KR20080066845A - Photosensitive composition, phososensitive film, permanent pattern, and method for formation of the permanent pattern - Google Patents
Photosensitive composition, phososensitive film, permanent pattern, and method for formation of the permanent pattern Download PDFInfo
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- KR20080066845A KR20080066845A KR1020087013225A KR20087013225A KR20080066845A KR 20080066845 A KR20080066845 A KR 20080066845A KR 1020087013225 A KR1020087013225 A KR 1020087013225A KR 20087013225 A KR20087013225 A KR 20087013225A KR 20080066845 A KR20080066845 A KR 20080066845A
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- South Korea
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- compound
- photosensitive
- mass
- film
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- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- 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
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- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
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Abstract
Description
본 발명은 보존시의 상온 하에서는 반응을 일으키지 않고, 가열에 의해 가교반응을 개시하고, 경화막의 양호한 막경도가 얻어지는 화합물을 함유하고, UV 노광에 의해 화상 형성가능하고, 표면의 택성(tacking property)이 작고, 라미네이트성 및 취급성이 양호하고, 보존 안정성이 우수하고, 고감도로 현상성도 우수하고, 현상 후에 우수한 내약품성, 표면 경도, 내열성, 유전 특성, 전기 절연성 등을 발현하는 감광성 조성물, 및 이것을 사용한 감광성 필름 및 고 정밀한 영구 패턴(보호막, 층간 절연막, 솔더 레지스트 패턴 등) 및 그 효율적인 형성 방법에 관한 것이다.The present invention contains a compound which does not cause a reaction at normal temperature at the time of storage, initiates a crosslinking reaction by heating, obtains a good film hardness of a cured film, is imageable by UV exposure, and has a tacking property on the surface. This small, good lamination and handling property, excellent storage stability, high sensitivity and developability, and after the development, a photosensitive composition expressing excellent chemical resistance, surface hardness, heat resistance, dielectric properties, electrical insulation, and the like, and It relates to a used photosensitive film and a high-precision permanent pattern (protective film, interlayer insulating film, solder resist pattern, etc.) and an efficient forming method thereof.
프린트 배선 기판의 분야에서는 반도체나 콘덴서, 저항 등의 부품이 프린트 배선 기판 상에 납땜된다. 이 경우, 예를 들면 IR 리플로우 등의 솔더링 공정에 있어서, 땜납이 납땜의 불필요한 부분에 부착되는 것을 방지하기 위해서, 보호막, 절연막으로서, 상기 납땜의 불필요 부분에 해당하는 영구 패턴을 형성하는 방법이 채용되고 있다. 또한 보호막의 영구 패턴으로서는 솔더 레지스트가 바람직하게 사용 되고 있다.In the field of a printed wiring board, components such as a semiconductor, a capacitor, and a resistor are soldered onto the printed wiring board. In this case, for example, in the soldering process such as IR reflow, in order to prevent the solder from adhering to unnecessary portions of the solder, a method of forming a permanent pattern corresponding to the unnecessary portion of the solder as a protective film and an insulating film is provided. It is adopted. As the permanent pattern of the protective film, a solder resist is preferably used.
종래, 솔더 레지스트로서는 열경화형의 재료가 많이 사용되고, 이것을 스크린 인쇄법으로 인쇄해서 실시하는 방법이 일반적이었다. 그러나, 최근, 프린트 배선판의 배선의 고밀도화에 따라서, 스크린 인쇄법으로는 해상도의 점에서 한계가 발생하고, 포토 리소그래피법으로 화상 형성을 행하는 포토 솔더 레지스트가 많이 사용되도록 되어 왔다. 그 중에서도, 탄산 소다 용액 등의 약알칼리 용액으로 현상가능한 알칼리 현상형의 포토 솔더 레지스트가 작업 환경, 지구 환경 보전의 점에서 주류로 되어 있다. 또한 일반적으로는 액상 솔더 레지스트를 스크린 인쇄, 스프레이 코트, 딥 코트 등에 의해 배선 형성이 완료된 기판의 한쪽 면에 도포하여 건조하고, 이어서 반대면에 도포하여 건조하는 제조방법이 사용되고 있다.Conventionally, many thermosetting materials are used as a soldering resist, and the method of printing and performing this by the screen printing method was common. However, in recent years, as the wiring density of printed wiring boards is increased, limitations arise in terms of resolution in the screen printing method, and many photo solder resists which perform image formation by the photolithography method have been used. Especially, the alkali developing type photo solder resist which can be developed by weak alkali solution, such as a soda carbonate solution, has become mainstream from the point of work environment and global environment conservation. Moreover, generally, the manufacturing method of apply | coating and drying a liquid solder resist to one side of the board | substrate with which wiring formation was completed by screen printing, a spray coat, a dip coat, etc., and then apply | coating on the opposite side and drying is used.
또한, 상기한 바와 같은 알칼리 현상형의 포토 솔더 레지스트로서는, 주성분으로서 에폭시 화합물에 에틸렌성 불포화 이중 결합 및 알칼리 현상성을 부여하기 위한 산기를 도입한 화합물(에폭시 아크릴레이트)과 에틸렌성 불포화 이중 결합을 갖는 부가 중합성 화합물(모노머)을 함유하는 조성물이 일반적으로 사용되고 있고, 구체적으로는 특허문헌 1에 기재되어 있다. 그러나, 특허문헌 1에 기재된 솔더 레지스트는 포스트 베이크 후에 높은 표면경도가 얻어지고, 내약품성이 우수하지만, 표면의 택(tack)이 남고, 이물이 부착되기 쉬워져 결함이 증대하거나 또는 포토마스크를 오염시키는 등, 취급성을 악화시킨다고 하는 문제가 있다. 여기서, 표면에 택이 남는 것은 알칼리 수용액에 가용성인 바인더인 에폭시 아크릴레이트의 분자량이 수 100정도로 저분자량이고, 모노머가 보통 비점이 높은 액체 또는 반고체인 것 에 의한 것이라고 생각된다.In addition, as an alkali developing type photo solder resist as mentioned above, the compound (epoxy acrylate) and ethylenically unsaturated double bond which introduce | transduced the ethylenically unsaturated double bond and acid group for providing alkali developability to an epoxy compound as a main component are used. The composition containing the addition polymeric compound (monomer) which has is generally used, and is specifically described by patent document 1. As shown in FIG. However, the solder resist described in Patent Literature 1 obtains high surface hardness after post-baking and is excellent in chemical resistance, but has a tack on the surface and foreign matters tend to adhere, resulting in increased defects or contaminating the photomask. There is a problem such as worsening the handleability. Here, it is considered that the tack remains on the surface because the molecular weight of the epoxy acrylate, which is a soluble binder in an aqueous alkali solution, is low molecular weight (around 100) and the monomer is usually a liquid or semisolid having a high boiling point.
또한, 이러한 솔더 레지스트의 노광 감도는 통상 300∼1,000mJ/cm2로 낮고, 제조 라인의 스피드 상승의 장애로 되어 있어, 감도 상승이 더욱 요청되고 있다. 상기 감도 상승을 위해서는 모노머의 배합량의 증량이 효과적이지만, 모노머류를 많이 배합해버리면, 상기 표면 택이 더욱 악화한다는 문제가 생기고, 해결책이 강구되어 있지 않고 있다.Moreover, the exposure sensitivity of such a soldering resist is 300-1,000mJ / cm <2> normally low, and it becomes an obstacle of the speed increase of a manufacturing line, and the sensitivity increase is requested | required further. Although the increase of the compounding quantity of a monomer is effective in order to raise the said sensitivity, when a lot of monomers are mix | blended, the problem that the said surface tack will worsen arises, and the solution is not devised.
또한, 최근 고밀도 실장이 급속하게 진행되고 있고, 고밀도 실장을 실현하는 점에서, 솔더 레지스트의 과제는 웨트 현상이나 웨트 에칭을 반복하는 포토 리소그래피 프로세스 중에서의 기판의 신축이나 포토 마스크 필름의 온도, 습도 변화에 따른 신축에 기인하는 배선 패턴이나 스루홀 랜드 패턴의 위치 어긋남이다.In addition, in recent years, high-density mounting is rapidly progressing, and in order to realize high-density mounting, the problem of solder resists is the expansion and contraction of the substrate and the change in temperature and humidity of the photomask film in the photolithography process in which wet phenomenon and wet etching are repeated. This is a misalignment of the wiring pattern and the through hole land pattern due to the expansion and contraction.
위치 어긋남 방지에는 지금까지는, 기판의 변형도가 적은 로트를 선별하거나, 미리 각종의 파라미터로 수정된 복수의 필름 마스크를 준비하거나, 고가인 글라스 마스크를 사용한다는 대책이 채용되어 왔다. 또한, 이 위치 어긋남 문제의 해결을 위해서, 레이저 다이렉트 이미징 시스템(LDI)의 적용이 진행되고 있다. 여기서, LDI는 디지탈 데이터의 고속 처리에 의한 보정에 의해, 기판의 변형에 대응한 노광 패턴을 형성하는 기술에 기초하는 것이다. Until now, countermeasures have been adopted so far in order to prevent lot misalignment, to select a lot having a small degree of deformation of the substrate, to prepare a plurality of film masks previously modified with various parameters, or to use an expensive glass mask. In addition, in order to solve this position shift problem, application of the laser direct imaging system (LDI) is progressing. Here, LDI is based on the technique of forming the exposure pattern corresponding to the deformation | transformation of a board | substrate by the correction by the high speed processing of digital data.
상기 LDI에 사용되는 솔더 레지스트에는 365nm 또는 405nm 등의 UV레이저에 대응하기 위해서, 100mJ/cm2 이상의 노광 감도가 요구된다. 이 때문에, 고감도가 얻어지기 쉬운 필름 타입의 솔더 레지스트가 필요로 되어 오고 있다. 그러나, 특허문 헌 1에 기재된 솔더 레지스트를 필름화하면, 표면의 택성이 강하고, 지지체나 보호막과 감광층이 박리되기 어렵고, 취급성이 나쁘고, 또한 -20℃이하의 냉동 보존에서도 2, 3개월의 보존밖에 할 수 없어, 보존 안정성의 문제가 있다. 또한, 파장 405nm의 레이저광에 대한 감도가 없다고 하는 결점을 갖고 있다.The soldering resist used for the LDI requires an exposure sensitivity of 100 mJ / cm 2 or more in order to correspond to a UV laser such as 365 nm or 405 nm. For this reason, the film-type soldering resist which is easy to obtain a high sensitivity has been required. However, when the solder resist described in Patent Literature 1 is formed into a film, the surface tackiness is strong, the support, the protective film and the photosensitive layer are hardly peeled off, the handleability is poor, and even in cryopreservation at -20 ° C or lower, for two or three months. Can only be preserved and there is a problem of storage stability. Moreover, it has the drawback that there is no sensitivity with respect to the laser beam of wavelength 405nm.
