resin (1') solution (solid content 64 mass %) was obtained. . The solid content acid value of unsaturated group containing alkali developable resin (1') was 85 mgKOH/g.
비교제조예 2 불포화기 함유 알칼리 현상성 수지(2')의 제조Comparative Preparation Example 2 Preparation of unsaturated group-containing alkali developable resin (2')
온도계, 교반기, 및 환류 냉각기를 구비한 플라스크에, 디에틸렌글리콜모노에틸에테르아세테이트 157질량부를 넣고, 오르토크레졸노볼락형 에폭시 수지(DIC가부시키가이샤제 『EPICLON N-695』 에폭시 당량 215g/당량) 430질량부를 용해하고, 산화방지제로서 디부틸히드록시톨루엔 1.6질량부, 열중합금지제로서 하이드로퀴논 0.3질량부를 더한 후, 아크릴산 101질량부, 무수메타크릴산(순도 94질량%) 98질량부, 트리페닐포스핀 3.1질량부를 첨가하고, 공기를 불어넣으면서 120℃에서 8시간 반응시켰다. 다음으로, 디에틸렌글리콜모노에틸에테르아세테이트 280질량부, 테트라히드로무수프탈산 182질량부를 더하고 110℃에서 2.5시간 반응시켜, 불포화기 함유 알칼리 현상성 수지(2') 용액(고형분 65질량%)을 얻었다. 불포화기 함유 알칼리 현상성 수지(2')의 고형분 산가는 85mgKOH/g, 수산기가는 19.2mgKOH/g이었다. 또, 아크릴산(B)과 무수메타크릴산(C)과의 몰비[(B)/(C)]는 2.20이었다.In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 157 parts by mass of diethylene glycol monoethyl ether acetate was put, and an orthocresol novolak type epoxy resin ("EPICLON N-695" manufactured by DIC Corporation, epoxy equivalent 215 g/equivalent) After dissolving 430 parts by mass and adding 1.6 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.3 parts by mass of hydroquinone as a thermal polymerization inhibitor, 101 parts by mass of acrylic acid, 98 parts by mass of methacrylic anhydride (purity 94% by mass), tri 3.1 mass parts of phenylphosphine was added, and it was made to react at 120 degreeC for 8 hours, blowing in air. Next, 280 mass parts of diethylene glycol monoethyl ether acetate and 182 mass parts of tetrahydrophthalic anhydride were added, and it was made to react at 110 degreeC for 2.5 hours, and the unsaturated group containing alkali developable resin (2') solution (solid content 65 mass %) was obtained. . The solid content acid value of unsaturated group containing alkali developable resin (2') was 85 mgKOH/g, and the hydroxyl value was 19.2 mgKOH/g. Moreover, the molar ratio [(B)/(C)] of acrylic acid (B) and methacrylic acid anhydride (C) was 2.20.
실시예 6 현상성의 평가Example 6 Evaluation of developability
하기 요령으로 광경화형 알칼리 현상성 수지 조성물(1-1)을 조제하여, 현상성의 평가로서, 광감도와 건조 관리폭을 평가했다.The photocurable alkali developable resin composition (1-1) was prepared in the following way, and the photosensitivity and dry management width were evaluated as developability evaluation.