한편, 특허문헌 2에서는 분자량 10,000이상의 비교적 고분자량의 알칼리 수용액에 가용성의 바인더를 사용한, 표면의 택이 작고, 내열성이 우수하고, 비교적 보존 안정성이 양호한 솔더 레지스트가 개시되어 있다. 그러나, 상기 솔더 레지스트는 표면 경도가 낮고, 라미네이트성이 열악하다는 문제가 있다. 따라서, 기포를 발생시키지 않고, 배선 형성이 완료된 프린트 배선 기판의 최외층에 미리 액상의 모노머를 언더층으로서 도포하여 둘 필요가 있어 공정이 번잡해지고, 취급성이 열악하게 된다는 결점을 갖고 있다. 그 이유로서는 메틸메타크릴레이트, 스티렌이라고 하는 경질의 폴리머를 형성하는 공중합 성분(각각의 호모 폴리머의 Tg는 105℃이상, 100℃이다)을 사용한 결과, 경화막이 유연성이 부족하여 취약해져서, 표면 경도가 높아지지 않고, 또한 진공 조건 하의 가열 적층 공정에서, 충분한 유동성이 얻어지지 않아서 기포 발생을 야기하고 있는 것이라 생각된다. 또한 파장 405nm의 레이저광에 대한 감도가 없다고 하는 결점을 갖고 있다.On the other hand, Patent Literature 2 discloses a solder resist having a small surface tack, excellent heat resistance, and relatively good storage stability using a soluble binder in a relatively high molecular weight alkali aqueous solution having a molecular weight of 10,000 or more. However, the solder resist has a problem of low surface hardness and poor lamination properties. Therefore, it is necessary to apply a liquid monomer as an underlayer to the outermost layer of the printed wiring board on which the wiring formation is completed, without generating bubbles, and the process is complicated and the handling is poor. As a reason for using the copolymer component (Tg of each homopolymer is 105 degreeC or more and 100 degreeC) which forms hard polymers, such as methyl methacrylate and styrene, as a result, a cured film lacks flexibility and is weak, and surface hardness Is not increased, and in the heat lamination step under vacuum conditions, sufficient fluidity is not obtained, which is considered to cause bubble generation. In addition, there is a drawback that there is no sensitivity to laser light having a wavelength of 405 nm.
또한 선단 전자 기기 분야에서는, 고주파 환경에서의 고속 전파성이 요구되고 있고, 특히 전자 계산기나 이동 휴대 통신 기기로 대표되는 전자 기기에 있어서는 처리 속도나 신호 전파 속도의 고속화, 사용 대역의 고주파화에 따라서, 적층판용 재료에는 저유전율화, 저유전 정접화가 요구되고 있다. 프린트 배선판 제조에 있어서의 솔더 레지스트에 저유전율화, 저유전 정접화가 요구되어 오고 있다. 그러나, 현재 상황의 알칼리 현상형의 솔더 레지스트에서는, 고주파수 영역에서의 유전 특성이 나빠서 고주파수용 수지로서 만족한 특성이 얻어지지 않는 것이 현재의 상태이다.In addition, in the field of leading electronic devices, high-speed propagation in a high frequency environment is required. In particular, in electronic devices represented by an electronic calculator or a mobile communication device, in accordance with the increase in the processing speed, the signal propagation speed, and the high frequency of the use band, Low dielectric constant and low dielectric loss tangent are demanded for a laminated plate material. Low dielectric constant and low dielectric loss tangent have been required for the solder resist in the manufacture of printed wiring boards. However, in the alkali developing solder resist of the present situation, the dielectric property in the high frequency region is bad, and it is a present state that the characteristic satisfy | filled as resin for high frequency is not obtained.
또한 상기 필름 타입의 솔더 레지스트로서, 일반적으로 시판되어 있는 제품에서는 이 필름화에 따라서, 감광층 중에 있어서 바인더 및 모노머와 열가교제가 혼재하기 위해서, 가교 반응이 일어나서 보존 안정성이 결핍되는 것이 문제가 되어 있다.In addition, as a film-type soldering resist, in general, a commercially available product has a problem that a crosslinking reaction occurs and the storage stability is insufficient in order to mix a binder, a monomer, and a thermal crosslinking agent in the photosensitive layer. have.
한편, 에폭시 수지 조성물 등의 열경화성 수지 조성물의 경화 촉진제로서, 상기 보존 안정성의 관점으로부터, 보존시에는 반응을 일으키지 않지만, 가열에 의해 반응해서 경화하는 성질을 지니는, 소위 잠재성 경화 촉진제를 사용한 제안이 있다. 예를 들면, 2-에틸헥실산아연과 트리에탄올아민으로 이루어지는 염, 트리에틸렌디아민과 지방족 카르복실산으로 이루어지는 염을 배합한 제안이 있다(비특허문헌 1 및 특허문헌 3 참조). 이들은 경화 촉진제를 착염으로 함으로써, 용해성을 저하시켜서 반응 활성을 억제하고, 보존 안정성을 향상시키고자 하는 것이다.On the other hand, as a curing accelerator of thermosetting resin compositions such as epoxy resin compositions, from the viewpoint of the above storage stability, a proposal using a so-called latent curing accelerator, which does not cause a reaction at the time of storage but has a property of reacting and curing by heating, have. For example, there exists the proposal which mix | blended the salt which consists of 2-ethylhexyl acid zinc and triethanolamine, and the salt which consists of triethylenediamine and aliphatic carboxylic acid (refer nonpatent literature 1 and patent document 3). These are intended to reduce the solubility, suppress the reaction activity and improve the storage stability by making the curing accelerator complexed.
또한, 에폭시 수지에 디메틸아민이나 디알킬아민을 반응시켜서 얻어지는 부가물(특허문헌 4 및 특허문헌 5 참조), 에폭시 수지에 3급 아민을 반응시켜서 얻어지는 부가물(특허문헌 6 및 특허문헌 7 참조) 등을 사용한 제안도 있다. 이렇게 에폭시 수지에 아민 화합물을 부가시켜서 고분자화, 불용화시킴으로써, 보존 안정성의 향상을 도모하고 있다.Moreover, the adduct obtained by making dimethylamine and dialkylamine react with an epoxy resin (refer patent document 4, and patent document 5), and the adduct obtained by making tertiary amine react with an epoxy resin (refer patent document 6 and patent document 7) There is also a proposal using such a method. Thus, by adding an amine compound to an epoxy resin and polymerizing and insolubilizing, improvement of storage stability is aimed at.
그러나, 이들의 문헌에서는 솔더 레지스트에 사용한 개시가 없고, 충분히 만족할 수 있는 높은 보존 안정 성능이 얻어지고, 또한, 저렴한 원료를 이용하여 간단하게 얻어지는 열가교제로서 작용하는 화합물은 아직 제공되어 있지 않고, 개량이 더욱 요구되고 있다.However, these documents do not disclose a compound used as a thermal crosslinking agent without any disclosure used in the soldering resist, a satisfactory satisfactory high storage stability performance is obtained, and a low-cost raw material is not yet provided. This is further demanded.
또한, 열가교제로서의 에폭시 수지 화합물을 난용성으로 함으로써, 보존 안정성의 향상을 도모한 것이 개시되어 있다(특허문헌 8 및 특허문헌 9 참조). 그러나, 이 경우, 노광 감도가 300∼500mJ/cm3로 낮고, 보존 안정성과 고감도나 현상성등을 양호한 발란스로 양립시키는 것은 곤란하였다.Moreover, what aimed at the improvement of storage stability is disclosed by making the epoxy resin compound as a heat crosslinking agent into poor solubility (refer patent document 8 and patent document 9). In this case, however, the exposure sensitivity was low at 300 to 500 mJ / cm 3 , and it was difficult to achieve both good balance between storage stability, high sensitivity, and developability.
따라서, 상온에서는 반응을 일으키지 않고, 가열에 의해 가교 반응을 개시하는 열가교제를 함유하고, UV노광에 의해 화상 형성 가능하고, 표면의 택성이 작고, 지지체 등과의 박리성이 우수하고, 라미네이트성 및 취급성이 양호하고, 보존 안정성이 우수하고, 고감도로 현상성도 우수하고, 현상 후에 우수한 내약품성, 표면경도, 내열성, 유전 특성 등을 발현 가능한 감광성 조성물, 및 이것을 사용한 감광성 필름, 및 고세밀한 영구 패턴 및 그 효율적인 형성 방법도 아직 충분히 만족할 수 있는 것이 제공되지 않어 있지 않는 것이 현재의 상태이다.Therefore, it contains a thermal crosslinking agent which initiates a crosslinking reaction by heating without causing a reaction at normal temperature, and is capable of forming an image by UV exposure, has a small surface tack, excellent peelability with a support, etc., lamination and Good handleability, excellent storage stability, high sensitivity and developability, and a photosensitive composition capable of expressing excellent chemical resistance, surface hardness, heat resistance, dielectric properties, and the like after development, a photosensitive film using the same, and a highly detailed permanent pattern And it is the present state that the efficient formation method is not yet provided with what is satisfactory enough.
특허문헌 1:일본특허공개 소 61-243869호 공보Patent Document 1: Japanese Patent Application Laid-Open No. 61-243869
특허문헌 2:일본특허공개 평 02-097502호 공보Patent Document 2: Japanese Patent Application Laid-Open No. 02-097502
특허문헌 3:일본특허공개 평 11-246651호 공보Patent Document 3: Japanese Patent Application Laid-Open No. 11-246651
특허문헌 4:일본특허공개 소 56-155222호 공보Patent Document 4: Japanese Patent Application Laid-open No. 56-155222
특허문헌 5:일본특허공개 소 57-100127호 공보Patent Document 5: Japanese Patent Application Laid-Open No. 57-100127
특허문헌 6:일본특허공개 소59-053526호 공보Patent Document 6: Japanese Patent Application Laid-Open No. 59-053526
특허문헌 7:일본특허공개 2000-001526호 공보Patent Document 7: Japanese Patent Application Laid-Open No. 2000-001526
특허문헌 8:일본특허 제2746009호 공보Patent Document 8: Japanese Patent No. 2746009
특허문헌 9:일본특허 제2707495호 공보Patent Document 9: Japanese Patent No. 2707495
비특허문헌 1:일본유지, 엔도 타케시(동경대공대)네트워크 폴리머 vol. 19, No.4, P228-235, 1998[Non-Patent Document 1] Yuji, Endo Takeshi (Tokyo University of Technology) Network Polymer vol. 19, No. 4, P228-235, 1998
본 발명은 종래에 있어서의 상기 모든 문제를 해결하고, 이하의 목적을 달성하는 것을 과제로 한다. 즉 본 발명은 보존시의 상온 하에서는 반응을 일으키지 않고, 가열에 의해 가교 반응을 개시하고, 경화막의 양호한 막경도가 얻어지는 화합물을 함유하고, UV노광에 의해 화상 형성 가능하고, 표면의 택성이 작고, 라미네이트성 및 취급성이 양호하고, 보존 안정성이 우수하고, 고감도로 현상성도 우수하고, 현상 후에 우수한 내약품성, 표면경도, 내열성, 유전 특성 등을 발현하는 감광성 조성물, 이것을 사용한 감광성 필름, 고정밀한 영구 패턴(보호막, 층간 절연막 및 솔더 레지스트 패턴 등) 및 그 효율적인 형성 방법을 제공하는 것을 목적으로 한다.This invention solves all the said problems in the past, and makes it a subject to achieve the following objectives. That is, this invention does not produce reaction at normal temperature at the time of preservation, contains a compound which starts a crosslinking reaction by heating, and obtains the favorable film hardness of a cured film, is image-formable by UV exposure, surface tackiness is small, Photosensitive composition having good lamination and handling properties, excellent storage stability, high sensitivity and developability, and excellent after chemical development, surface hardness, heat resistance, dielectric properties, photosensitive film using the same, high precision permanent It is an object to provide a pattern (protective film, interlayer insulating film, solder resist pattern, etc.) and an efficient forming method thereof.
상기 과제를 해결하기 위한 수단으로서는 이하와 같다. 즉,Means for solving the above problems are as follows. In other words,
<1> (A) 1분자 중에 1개 이상의 카르복실기 및 에스테르기의 적어도 어느 하나를 갖는 중합체, (B) 중합성 화합물, (C) 광중합 개시제, 및 (D) 하기 일반식(1)∼(3)로 나타내어지는 화합물로부터 선택되는 적어도 1종의 화합물을 함유하는 것을 특징으로 하는 감광성 조성물이다.<1> (A) A polymer having at least one of at least one carboxyl group and ester group in one molecule, (B) polymerizable compound, (C) photopolymerization initiator, and (D) the following general formulas (1) to (3 It is a photosensitive composition characterized by containing at least 1 sort (s) of compound chosen from the compound represented by ().
단, 상기 일반식(1), (2) 및 (3)중, P는 산소 원자, 카르보닐기, 아미드기, 우레탄기, 알킬렌 및 아릴렌 중 어느 하나를 나타낸다. Q는 붕소 원자, 질소 원자, 알킬렌 및 아릴렌 중 어느 하나를 나타낸다. W는 2개의 X부와 결합을 갖는 나프탈렌을 나타낸다. A1∼A5는 단일 결합, 알킬렌 및 아릴렌 중 어느 하나를 나타내고, X1∼X6은 -OCONH-, -NHCOO-, -NHCO- 및 -CONH- 중 어느 하나를 나타낸다. R1∼R6은 수소 원자, 할로겐 원자, 알킬기 및 아릴기 중 어느 하나를 나타낸다.However, in said General Formula (1), (2), and (3), P represents either an oxygen atom, a carbonyl group, an amide group, a urethane group, alkylene, and arylene. Q represents any one of a boron atom, a nitrogen atom, alkylene and arylene. W represents naphthalene having a bond with two X moieties. A 1 to A 5 represent any one of a single bond, alkylene and arylene, and X 1 to X 6 represent any one of -OCONH-, -NHCOO-, -NHCO- and -CONH-. R 1 to R 6 represent any one of a hydrogen atom, a halogen atom, an alkyl group and an aryl group.
상기 <1>에 기재된 감광성 조성물에 있어서는 저온 또는 상온에서의 보존시에는 경화를 일으키지 않고, 보존 안정성 및 취급성 등이 우수하여 가열에 의해 반응을 일으키기고, 경화막의 우수한 막경도가 얻어진다. 상기 감광성 조성물을 이용하여 영구 패턴을 형성했을 경우, 고감도인 패턴 형성이 가능하고, 경화막의 내약품성, 표면경도, 내열성, 유전 특성의 향상이 도모되고, 고정밀한 영구 패턴이 얻어진다.In the photosensitive composition as described in said <1>, it does not produce hardening at the time of low temperature or normal temperature, it is excellent in storage stability, handleability, etc., it raises reaction by heating, and the excellent film hardness of a cured film is obtained. When a permanent pattern is formed using the said photosensitive composition, highly sensitive pattern formation is possible, the chemical-resistance, surface hardness, heat resistance, and dielectric property of a cured film are aimed at, and a high precision permanent pattern is obtained.
<2> (D) 일반식(1)∼(3)으로 나타내지는 화합물로부터 선택되는 적어도 1종의 화합물이 하기 구조식(1)∼(10)으로 나타내지는 화합물인 상기 <1>에 기재된 감광성 조성물이다.<2> Photosensitive composition as described in said <1> whose at least 1 sort (s) of compound chosen from the compound represented by General formula (1)-(3) is a compound represented by following structural formula (1)-(10) to be.
<3> (D) 일반식(1)∼(3)으로 나타내지는 화합물로부터 선택되는 적어도 1종의 화합물의 함유량의 함유량이 1∼50질량%인 상기 <1> 또는 <2>에 기재된 감광성 조성물이다.<3> Photosensitive composition as described in said <1> or <2> whose content of content of at least 1 sort (s) of compound chosen from the compound represented by General formula (1)-(3) is 1-50 mass%. to be.
<4> (D) 일반식(1)∼(3)으로 나타내지는 화합물로부터 선택되는 적어도 1종의 화합물과 병용하는 열가교제를 더 함유하는 상기 <1> 내지 <3> 중 어느 하나에 기재된 감광성 조성물이다.<4> Photosensitive property in any one of said <1> to <3> which further contains the thermal crosslinking agent used together with at least 1 sort (s) of compound chosen from the compound represented by General formula (1)-(3). Composition.
<5> 병용하는 열가교제가 에폭시 화합물, 옥세탄 화합물, 폴리이소시아네이트 화합물, 폴리이소시아네이트 화합물에 블록제를 반응시켜서 얻어지는 화합물 및 멜라민 유도체로부터 선택되는 적어도 1종인 상기 <4>에 기재된 감광성 조성물이다.The thermal crosslinking agent used together with <5> is the photosensitive composition as described in said <4> which is at least 1 sort (s) chosen from the compound obtained by making a blocking agent react with an epoxy compound, an oxetane compound, a polyisocyanate compound, and a polyisocyanate compound.
<6> 병용하는 열가교제가 다가 페놀 화합물과 β-알킬에피할로히드린으로부터 유도된 에폭시 화합물인 상기 <4> 또는 <5>에 기재된 감광성 조성물이다.The thermal crosslinking agent used together with <6> is the photosensitive composition as described in said <4> or <5> which is an epoxy compound derived from a polyhydric phenol compound and (beta) -alkyl epihalohydrin.
<7> 병용하는 열가교제가 분자내에 2개 이상의 옥시란기를 갖는 에폭시 화합물인 상기 <4> 내지 <6> 중 어느 하나에 기재된 감광성 조성물이다.The thermal crosslinking agent used together with <7> is the photosensitive composition in any one of said <4> to <6> which is an epoxy compound which has two or more oxirane groups in a molecule | numerator.
<8> 병용하는 열가교제가 분자내에 2개 이상의 옥세타닐기를 갖는 옥세탄 화합물인 상기 <4> 내지 <7> 중 어느 하나에 기재된 감광성 조성물이다.The thermal crosslinking agent used together with <8> is the photosensitive composition in any one of said <4> to <7> which is an oxetane compound which has two or more oxetanyl groups in a molecule | numerator.
<9> 병용하는 열가교제가 하기 구조식(I) 및 (II) 중 어느 하나로 나타내어지는 상기 <4> 내지 <8> 중 어느 하나에 기재된 감광성 조성물이다.The heat crosslinking agent used together with <9> is the photosensitive composition in any one of said <4> to <8> represented by either of following structural formula (I) and (II).
단, 상기 구조식(I) 중, R은 수소 원자 및 탄소수 1∼6개의 알킬기 중 어느하나를 나타내고, n은 0∼20의 정수를 나타낸다.However, in said structural formula (I), R represents either a hydrogen atom and a C1-C6 alkyl group, and n represents the integer of 0-20.
단, 상기 구조식(II) 중, R은 수소 원자 및 탄소수 1∼6개의 알킬기 중 어느하나를 나타내고, R'은 수소 원자, 및 CH3 중 어느하나를 나타내고, n은 0∼20의 정수를 나타낸다.Of the stage, the structural formula (II), R represents one of a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, R 'represents either a hydrogen atom, and CH 3, n is an integer of 0 to 20 .
<10> 병용하는 열가교제가 헥사메틸화 메틸올 멜라민인 상기 <4> 내지 <6> 중 어느 하나에 기재된 감광성 조성물이다.The thermal crosslinking agent used together with <10> is the photosensitive composition in any one of said <4> to <6> which is hexamethylated methylol melamine.
<11> (A) 중합체가 에폭시아크릴레이트 화합물인 상기 <1> 내지 <10> 중 어느 하나에 기재된 감광성 조성물이다.<11> (A) Polymer is a photosensitive composition in any one of said <1> to <10> which is an epoxy acrylate compound.
<12> (A) 중합체가 측쇄에 (메타)아크릴로일기 및 산성기를 갖는 비닐 공중합체 중 적어도 1종을 함유하는 상기 <1> 내지 <11> 중 어느 하나에 기재된 감광성 조성물이다.<12> Photosensitive composition in any one of said <1> to <11> in which (A) polymer contains at least 1 sort (s) of the vinyl copolymer which has a (meth) acryloyl group and an acidic group in a side chain.
<13> (A) 중합체가 에폭시아크릴레이트 화합물과 측쇄에 (메타)아크릴로일 기 및 산성기를 갖는 비닐공중합체 중 적어도 1종을 함유하는 상기 <1> 내지 <12> 중 어느 하나에 기재된 감광성 조성물이다.The photosensitive property in any one of said <1> to <12> in which a <13> (A) polymer contains at least 1 sort (s) of an epoxy acrylate compound and the vinyl copolymer which has a (meth) acryloyl group and an acidic group in a side chain. Composition.
<14> (A) 중합체가 하기 구조식(III)으로 나타내어지는 상기 <11> 내지 <13> 중 어느 하나에 기재된 감광성 조성물이다.<14> (A) A polymer is a photosensitive composition in any one of said <11> to <13> represented by the following structural formula (III).
단, 상기 구조식(III) 중 X는 수소 원자 및 적어도 산성기를 함유하는 치환 기 중 어느 하나를 나타내고, Y는 메틸렌기, 이소프로피리덴기 및 술포닐기 중 어느 하나를 나타내고, n은 1∼20의 정수를 나타낸다.In the formula (III), X represents any one of a substituent containing a hydrogen atom and at least an acidic group, Y represents any one of a methylene group, an isopropylidene group, and a sulfonyl group, and n represents 1-20. Represents an integer.