◆광경화형 알칼리 현상성 수지 조성물의 조제Preparation of photocurable alkali developable resin composition
실시예 1에서 얻은 불포화기 함유 알칼리 현상성 수지(1) 용액 100질량부, 경화제로서 오르토크레졸노볼락형 에폭시 수지(DIC가부시키가이샤제 『EPICLON N-680』) 24질량부, 광중합개시제로서 2-메틸-1-(4-메틸티오페닐)-2-모르폴리노프로판-1-온(BASF사제 『이르가큐어907』) 5.0질량부, 경화촉진제로서 2-에틸-4-메틸이미다졸 0.5질량부, 유기 용제로서 디에틸렌글리콜모노에틸에테르아세테이트 13질량부, 안료로서 프탈로시아닌그린 0.65질량부를 배합하고, 롤 밀에 의해 혼련(混練)해서 광경화형 알칼리 현상성 수지 조성물(1-1)을 얻었다.100 parts by mass of the solution of the unsaturated group-containing alkali developable resin (1) obtained in Example 1, 24 parts by mass of an orthocresol novolak-type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation) as a curing agent, 2 as a photoinitiator -Methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one ("Irgacure 907" manufactured by BASF) 5.0 parts by mass, 2-ethyl-4-methylimidazole as a curing accelerator 0.5 parts by mass, 13 parts by mass of diethylene glycol monoethyl ether acetate as an organic solvent, and 0.65 parts by mass of phthalocyanine green as a pigment were blended, and kneaded with a roll mill to obtain a photocurable alkali developable resin composition (1-1) got it
◆광감도의 측정Measurement of light sensitivity
유리 기재 상에 앞서 얻은 광경화형 알칼리 현상성 수지 조성물(1-1)을 50㎛의 애플리케이터로 도포하고, 80℃에서 30분 건조시켰다. 다음으로, 코닥사제의 스텝 태블릿 No.2를 개재하고, 메탈할라이드 램프를 사용해서 750mJ/㎠의 자외선을 조사했다. 이것을 1질량%의 탄산나트륨 수용액으로 180초 현상하고, 잔존한 단수(段數)로 평가했다. 잔존 단수가 많을수록 광감도가 높다.The photocurable alkali-developable resin composition (1-1) obtained previously on a glass substrate was apply|coated with a 50-micrometer applicator, and it dried at 80 degreeC for 30 minutes. Next, 750 mJ/cm<2> ultraviolet-ray was irradiated using the metal halide lamp through step tablet No. 2 by Kodak company. This was developed for 180 second with a 1 mass % sodium carbonate aqueous solution, and it evaluated by the residual water level. The more the number of remaining stages, the higher the photosensitivity.
◆건조 관리폭의 측정Measurement of dry management width
유리 기재 상에 앞서 얻은 광경화형 알칼리 현상성 수지 조성물(1-1)을 50㎛의 애플리케이터로 도포하고, 80℃에서의 건조 시간이 각각 30분, 40분, 50분, 60분인 샘플을 작성했다. 이들을 1질량%의 탄산나트륨 수용액으로 180초 현상하고, 잔사가 남지 않은 샘플의 80℃ 건조 시간을 건조 관리폭으로서 평가했다. 건조 관리폭이 길수록 알칼리 현상성이 우수하다.The photocurable alkali-developable resin composition (1-1) obtained earlier was applied on a glass substrate with an applicator of 50 µm, and samples having drying times at 80°C of 30 minutes, 40 minutes, 50 minutes, and 60 minutes were prepared, respectively. . These were developed for 180 second with a 1 mass % sodium carbonate aqueous solution, and the 80 degreeC drying time of the sample which a residue does not remain was evaluated as a drying control range. The longer the drying range, the better the alkali developability.
실시예 7∼10 및 비교예 1, 2Examples 7 to 10 and Comparative Examples 1 and 2
실시예 1과 같은 요령으로 광경화형 알칼리 현상성 수지 조성물(2-1)∼(5-1) 및 (1'-1), (2'-1)을 제작하여, 광감도와 건조 관리폭을 측정했다. 결과를 표 1에 나타냈다.In the same manner as in Example 1, photocurable alkali-developable resin compositions (2-1) to (5-1) and (1'-1) and (2'-1) were prepared, and photosensitivity and dry control width were measured. did. The results are shown in Table 1.
[표 1] [Table 1]
실시예 11 경화물의 평가Example 11 Evaluation of cured product
하기 요령으로 광경화형 알칼리 현상성 수지 조성물(1-2)을 조제하여, 경화물의 내열성과 유전 특성을 평가했다.The photocurable alkali developable resin composition (1-2) was prepared in the following way, and the heat resistance and dielectric characteristic of hardened|cured material were evaluated.
◆광경화형 알칼리 현상성 수지 조성물의 조제Preparation of photocurable alkali developable resin composition
실시예 1에서 얻은 불포화기 함유 알칼리 현상성 수지(1) 용액 100질량부, 경화제로서 오르토크레졸노볼락형 에폭시 수지(DIC가부시키가이샤제 『EPICLON N-680』) 24질량부, 광중합개시제로서 2-메틸-1-(4-메틸티오페닐)-2-모르폴리노프로판-1-온(BASF사제 『이르가큐어907』) 5.0질량부, 경화촉진제로서 2-에틸-4-메틸이미다졸 0.5질량부, 유기 용제로서 디에틸렌글리콜모노에틸에테르아세테이트 13질량부를 배합하고, 롤 밀에 의해 혼련해서 광경화형 알칼리 현상성 수지 조성물(1-2)을 얻었다.100 parts by mass of the solution of the unsaturated group-containing alkali developable resin (1) obtained in Example 1, 24 parts by mass of an orthocresol novolak-type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation) as a curing agent, 2 as a photoinitiator -Methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one ("Irgacure 907" manufactured by BASF) 5.0 parts by mass, 2-ethyl-4-methylimidazole as a curing accelerator As 0.5 mass parts and an organic solvent, 13 mass parts of diethylene glycol monoethyl ether acetate was mix|blended, it knead|mixed with the roll mill, and the photocurable alkali developable resin composition (1-2) was obtained.