<15> (A) 중합체가 무수 말레인산 공중합체의 무수물기에 대하여 0.1∼1.2당량의 1급 아민 화합물을 반응시켜서 얻어지는 공중합체인 상기 <1> 내지 <5> 및 <10> 중 어느 하나에 기재된 감광성 조성물이다.The photosensitive composition as described in any one of said <1>-<5> and <10> which is a copolymer obtained by making a <15> (A) polymer react with 0.1-1.2 equivalent primary amine compound with respect to the anhydride group of a maleic anhydride copolymer. to be.
<16> (A) 중합체가 (a) 무수 말레인산, (b) 방향족 비닐 단량체 및 (c) 비닐 단량체로서, 상기 비닐 단량체의 호모 폴리머의 유리전이온도(Tg)가 80℃미만인 비닐 단량체로 이루어지는 공중합체의 무수물기에 대하여 0.1∼1.0당량의 1급 아민 화합물을 반응시켜서 얻어지는 공중합체인 상기 <1> 내지 <5>, <10> 및 <15> 중 어느 하나에 기재된 감광성 조성물이다.<16> The polymer (A) is an air comprising (a) maleic anhydride, (b) an aromatic vinyl monomer, and (c) a vinyl monomer, wherein the vinyl monomer having a glass transition temperature (Tg) of the homopolymer of the vinyl monomer is less than 80 ° C. It is a photosensitive composition in any one of said <1>-<5>, <10>, and <15> which is a copolymer obtained by making a 0.1-1.0 equivalent primary amine compound react with the anhydride group of a copolymer.
<17> (B) 중합성 화합물이 (메타)아크릴기를 갖는 모노머로부터 선택되는 적어도 1종을 함유하는 상기 <1> 내지 <16> 중 어느 하나에 기재된 감광성 조성물이다.<17> (B) Polymeric compound is the photosensitive composition in any one of said <1> to <16> containing at least 1 sort (s) chosen from the monomer which has a (meth) acryl group.
<18> (C) 광중합 개시제가 할로겐화 탄화 수소 유도체, 포스핀 옥사이드, 헥사아릴 비이미다졸, 옥심 유도체, 유기과산화물, 티오 화합물, 케톤 화합물, 방향족 오늄염 및 케토옥심에테르로부터 선택되는 적어도 1종을 함유하는 상기 <1>부터 <17> 중 어느 하나에 기재된 감광성 조성물이다.(C) The photopolymerization initiator is at least one selected from halogenated hydrocarbon derivatives, phosphine oxides, hexaaryl biimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts and ketooxime ethers. It is the photosensitive composition in any one of said <1> to <17> to contain.
<19> 지지체와 상기 지지체 상에 상기 <1> 내지 <18> 중 어느 하나에 기재된 감광성 조성물이 적층되어서 이루어지는 감광층을 갖는 것을 특징으로 하는 감광성 필름이다.It has a photosensitive layer formed by laminating | stacking the photosensitive composition in any one of said <1>-<18> on a <19> support body and the said support body.
<20> 감광층을 노광하여 현상하는 경우에 있어서, 상기 감광층의 노광하는 부분의 두께를 상기 노광 및 현상 후에 있어서 변화시키지 않는 상기 노광에 사용하는 광의 최소 에너지가 0.1∼100mJ/cm2인 상기 <19>에 기재된 감광성 필름이다.<20> In the case of exposing and developing the photosensitive layer, the minimum energy of light used for the exposure which does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is 0.1 to 100 mJ / cm 2 . It is a photosensitive film as described in <19>.
<21> 지지체가 합성 수지를 포함하고, 또한 투명한 상기 <19> 내지 <21> 중 어느 하나에 기재된 감광성 필름이다.<21> support body is a photosensitive film in any one of said <19> to <21> which contains a synthetic resin and is transparent.
<22> 지지체가 장척상인 상기 <19> 내지 <21> 중 어느 하나에 기재된 감광성 필름이다.The <22> support body is the photosensitive film in any one of said <19>-<21> which is a long picture.
<23> 장척상이고, 롤상으로 권취되어 이루어지는 상기 <19> 내지 <22> 중 어느 하나에 기재된 감광성 필름이다.It is a <23> elongate shape and is the photosensitive film in any one of said <19> to <22> which is wound up in roll shape.
<24> 감광층상에 보호 필름을 포함하여 이루어지는 상기 <19> 내지 <23> 중 어느 하나에 기재된 감광성 필름이다.It is the photosensitive film in any one of said <19> to <23> which comprises a protective film on a <24> photosensitive layer.
<25> 감광층의 두께가 3∼100㎛인 상기 <19> 내지 <24> 중 어느 하나에 기재된 감광성 필름이다.It is a photosensitive film in any one of said <19> to <24> whose thickness of a <25> photosensitive layer is 3-100 micrometers.
<26> 감광층이 광조사 수단으로부터의 광을 수광하여 출사하는 묘소부를 n개 갖는 광변조 수단에 의해, 상기 광조사 수단으로부터의 광을 변조시킨 후, 상기 묘소부에 있어서의 출사면의 변형에 의한 수차를 보정가능한 비구면을 갖는 마이크로렌즈를 배열한 마이크로렌즈 어레이를 통과한 광으로 노광되는 상기 <19> 내지 <25>에 기재된 감광성 필름이다.<26> Deformation of the exit surface in the drawing section after modulating the light from the light irradiation means by the light modulating means having n ridges for receiving the light from the light irradiation means and emits light It is a photosensitive film as described in said <19>-<25> exposed by the light which passed through the microlens array which arrange | positioned the microlens which has the aspherical surface which can correct aberration by this.
<27> 상기 <1> 내지 <18> 중 어느 하나에 기재된 감광성 조성물을 기재의 표면에 도포하고, 건조해서 감광층을 형성한 후, 노광하고, 현상하고, 가열하는 것을 특징으로 하는 영구 패턴 형성 방법이다. 상기 <27>에 기재된 영구 패턴 형성 방법에 있어서는 상기 감광성 조성물이 상기 기재의 표면에 도포되어 상기 도포된 감광성 조성물이 건조되어서 상기 감광층이 형성된다. 상기 감광층이 노광되고, 상기 노광된 감광층이 현상되고, 상기 현상된 감광층이 가열된다. 상기 감광층이 가열됨으로써 가교 반응을 개시하고, 상기 감광층의 경화 영역의 막강도가 높아진다. 그 결과, 표면 경도가 높고, 보호막, 층간 절연막 및 솔더 레지스트 패턴 등에 최적인 영구 패턴이 형성된다. 상기 가열 처리는 전체면 가열 처리이어도 좋고, 패턴 모양으로 가열하는 처리이어도 좋다.<27> After applying the photosensitive composition in any one of said <1>-<18> to the surface of a base material, drying and forming a photosensitive layer, it exposes, develops, and heats, The permanent pattern formation characterized by the above-mentioned. Way. In the permanent pattern formation method as described in said <27>, the said photosensitive composition is apply | coated to the surface of the said base material, and the said photosensitive composition is dried and the said photosensitive layer is formed. The photosensitive layer is exposed, the exposed photosensitive layer is developed, and the developed photosensitive layer is heated. By heating the said photosensitive layer, a crosslinking reaction is started and the film strength of the hardened area | region of the said photosensitive layer becomes high. As a result, a permanent pattern which is high in surface hardness and is optimal for a protective film, an interlayer insulating film, a solder resist pattern, or the like is formed. The heat treatment may be a whole surface heat treatment, or may be a pattern heating.
<28> 상기 <19> 내지 <26> 중 어느 하나에 기재된 감광성 필름을 가열 하 및 가압 하 중 적어도 어느 하나에서 기재의 표면에 적층한 후, 노광하고, 현상하고, 가열하는 것을 특징으로 하는 영구 패턴 형성 방법이다. 상기 <28>에 기재된 영구 패턴 형성 방법에 있어서는 상기 감광성 필름이 가열 및 가압 하에서 상기 기재의 표면에 적층된다. 상기 적층된 감광성 필름에 있어서의 상기 감광층이 노광되고, 상기 노광된 감광층이 현상되고, 상기 현상된 감광층이 가열된다. 상기 감광층이 가열됨으로써 상기 일반식(1)∼(3)으로 나타내지는 화합물의 가교 효과에 의해, 상기 감광층의 경화 영역의 막강도가 향상된다. 그 결과, 표면 경도가 높고, 보호막, 층간 절연막 및 솔더 레지스트 패턴 등에 최적인 영구 패턴이 형성된다.<28> A permanent film characterized in that the photosensitive film according to any one of the above <19> to <26> is laminated on the surface of the substrate under at least one of heating and pressurization, followed by exposure, development and heating. Pattern formation method. In the permanent pattern formation method as described in said <28>, the said photosensitive film is laminated | stacked on the surface of the said base material under heating and pressurization. The photosensitive layer in the laminated photosensitive film is exposed, the exposed photosensitive layer is developed, and the developed photosensitive layer is heated. The film strength of the hardened area | region of the said photosensitive layer improves by the crosslinking effect of the compound represented by the said General Formula (1)-(3) by heating the said photosensitive layer. As a result, a permanent pattern which is high in surface hardness and is optimal for a protective film, an interlayer insulating film, a solder resist pattern, or the like is formed.
<29> 기재가 배선 형성이 완료된 프린트 배선 기판인 상기 <27> 또는 <28> 중 어느 하나에 기재된 영구 패턴 형성 방법이다. 상기 영구 패턴 형성 방법을 이용함으로써, 반도체 부품의 다층 배선 기판이나 빌드업 배선 기판 등으로의 고밀도 실장이 가능하다.<29> base material is a permanent pattern formation method in any one of said <27> or <28> which is a printed wiring board in which wiring formation was completed. By using the permanent pattern forming method described above, high-density mounting on a multilayer wiring board, a buildup wiring board, or the like of a semiconductor component is possible.
<30> 노광이 형성하는 패턴 정보에 기초하여 상형상으로 행하여지는 상기 <27> 내지 <29> 중 어느 하나에 기재된 영구 패턴 형성 방법이다.It is a permanent pattern formation method in any one of said <27>-<29> performed in image shape based on the pattern information formed by <30> exposure.
<31> 노광이 형성하는 패턴 정보에 기초하여 제어 신호를 생성하고, 상기 제어 신호에 따라서 변조시킨 광을 이용하여 행하여지는 상기 <27> 내지 <30> 중 어느 하나에 기재된 영구 패턴 형성 방법이다.It is a permanent pattern formation method in any one of said <27> to <30> which produces | generates a control signal based on the pattern information formed by <31> exposure, and uses the light modulated according to the said control signal.
<32> 노광이 광을 조사하는 광조사 수단 및 형성하는 패턴 정보에 기초하여 상기 광조사 수단으로부터 조사되는 광을 변조시키는 광변조 수단을 이용하여 행하여지는 상기 <27> 내지 <31> 중 어느 하나에 기재된 영구 패턴 형성 방법이다.<32> Any one of the above <27> to <31> performed using light irradiation means for irradiating light and light modulating means for modulating the light irradiated from the light irradiation means on the basis of the pattern information to be formed. It is a permanent pattern formation method of description.
<33> 광변조 수단이 형성하는 패턴 정보에 기초하여 제어 신호를 생성하는 패턴 신호 생성 수단을 더 가져서 이루어지고, 상기 광조사 수단으로부터 조사되는 광을 상기 패턴 신호 생성 수단이 생성한 제어 신호에 따라서 변조시키는 상기 <32>에 기재된 영구 패턴 형성 방법이다.And a pattern signal generating means for generating a control signal based on the pattern information formed by the light modulating means, wherein the light irradiated from the light irradiation means is generated in accordance with the control signal generated by the pattern signal generating means. It is a permanent pattern formation method as described in said <32> which modulates.
<34> 광변조 수단이 n개의 묘소부를 가져서 이루어지고, 상기 n개의 묘소부 중에서 연속적으로 배치된 임의의 n개 미만의 상기 묘소부를 형성하는 패턴 정보 에 따라서 제어 가능한 상기 <32> 또는 <33> 중 어느 하나에 기재된 영구 패턴 형성 방법이다. 상기 <34>에 기재된 영구 패턴 형성 방법에 있어서는 상기 광변조 수단에 있어서의 n개의 묘소부 중에서 연속적으로 배치된 임의의 n개 미만의 묘소부를 패턴 정보에 따라서 제어함으로써, 상기 광조사 수단으로부터의 광이 고속으로 변조된다.The light modulating means has n drawing parts and is controllable in accordance with the pattern information for forming any less than n drawing parts arranged consecutively among the n drawing parts. It is a permanent pattern formation method in any one of. In the permanent pattern forming method according to the above <34>, the light from the light irradiation means is controlled by controlling any less than n seedling portions continuously arranged among the n drawing portions in the light modulating means according to the pattern information. This is modulated at high speed.
<35> 광변조 수단이 공간 광변조 소자인 상기 <32> 내지 <34> 중 어느 하나에 기재된 영구 패턴 형성 방법이다.<35> light modulation means is a permanent pattern formation method in any one of said <32> to <34> which is a spatial light modulation element.
<36> 공간 광변조 소자가 디지털·마이크로 미러·디바이스(DMD)인 상기 <35>에 기재된 영구 패턴 형성 방법이다.The <36> spatial light modulator is a permanent pattern formation method as described in said <35> which is a digital micro mirror device (DMD).
<37> 묘소부가 마이크로 미러인 상기 <34> 내지 <36> 중 어느 하나에 기재된 영구 패턴 형성 방법이다.<37> drawing parts are the permanent pattern formation methods in any one of said <34> to <36> which is a micro mirror.
<38> 노광이 광변조 수단에 의해 광을 변조시킨 후, 상기 광변조 수단에 있어서의 묘소부의 출사면의 변형에 의한 수차를 보정가능한 비구면을 갖는 마이크로렌즈를 배열한 마이크로렌즈 어레이를 통과시켜서 행하여지는 상기 <34> 내지 <37>중 어느 하나에 기재된 영구 패턴 형성 방법이다.After the exposure modulates the light by the light modulating means, the aberration caused by the deformation of the exit face of the drawing part in the light modulating means is passed through a microlens array in which the microlenses having the aspherical surface correctable are arranged. Paper is the permanent pattern formation method in any one of said <34>-<37>.
<39> 비구면이 토릭면인 상기 <38>에 기재된 영구 패턴 형성 방법이다. 상기 <39>에 기재된 영구 패턴 형성 방법에 있어서는 상기 비구면이 토릭면이므로 상기 묘소부에 있어서의 방사면의 변형에 의한 수차가 효율적으로 보정되어 상기 감광층 상에 결상시키는 상의 변형이 효율적으로 억제된다. 그 결과, 상기 감광층으로의 노광이 고정밀하게 행하여진다. 그 후, 상기 감광층을 현상함으로써 고정밀한 영구 패턴이 형성된다.<39> aspherical surface is a toric surface, The permanent pattern formation method as described in said <38>. In the method for forming a permanent pattern according to the above <39>, since the aspherical surface is a toric surface, aberration due to deformation of the radiation surface in the tomb is effectively corrected, and deformation of an image formed on the photosensitive layer is effectively suppressed. . As a result, exposure to the photosensitive layer is performed with high precision. Thereafter, the photosensitive layer is developed to form a high-precision permanent pattern.
<40> 노광이 애퍼쳐 어레이를 통하여 행하여지는 상기 <27> 내지 <39> 중 어느 하나에 기재된 영구 패턴 형성 방법이다. 상기 <40>에 기재된 영구 패턴 형성 방법에 있어서는 노광이 상기 애퍼쳐 어레이를 통하여 행하여짐으로써, 소광비가 향상한다. 그 결과, 노광이 매우 고정밀하게 행하여진다. 그 후, 상기 감광층을 현상함으로써, 매우 고정밀한 영구 패턴이 형성된다.<40> exposure is a permanent pattern formation method in any one of said <27> to <39> which is performed through an aperture array. In the permanent pattern formation method as described in said <40>, an extinction ratio improves because exposure is performed through the said aperture array. As a result, exposure is performed very precisely. Thereafter, by developing the photosensitive layer, a very high precision permanent pattern is formed.
<41> 노광이 노광광과 감광층을 상대적으로 이동시키면서 행하여지는 상기 <27> 내지 <40> 중 어느 하나에 기재된 영구 패턴 형성 방법이다. 상기 <41>에 기재된 영구 패턴 형성 방법에 있어서는 상기 변조시킨 광과 상기 감광층을 상대적으로 이동시키면서 노광함으로써, 노광이 고속으로 행하여진다. <41> exposure is the permanent pattern formation method in any one of said <27> to <40> performed while moving exposure light and a photosensitive layer relatively. In the permanent pattern formation method as described in said <41>, exposure is performed at high speed by exposing and moving the modulated light and the said photosensitive layer relatively.
<42> 노광이 감광층의 일부 영역에 대하여 행하여지는 상기 <27> 내지 <41> 중 어느 하나에 기재된 영구 패턴 형성 방법이다.<42> exposure is the permanent pattern formation method in any one of said <27> to <41> performed with respect to the some area | region of a photosensitive layer.
<43> 광조사 수단이 2개 이상의 광을 합성해서 조사 가능한 상기 <32> 내지 <42> 중 어느 하나에 기재된 영구 패턴 형성 방법이다. 상기 <43>에 기재된 영구 패턴 형성 방법에 있어서는 상기 광조사 수단이 2이상의 광을 합성해서 조사 가능함으로써 노광이 초점 심도가 깊은 노광광으로 행하여진다. 그 결과, 상기 감광층으로의 노광이 매우 고정밀하게 행하여진다. 그 후, 상기 감광층을 현상함으로써, 매우 고정밀한 영구 패턴이 형성된다.<43> light irradiation means is a permanent pattern formation method in any one of said <32> to <42> which can synthesize | combine two or more lights, and can irradiate. In the permanent pattern formation method as described in said <43>, since the said light irradiation means synthesize | combines and irradiates two or more lights, exposure is performed as exposure light with a deep depth of focus. As a result, exposure to the photosensitive layer is performed with high accuracy. Thereafter, by developing the photosensitive layer, a very high precision permanent pattern is formed.
<44> 광조사 수단이 복수의 레이저, 멀티 모드 광파이버, 및 상기 복수의 레이저로부터 각각 조사된 레이저광을 집광하여 상기 멀티 모드 광파이버에 결합시키는 집합 광학계를 갖는 상기<32> 내지 <43> 중 어느 하나에 기재된 영구 패턴 형성 방법이다. 상기 <44>에 기재된 영구 패턴 형성 방법에 있어서는 상기 광조사 수단에 의해, 상기 복수의 레이저로부터 각각 조사된 레이저광이 상기 집합 광학계에 의해 수광하여, 상기 멀티 모드 광파이버에 결합 가능하게 함으로써 노광이 초점 심도가 깊은 노광광으로 행하여진다. 그 결과, 상기 감광층으로의 노광이 매우 고정밀하게 행하여진다. 그 후에 상기 감광층을 현상함으로써, 지극히 고정밀한 영구 패턴이 형성된다.<44> Any of the above <32> to <43>, wherein the light irradiation means has a plurality of lasers, a multi-mode optical fiber, and a collective optical system for collecting and coupling the laser light irradiated from the plurality of lasers, respectively, to the multi-mode optical fiber It is a permanent pattern formation method of one. In the method for forming a permanent pattern according to the above <44>, exposure is focused by allowing the laser light irradiated from the plurality of lasers to be received by the collective optical system and coupled to the multi-mode optical fiber by the light irradiation means. Depth is performed with deep exposure light. As a result, exposure to the photosensitive layer is performed with high accuracy. Thereafter, by developing the photosensitive layer, an extremely high precision permanent pattern is formed.
<45> 노광이 395∼415nm의 파장의 레이저광을 이용하여 행하여지는 상기 <27> 내지 <44> 중 어느 하나에 기재된 영구 패턴 형성 방법이다.<45> exposure is the permanent pattern formation method in any one of said <27> to <44> performed using the laser beam of the wavelength of 395-415 nm.
<46> 가열이 120∼250℃에서 행하여지는 상기 <27> 내지 <45> 중 어느 하나에 기재된 영구 패턴 형성 방법이다. 상기 <46>에 기재된 영구 패턴 형성 방법에서는, 상기 온도 조건에서 행하여지는 가열 처리에 있어서, 경화막의 막강도가 높아진다.<46> heating is a permanent pattern formation method in any one of said <27> to <45> performed at 120-250 degreeC. In the permanent pattern formation method as described in said <46>, the film strength of a cured film becomes high in the heat processing performed on the said temperature conditions.
<47> 현상이 행하여진 후, 감광층에 대하여 전체면 노광 처리를 행하는 상기 <27> 내지 <46>에 기재된 영구 패턴 형성 방법이다. 상기 <46>에 기재된 영구 패턴 형성 방법에서는 상기 전체면 노광 처리에 있어서, 상기 감광성 조성물 중의 수지의 경화가 촉진된다.After <47> image development is performed, it is a permanent pattern formation method as described in said <27>-<46> which performs a whole surface exposure process with respect to a photosensitive layer. In the permanent pattern formation method as described in said <46>, hardening of resin in the said photosensitive composition is accelerated in the said whole surface exposure process.
<48> 보호막, 층간 절연막 및 솔더 레지스트 패턴 중 적어도 어느 하나를 형성하는 상기 <27> 내지 <47> 중 어느 하나에 기재된 영구 패턴 형성 방법이다. 상기 <48>에 기재된 영구 패턴 형성 방법에서는 보호막, 층간 절연막 및 솔더 레지스트 패턴 중 적어도 어느 하나가 형성되므로, 상기 막이 갖는 절연성, 내열성 등에 의해 배선이 외부로부터의 충격이나 구부러짐 등으로부터 보호된다.It is a permanent pattern formation method in any one of said <27> to <47> which forms at least any one of a <48> protective film, an interlayer insulation film, and a soldering resist pattern. In the method for forming a permanent pattern described in the above <48>, at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed, so that the wiring is protected from an impact or bending from the outside due to insulation, heat resistance, and the like of the film.