◆경화물의 작성Making hardened material
유리 기재 상에 앞서 얻은 광경화형 알칼리 현상성 수지 조성물(1-2)을 76㎛의 애플리케이터로 도포하고, 80℃에서 30분간 건조시켰다. 다음으로, 메탈할라이드 램프를 사용해서 750mJ/㎠의 자외선을 조사한 후, 150℃에서 1시간 가열하고, 경화물을 유리 기재로부터 박리하여, 경화물(1)을 얻었다.The photocurable alkali-developable resin composition (1-2) obtained previously on a glass substrate was apply|coated with a 76 micrometers applicator, and it dried at 80 degreeC for 30 minutes. Next, after irradiating the ultraviolet-ray of 750 mJ/cm<2> using the metal halide lamp, it heated at 150 degreeC for 1 hour, the hardened|cured material was peeled from the glass base material, and the hardened|cured material (1) was obtained.
◆내열성의 평가Evaluation of heat resistance
경화물(1)로부터 6㎜×35㎜의 시험편을 잘라내어, 점탄성 측정 장치(DMA : 레오매트릭스샤제 고체 점탄성 측정 장치 「RSAII」, 인장법 : 주파수 1Hz, 승온 속도 3℃/분)를 사용해서, 탄성율 변화가 최대로 되는(tanδ 변화율이 가장 큰) 온도를 유리 전이 온도로서 평가했다.A 6 mm x 35 mm test piece was cut out from the cured product 1, and using a viscoelasticity measuring device (DMA: Rheomatrix Co., Ltd. solid viscoelasticity measuring device “RSAII”, tensile method: frequency 1 Hz, temperature increase rate 3 ° C./min), The temperature at which the change in the elastic modulus becomes maximum (the rate of change in tan δ is greatest) was evaluated as the glass transition temperature.
◆유전 특성의 평가Evaluation of genetic characteristics
애질런트·테크놀로지가부시키가이샤제 임피던스·머티리얼·애널라이저 「HP4291B」에 의해, 절건(絶乾) 후 23℃, 습도 50%의 실내에 24시간 보관한 후의 경화물(1)의 1GHz에서의 유전율 및 유전정접을 용량법에 의해 측정했다.The dielectric constant at 1 GHz of the cured product (1) at 1 GHz after being stored for 24 hours at 23° C. and 50% humidity after being thoroughly dried by an impedance material analyzer “HP4291B” manufactured by Agilent Technology Co., Ltd. The dielectric loss tangent was measured by the capacitance method.
실시예 12∼15 및 비교예 3, 4Examples 12 to 15 and Comparative Examples 3 and 4
실시예 1과 같은 요령으로 광경화형 알칼리 현상성 수지 조성물(2-2)∼(5-2) 및 (1'-2), (2'-2)을 제작하여, 경화물의 내열성과 유전 특성을 평가했다. 결과를 표 2에 나타냈다.In the same manner as in Example 1, photocurable alkali-developable resin compositions (2-2) to (5-2) and (1'-2) and (2'-2) were prepared, and the heat resistance and dielectric properties of the cured product were tested. evaluated. The results are shown in Table 2.
[표 2] [Table 2]
Claims (7)
상기 폴리에폭시 화합물(A)이, 노볼락형 에폭시 수지(A1)인 불포화기 함유 알칼리 현상성 수지.The method of claim 1,
The said polyepoxy compound (A) is an unsaturated group containing alkali developable resin whose novolak-type epoxy resin (A1).
상기 불포화카르복시산(B)과 상기 불포화카르복시산무수물(C)과의 몰비[(B)/(C)]의 값이, 0.5∼1.4의 범위인 불포화기 함유 알칼리 현상성 수지.The method of claim 1,
An unsaturated group-containing alkali developable resin wherein the value of the molar ratio [(B)/(C)] of the unsaturated carboxylic acid (B) to the unsaturated carboxylic acid anhydride (C) is in the range of 0.5 to 1.4.
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