<49> 상기 <27> 내지 <48> 중 어느 하나에 기재된 영구 패턴 형성 방법에 의해 형성되는 것을 특징으로 하는 영구 패턴이다. 상기 <49>에 기재된 영구 패턴은 상기 영구 패턴 형성 방법에 의해 형성되므로, 우수한 내약품성, 표면경도, 내열성등을 갖고, 또한 고정밀하고, 반도체 부품의 다층 배선 기판이나 빌드업 배선 기판 등으로의 고밀도 실장에 유용하다.<49> It is a permanent pattern formed by the permanent pattern formation method in any one of said <27>-<48>. Since the permanent pattern described in the above <49> is formed by the above-mentioned permanent pattern forming method, it has excellent chemical resistance, surface hardness, heat resistance, and the like, and is highly accurate, and has high density to a multilayer wiring board, a buildup wiring board, or the like of a semiconductor component. Useful for mounting.
<50> 보호막, 층간 절연막 및 솔더 레지스트 패턴 중 적어도 어느 하나인 상기 <49>에 기재된 영구 패턴이다. 상기 <50>에 기재된 영구 패턴은 보호막, 층간 절연막 및 솔더 레지스트 패턴 중 적어도 어느 하나이므로, 상기 막이 갖는 절연성, 내열성 등에 의해, 배선이 외부로부터의 충격이나 구부러짐 등으로부터 보호된다.It is a permanent pattern as described in said <49> which is at least any one of a <50> protective film, an interlayer insulation film, and a soldering resist pattern. The permanent pattern described in the above <50> is at least one of a protective film, an interlayer insulating film, and a solder resist pattern, so that the wiring is protected from external shock, bending, or the like due to insulation, heat resistance, and the like of the film.
(발명의 효과)(Effects of the Invention)
본 발명에 의하면, 종래에 있어서의 문제를 해결할 수 있고, 보존시의 상온하에서는 반응을 일으키지 않고, 가열에 의해 가교 반응을 개시하고, 경화막의 양호한 막경도가 얻어지는 화합물을 함유하고, UV 노광에 의해 화상 형성 가능하고, 표면의 택성이 작고, 라미네이트성 및 취급성이 양호하고, 보존 안정성이 우수하고, 고감도로 현상성도 우수하고, 현상 후에 우수한 내약품성, 표면 경도, 내열성, 유전 특성 등을 발현하는 감광성 조성물 및 이것을 사용한 감광성 필름, 및 고정밀한 영구 패턴(보호막, 층간 절연막 및 솔더 레지스트 패턴 등) 및 그 효율적인 형성 방법을 제공할 수 있다.According to the present invention, a problem in the prior art can be solved, and the compound does not cause a reaction under normal temperature at the time of storage, contains a compound which starts a crosslinking reaction by heating, and obtains a favorable film hardness of the cured film, and by UV exposure. It is capable of forming an image, has low surface tack, good lamination and handling properties, excellent storage stability, high sensitivity and developability, and shows excellent chemical resistance, surface hardness, heat resistance and dielectric properties after development. The photosensitive composition, the photosensitive film using the same, and high-precision permanent pattern (protective film, an interlayer insulation film, a soldering resist pattern, etc.), and its efficient formation method can be provided.
(감광성 조성물)(Photosensitive composition)
본 발명의 감광성 조성물은 (A) 1분자 중에 1개 이상의 카르복실기 및 에스 테르기 중 어느 하나를 갖는 중합체, (B) 중합성 화합물, (C) 광중합 개시제 및 (D) 후술의 일반식(1)∼(3)으로 나타내어지는 화합물로부터 선택되는 적어도 1종의 화합물을 적어도 함유하고, 병용하는 열가교제를 함유하고 있어도 좋고, 또한 필요에 따라서, 착색 안료, 체질 안료, 열중합 금지제 및 계면활성제 등의 그 밖의 성분을 함유해서 이루어진다.The photosensitive composition of this invention is a polymer which has any one or more of carboxyl groups and an ester group in (A) 1 molecule, (B) polymeric compound, (C) photoinitiator, and (D) general formula (1) mentioned later It may contain at least one compound selected from the compounds represented by (3) at least and may contain a thermal crosslinking agent to be used in combination, and if necessary, color pigments, extender pigments, thermal polymerization inhibitors, surfactants and the like. It is made by containing other components of.
[(A)바인더(중합체)][(A) Binder (Polymer)]
상기 바인더로서는 알칼리성 수용액에 대하여 팽윤성을 나타내는 화합물이 바람직하고, 알칼리성 수용액에 대하여 가용성인 화합물이 보다 바람직하다.As said binder, the compound which shows swelling property with respect to alkaline aqueous solution is preferable, and the compound which is soluble with respect to alkaline aqueous solution is more preferable.
알칼리성 수용액에 대하여 팽윤성 또는 용해성을 나타내는 바인더로서는, 예를 들면, 산성기를 갖는 것이 바람직하게 열거되고, 구체적으로는 에폭시 화합물에 에틸렌성 불포화 이중 결합과 산성기를 도입한 화합물(에폭시아크릴레이트 화합물), 측쇄에 (메타)아크릴로일기, 및 산성기를 갖는 비닐 공중합체, 에폭시아크릴레이트 화합물과 측쇄에 (메타)아크릴로일기 및 산성기를 갖는 비닐공중합체의 혼합물, 말레아미드산계 공중합체 등이 바람직하다.As a binder which shows swelling property or solubility with respect to alkaline aqueous solution, what has an acidic group is mentioned preferably, for example, The compound (epoxyacrylate compound) which introduce | transduced an ethylenically unsaturated double bond and an acidic group into an epoxy compound specifically, a side chain The vinyl copolymer which has an (meth) acryloyl group and an acidic group, the mixture of an epoxy acrylate compound and the vinyl copolymer which has a (meth) acryloyl group and an acidic group in a side chain, a maleamic acid type copolymer, etc. are preferable.
상기 산성기로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있고, 예를 들면, 카르복실기, 술폰산기, 인산기 등이 열거되고, 이들 중에서도 원료의 입수성 등의 관점으로부터, 카르복실기가 바람직하게 열거된다.There is no restriction | limiting in particular as said acidic group, According to the objective, it can select suitably, For example, a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. are mentioned, Among these, a carboxyl group is preferably listed from a viewpoint of the availability of a raw material, etc. among these. .
<에폭시아크릴레이트 화합물><Epoxyacrylate Compound>
상기 에폭시 화합물에 에틸렌성 불포화 이중 결합과 산성기를 도입한 화합물(에폭시아크릴레이트 화합물)로서는, 특별히 제한은 없고, 목적에 따라서 적당하 게 선택할 수 있고, 예를 들면 다관능 에폭시 화합물과 카르복실기 함유 모노머를 반응시키고, 또한, 다염기산 무수물을 부가시키는 방법 등으로 얻어진다.There is no restriction | limiting in particular as a compound (epoxy acrylate compound) which introduce | transduced ethylenically unsaturated double bond and an acidic group into the said epoxy compound, According to the objective, it can select suitably, For example, a polyfunctional epoxy compound and a carboxyl group-containing monomer are used. It is made to react, and also obtained by the method of adding a polybasic acid anhydride.
상기 다관능 에폭시 화합물로서는 예를 들면 비크실레놀형 또는 비스페놀형 에폭시 수지(「YX4000; 재팬 에폭시 레진사 제작」등) 또는 이들 혼합물, 이소시아누레이트 골격 등을 갖는 복소환식 에폭시 수지(「TEPIC; 닛산화학공업사 제작」, 「아랄다이트 PT810; 치바 스페셜티 케미컬즈사 제작」등), 비스페놀 A형 에폭시 수지, 비스페놀 F형 에폭시 수지, 수소 첨가 비스페놀 A형 에폭시 수지, 비스페놀 S형 에폭시 수지, 페놀노볼락형 에폭시 수지, 크레졸 노볼락형 에폭시 수지, 할로겐화 페놀노볼락형 에폭시 수지, 글리시딜 아민형 에폭시 수지(예를 들면, 테트라글리시딜디아미노디페닐메탄 등), 히단토인형 에폭시 수지, 지환식 에폭시 수지, 트리히드록시 페닐 메탄형 에폭시 수지, 비스페놀 A 노볼락형 에폭시 수지, 테트라페닐에탄형 에폭시 수지, 글리시딜 프탈레이트 수지, 테트라글리시딜크실레노일에탄수지, 나프탈렌기 함유 에폭시 수지(「ESN-190, ESN-360; 신일본제철화학사 제작」, 「HP-4032,EXA-4750,EXA-4700; 다이니폰잉크 화학공업사 제작」등) 디시클로펜타디엔 골격을 갖는 에폭시 수지(「HP-7200, HP-7200H; 다이니폰 잉크 화학공업사 제작」등); 페놀, o-크레졸, 나프톨 등의 페놀 화합물과, 페놀성 수산기를 갖는 방향족 알데히드(예를 들면, p-히드록시벤즈알데히드)와의 축합 반응에 의해 얻어지는 폴리페놀 화합물과 에피클로로히드린의 반응물; 페놀 화합물과 디비닐벤젠이나 디시클로펜타디엔 등의 디올레핀 화합물의 부가 반응에 의하여 얻어지는 폴리페놀 화합물과 에피클로로히드린의 반응물; 4-비닐시클로헥센-1-옥사이드의 개환 중합물 을 과아세트산 등으로 에폭시화한 것; 트리글리시딜이소시아누레이트 등의 복소환을 갖는 에폭시 수지; 글리시딜메타아크릴레이트 공중합계 에폭시 수지(「CP-50S, CP-50M; 일본유지사 제작」등), 시클로헥실 말레이미드와 글리시딜 메타아크릴레이트의 공중합 에폭시 수지 등이 열거된다. 이들은 1종 단독으로 사용해도 좋고, 2종 이상을 병용해도 좋다.As said polyfunctional epoxy compound, the heterocyclic epoxy resin ("TEPIC; Nissan") which has a bixylenol type or bisphenol-type epoxy resin ("YX4000; Japan epoxy resin company", etc.) or these mixtures, an isocyanurate skeleton etc. Chemical industry production "," Araldite PT810; Chiba specialty chemicals company production ", bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolak type Epoxy resin, cresol novolak type epoxy resin, halogenated phenol novolak type epoxy resin, glycidyl amine type epoxy resin (for example, tetraglycidyl diaminodiphenylmethane, etc.), hydantoin type epoxy resin, alicyclic type Epoxy resin, trihydroxy phenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylethane type epoxy resin, gly Dyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group containing epoxy resin ("ESN-190, ESN-360; the product made by Nippon Steel Chemical Co., Ltd.", "HP-4032, EXA-4750, EXA-4700; Dainippon) Ink chemical company ", etc.) Epoxy resins having a dicyclopentadiene skeleton (" HP-7200, HP-7200H; Dainippon ink chemical company ", etc.); Reactant of the polyphenol compound and epichlorohydrin obtained by condensation reaction of phenol compounds, such as a phenol, o-cresol, a naphthol, and aromatic aldehyde which has a phenolic hydroxyl group (for example, p-hydroxybenzaldehyde); Reactant of the polyphenol compound and epichlorohydrin obtained by addition reaction of a phenol compound and diolefin compounds, such as divinylbenzene and dicyclopentadiene; Epoxidation of the ring-opened polymer of 4-vinylcyclohexene-1-oxide with peracetic acid or the like; Epoxy resins having heterocycles such as triglycidyl isocyanurate; The glycidyl methacrylate copolymer type epoxy resin ("CP-50S, CP-50M; the Japan oil company make", etc.), the copolymerization epoxy resin of cyclohexyl maleimide, glycidyl methacrylate, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
또한, 상기 카르복실기 함유 모노머의 예로서는 예를 들면 (메타)아크릴산, 비닐안식향산, 말레인산, 말레인산 모노알킬에스테르, 푸말산, 이타콘산, 크로톤 산, 계피산, 소르빈산, α-시아노 신남산, 아크릴산 다이머; 그 밖에 2-히드록시에틸(메타)아크릴레이트 등의 수산기를 갖는 단량체와 무수 말레인산, 무수 프탈산, 시클로헥산 디카르복실산 무수물 등의 환상 산무수물의 부가 반응물; 할로겐 함유 카르복실산 화합물의 반응생성물, ω-카르복시폴리카프로락톤모노(메타)아크릴레이트등이 열거된다. 또한, 시판품으로서는, 동아합성화학공업(주) 제작 아로닛쿠스 M-5300, M-5400, M-5500 및 M-5600, 신나카무라화학공업(주) 제작 NK에스테르 CB-1 및 CBX-1, 교에샤유지화학공업(주) 제작 HOA-MP 및 HOA-MS, 오사카유기화학공업(주) 제작 비스 코트#2100 등을 사용할 수 있다. 이들은 1종 단독으로 사용해도 좋고, 2종 이상을 병용해도 좋다.Examples of the carboxyl group-containing monomers include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl esters, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyano cinnamic acid, acrylic acid dimers; In addition, addition reaction products of monomers which have hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate, and cyclic acid anhydrides, such as maleic anhydride, a phthalic anhydride, cyclohexane dicarboxylic anhydride; The reaction product of a halogen containing carboxylic acid compound, (omega)-carboxy polycaprolactone mono (meth) acrylate, etc. are mentioned. Moreover, as a commercial item, NK ester CB-1 and CBX-1 by Aronikkusu M-5300, M-5400, M-5500, and M-5600, Shin-Nakamura Chemical Co., Ltd., HOA-MP and HOA-MS manufactured by Kyoesha Oil & Chemicals Co., Ltd., and Biscoat # 2100 produced by Osaka Organic Chemicals Co., Ltd. can be used. These may be used individually by 1 type and may use 2 or more types together.
또한, 상기 다염기산 무수물로서는, 예를 들면, 무수 숙신산, 무수 메틸 숙신산, 무수 2,3-디메틸 숙신산, 무수 2,2-디메틸 숙신산, 무수 에틸 숙신산, 무수 도데세닐 숙신산, 무수 노네닐 숙신산, 무수 말레인산, 무수 메틸말레인산, 무수2,3-디메틸 말레인산, 무수 2-클로로말레인산, 무수 2,3-디클로로말레인산, 무수 브로모말레인산, 무수 이타콘산, 무수 시트라콘산, 무수 시스아코닛산, 무수 프탈산, 테트라히드로 무수 프탈산, 테트라클로로 무수 프탈산, 테트라브로모 무수 프탈산, 헥사히드로 무수 프탈산, 메틸테트라히드로 무수 프탈산, 메틸헥사히드로 무수 프탈산, 엔도메틸렌테트라히드로 무수 프탈산, 메틸엔도메틸렌테트라히드로 무수 프탈산, 무수 클로렌드산 및 5-(2,5-디옥소테트라히드로푸릴)-3-메틸-3-시클로헥센-1,2-디카르복실산 무수물 등의 이염기산 무수물, 무수 트리멜리트산, 무수 피로멜리트산, 3,3',4,4'-벤조페논테트라카르복실산 등의 다염기산 무수물 등도 사용할 수 있다. 이들은 1종 단독으로 사용해도 좋고, 2종 이상을 병용해도 좋다.Moreover, as said polybasic acid anhydride, for example, succinic anhydride, methyl succinic anhydride, 2,3-dimethyl succinic anhydride, 2,2-dimethyl succinic anhydride, ethyl succinic anhydride, dodecenyl succinic anhydride, nonenyl succinic anhydride, maleic anhydride , Methyl maleic anhydride, 2,3-dimethyl maleic anhydride, 2-chloro maleic anhydride, 2,3-dichloro maleic anhydride, bromomaleic anhydride, itaconic anhydride, citraconic anhydride, cisaconic anhydride, phthalic anhydride, tetra Hydrophthalic anhydride, tetrachloro phthalic anhydride, tetrabromo phthalic anhydride, hexahydro phthalic anhydride, methyltetrahydro phthalic anhydride, methylhexahydro phthalic anhydride, endomethylenetetrahydro phthalic anhydride, methylendomethylenetetrahydro phthalic anhydride, chlorine anhydride Acids and 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride Polybasic acid anhydrides, such as a dibasic acid anhydride, a trimellitic anhydride, a pyromellitic anhydride, and a 3,3 ', 4,4'- benzophenone tetracarboxylic acid, etc. can also be used. These may be used individually by 1 type and may use 2 or more types together.
각각을 순차적으로 반응시켜서, 에폭시아크릴레이트를 얻지만, 그들을 반응시키는 비율은 다관능 에폭시 화합물의 에폭시기 1당량에 대하여, 카르복실기 함유 모노머의 카르복실기 0.8∼1.2당량, 바람직하게는, 0.9∼1.1당량이며, 다염기산 무수물 0.1∼1.0당량, 바람직하게는 0.3∼1.0당량이다.Each reacted sequentially to obtain an epoxy acrylate, but the ratio of reacting them was 0.8 to 1.2 equivalents, preferably 0.9 to 1.1 equivalents, of the carboxyl group-containing monomer relative to 1 equivalent of the epoxy group of the polyfunctional epoxy compound. 0.1-1.0 equivalent, Preferably it is 0.3-1.0 equivalent.
또한, 일본특허공개 평5-70528호 공보 기재의 플루오렌 골격을 갖는 에폭시아크릴레이트(카르복실기를 갖고 있지 않은 화합물)에 상기 다염기산 무수물을 부가시켜서 얻어지는 화합물 등도 본 발명의 에폭시아크릴레이트로서 이용할 수 있다.Moreover, the compound etc. which are obtained by adding the said polybasic acid anhydride to the epoxy acrylate (compound which does not have a carboxyl group) which have a fluorene frame | skeleton of Unexamined-Japanese-Patent No. 5-70528 can also be used as an epoxy acrylate of this invention.
상기 에폭시 화합물에 에틸렌성 불포화 이중결합과 산성기를 도입한 화합물 중에서도 하기 구조식(III) 및 (IV)로 나타내어지는 에폭시아크릴레이트 화합물이 바람직하다.Among the compounds in which an ethylenically unsaturated double bond and an acidic group are introduced into the epoxy compound, an epoxy acrylate compound represented by the following structural formulas (III) and (IV) is preferable.
단, 상기 일반식(III) 중, X는 수소 원자 및 적어도 산성기를 함유하는 치환 기 중 어느 하나를 나타내고, Y는 메틸렌기, 이소프로필리덴기 및 술포닐기 중 어느 하나를 나타내고, n은 1∼20의 정수를 나타낸다.In the above general formula (III), X represents any one of a substituent containing a hydrogen atom and at least an acidic group, Y represents any one of a methylene group, an isopropylidene group and a sulfonyl group, and n represents 1 to 1 The integer of 20 is shown.
단, 상기 일반식(IV) 중 n은 1∼20의 정수를 나타낸다.However, in said general formula (IV), n represents the integer of 1-20.
또한, 상기 구조식(III)으로 나타내어지는 에폭시아크릴레이트 화합물로서는 구체적으로는 하기 구조식(V)으로 나타내어지는 비스페놀 F형 에폭시아크릴레이트 화합물 및 하기 구조식(VI)으로 나타내지는 비스페놀 A형 에폭시아크릴레이트 화합물이 보다 바람직하다.As the epoxy acrylate compound represented by the structural formula (III), specifically, a bisphenol F-type epoxy acrylate compound represented by the following structural formula (V) and a bisphenol A type epoxy acrylate compound represented by the following structural formula (VI) More preferred.
상기 에폭시아크릴레이트 화합물의 분자량으로서는, 1,000∼100,000이 바람직하고, 2,000∼50,000이 보다 바람직하다. 상기 분자량이 1,000미만이면, 감광층표면의 택성이 강해지는 경우가 있고, 후술하는 감광층의 경화 후에 있어서, 막질이 무르게 되거나 또는 표면경도가 열화하는 경우가 있고, 100,000을 초과하면, 현상성이 열화하는 경우가 있다. 또한, 수지의 합성도 곤란해진다.As molecular weight of the said epoxy acrylate compound, 1,000-100,000 are preferable and 2,000-50,000 are more preferable. When the said molecular weight is less than 1,000, the tackiness of the surface of a photosensitive layer may become strong, and after hardening of the photosensitive layer mentioned later, a film quality may become soft or surface hardness may deteriorate, and when it exceeds 100,000, developability will be It may deteriorate. In addition, the synthesis of the resin also becomes difficult.
<측쇄에 (메타)아크릴로일기 및 산성기를 갖는 비닐 공중합체><Vinyl copolymer having a (meth) acryloyl group and an acidic group in the side chain>
상기 측쇄에 (메타)아크릴로일기 및 산성기를 갖는 비닐 공중합체로서는 예를 들면, (1) 산성기를 갖는 비닐 모노머, (2) 필요에 따라서 후술하는 고분자 반응에 이용 가능한 관능기를 갖는 비닐 모노머, 및 (3) 필요에 따라서 기타의 공중합 가능한 비닐 모노머의 비닐(공)중합으로 얻어지는 (공)중합체를 합성하고, 또한 (4) 상기 (공)중합체 중의 산성기 또는 고분자 반응에 이용 가능한 관능기 중 적어도 1종에 대하여 반응성을 갖는 관능기와 (메타)아크릴로일기를 갖는 화합물을 고 분자 반응시킴으로써 얻어진다.As a vinyl copolymer which has a (meth) acryloyl group and an acidic group in the said side chain, For example, (1) the vinyl monomer which has an acidic group, (2) the vinyl monomer which has a functional group which can be used for the polymer reaction mentioned later as needed, and (3) Synthesizing (co) polymers obtained by vinyl (co) polymerization of other copolymerizable vinyl monomers as necessary, and (4) at least one of the acidic groups in the (co) polymers or functional groups available for polymer reactions. It is obtained by making high molecular reaction of the compound which has the functional group and (meth) acryloyl group which are reactive with respect to a species.
상기 (1) 산성기를 갖는 비닐 모노머의 산성기로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있고, 예를 들면, 일본특허공개 2005-258431호 공보에 기재된 [0164]에 기재되어 있는 화합물 등이 열거된다. 또한, 이들의 모노머는 1종 단독으로 사용해도 좋고, 2종 이상을 병용해도 좋다.There is no restriction | limiting in particular as an acidic group of the vinyl monomer which has the said (1) acidic group, According to the objective, it can select suitably, For example, the compound described in Unexamined-Japanese-Patent No. 2005-258431, etc. This is listed. In addition, these monomers may be used individually by 1 type, and may use 2 or more types together.
또한, 카르복실기의 전구체로서 무수 말레인산, 무수 이타콘산, 무수 시트라콘산 등의 무수물을 갖는 모노머를 사용해도 좋다.Moreover, you may use the monomer which has anhydrides, such as maleic anhydride, itaconic anhydride, a citraconic acid anhydride, as a precursor of a carboxyl group.
상기 (2)의 고분자 반응에 이용 가능한 관능기를 갖는 비닐 모노머에 있어서의 고분자 반응에 이용 가능한 관능기로서는 수산기, 아미노기, 이소시아네이트기, 에폭시기, 산 할라이드기, 활성 할라이드기 등이 열거된다. 또한, 상술 (1)의 카르복실기나 산무수물기도 이용 가능한 관능기로서 열거된다.As a functional group which can be used for the polymer reaction in the vinyl monomer which has a functional group which can be used for the polymer reaction of said (2), a hydroxyl group, an amino group, an isocyanate group, an epoxy group, an acid halide group, an active halide group, etc. are mentioned. Moreover, the carboxyl group and acid anhydride of above-mentioned (1) are also listed as a functional group which can be used.
상기 수산기를 갖는 비닐모노머로서는 예를 들면, 일본특허공개 2005-258431호 공보의 [0182]∼[0192]에 기재되어 있는 화합물이 열거된다.As a vinyl monomer which has the said hydroxyl group, the compound described in [0182]-[0192] of Unexamined-Japanese-Patent No. 2005-258431 is mentioned, for example.
상기 아미노기를 갖는 비닐 모노머로서는 예를 들면, 비닐벤질아민, 아미노에틸메타크릴레이트 등이 열거된다.As a vinyl monomer which has the said amino group, vinylbenzylamine, aminoethyl methacrylate, etc. are mentioned, for example.
상기 이소시아네이트기를 갖는 모노머로서는 예를 들면, 일본특허공개 2005-258431호 공보의 [0176]∼[0180]에 기재되어 있는 화합물이 열거된다.As a monomer which has the said isocyanate group, the compound described in [0176]-[0180] of Unexamined-Japanese-Patent No. 2005-258431 is mentioned, for example.
상기 에폭시기를 갖는 비닐 모노머로서는 예를 들면, 글리시딜(메타)아크릴레이트, 하기 구조식(45)으로 나타내어지는 화합물 등이 열거된다.As a vinyl monomer which has the said epoxy group, glycidyl (meth) acrylate, the compound represented by following structural formula (45), etc. are mentioned, for example.
단, 상기 구조식(45) 중 R은 H 및 Me중 어느 하나를 나타낸다.However, in the formula (45), R represents any one of H and Me.
상기 산 할라이드기를 갖는 비닐 모노머로서는 예를 들면, (메타)아크릴산 클로라이드 등이 열거된다.As a vinyl monomer which has the said acid halide group, (meth) acrylic acid chloride etc. are mentioned, for example.
상기 활성 할라이드기를 갖는 비닐 모노머로서는 예를 들면, 클로로메틸스티렌 등이 열거된다.As a vinyl monomer which has the said active halide group, chloromethyl styrene etc. are mentioned, for example.
이들의 시판품으로서는, 예를 들면 「카네카 레진 AXE; 가네가후치화학공업(주) 제작」, 「사이클로머(CYCLOMER) A-200; 다이셀화학공업(주) 제작」, 「사이클로머(CYCLOMER) M-200; 다이셀화학공업(주) 제작」, 「SPCP1X, SPCP2X, SPCP3X; 쇼와고분자(주) 제작」등을 사용할 수 있다.As these commercial items, it is "Kaneka resin AXE; Kanegafuchi Chemical Co., Ltd. product "," CYCLOMER A-200; Daicel Chemical Co., Ltd. product "," CYCLOMER M-200; Daicel Chemical Industries, Ltd. "," SPCP1X, SPCP2X, SPCP3X; "Showa Polymer Co., Ltd." etc. can be used.
또한, 상기 각 모노머는 1종 단독으로 사용해도 좋고, 2종 이상을 병용해도 좋다.In addition, each said monomer may be used individually by 1 type, and may use 2 or more types together.
상기 (3)의 필요에 따라서 사용되는 그 밖의 공중합 가능한 모노머로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있지만, 예를 들면 일본특허공개 2005-258431호 공보의 [0165]∼[0174]에 기재되어 있는 화합물 등이 열거된다.There is no restriction | limiting in particular as another copolymerizable monomer used as needed of said (3), Although it can select suitably according to the objective, For example, in Unexamined-Japanese-Patent No. 2005-258431, [0165]-[0174] The compound described, etc. are mentioned.
상기 관능기로서 우레탄기 또는 우레아기를 갖는 비닐 모노머의 합성 방법으로서는, 예를 들면 이소시아나토기와 수산기 또는 아미노기의 부가 반응이 열거되 고, 구체적으로는 이소시아나토기를 갖는 모노머와 수산기를 1개 함유하는 화합물, 또는 1급 또는 2급 아미노기를 1개 갖는 화합물의 부가반응, 수산기를 갖는 모노머, 또는 1급 또는 2급 아미노기를 갖는 모노머와 모노이소시아나토의 부가 반응이 열거된다.As a synthesis method of the vinyl monomer which has a urethane group or a urea group as the said functional group, addition reaction of an isocyanato group, a hydroxyl group, or an amino group is mentioned, for example, One monomer and hydroxyl group which have an isocyanato group specifically, are mentioned. The addition reaction of the compound containing, or the compound which has one primary or secondary amino group, the monomer which has a hydroxyl group, or the addition reaction of the monomer which has a primary or secondary amino group, and monoisocyanato is mentioned.
상기 이소시아나토기를 갖는 모노머로서는, 예를 들면, 일본특허공개 2005-258431호 공보의 [0176]∼[0180]에 기재되어 있는 화합물이 열거된다.As a monomer which has the said isocyanato group, the compound described in [0176]-[0180] of Unexamined-Japanese-Patent No. 2005-258431 is mentioned, for example.
상기 모노이소시아네이트로서는 예를 들면, 일본특허공개 2005-258431호 공보의 [0181]에 기재되어 있는 화합물 등이 열거된다.As said monoisocyanate, the compound etc. which are described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.
상기 수산기를 갖는 모노머로서는 예를 들면, 일본특허공개 2005-258431호 공보의 [0182]∼[0192]에 기재되어 있는 화합물이 열거된다.As a monomer which has the said hydroxyl group, the compound described in [0182]-[0192] of Unexamined-Japanese-Patent No. 2005-258431 is mentioned, for example.
상기 수산기를 1개 함유하는 화합물로서는 예를 들면, 일본특허공개 2005-258431호 공보의 [0193]에 기재되어 있는 화합물 등이 열거된다.As a compound containing one said hydroxyl group, the compound etc. which are described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.
상기 1급 또는 2급 아미노기를 갖는 모노머로서는 예를 들면, 비닐벤질아민 등이 열거된다.As a monomer which has the said primary or secondary amino group, vinylbenzylamine etc. are mentioned, for example.
상기 1급 또는 2급 아미노기를 1개 함유하는 화합물로서는 예를 들면, 일본특허공개 2005-258431호 공보의 [0195]에 기재되어 있는 화합물 등이 열거된다.As a compound containing one said primary or secondary amino group, the compound etc. which are described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.
또한 이들의 모노머는 1종 단독으로 사용해도 좋고, 2종 이상을 병용해도 좋다.In addition, these monomers may be used individually by 1 type, and may use 2 or more types together.
이들을 비닐(공)중합시킴으로써 산성기, 산무수물기 및 필요에 따라서 수산기, 아미노기, 이소시아네이트기, 에폭시기, 산 할라이드기, 활성 할라이드기 등을 함유하는 (공)중합체가 얻어진다. 상기 비닐(공)중합체는 각각 해당하는 모노머를 공지의 방법에 의해 통상의 방법을 따라서 공중합시킴으로써 조제할 수 있다. 예를 들면, 일본특허공개 2005-258431호 공보의 [0198]에 기재되어 있는 방법에 의해 조제할 수 있다.By vinyl (co) polymerizing these, the (co) polymer containing an acidic group, an acid anhydride group, and if necessary, a hydroxyl group, an amino group, an isocyanate group, an epoxy group, an acid halide group, an active halide group, etc. is obtained. The said vinyl (co) polymer can be prepared by copolymerizing the corresponding monomer, respectively by a well-known method according to a conventional method. For example, it can prepare by the method of Unexamined-Japanese-Patent No. 2005-258431.
이렇게 하여 얻어진 (공)중합체에 대하여, 상기 (4)로서, 이들의 공중합체 중의 산성기 및 필요에 따라서 수산기, 아미노기, 이소시아네이트기, 글리시딜기, 산할라이드기 중 적어도 1종에 대하여 반응성을 갖는 관능기와 (메타)아크릴로일 기를 갖는 화합물을 고분자 반응시킴으로써 얻어진다.The (co) polymer obtained in this way has the reactivity with at least one of the acidic groups in these copolymers and, if necessary, hydroxyl groups, amino groups, isocyanate groups, glycidyl groups and acid halide groups. It is obtained by polymer-reacting the compound which has a functional group and a (meth) acryloyl group.
상기 (4)의 (공)중합체 중의 산성기 또는 고분자 반응에 이용 가능한 관능기중 적어도 1종에 대하여 반응성을 갖는 관능기와 (메타)아크릴로일기를 갖는 화합물로서는 상술의 (2)에 나타낸 화합물 등을 이용할 수 있다.As a compound which has the functional group and (meth) acryloyl group which are reactive with at least 1 sort (s) among the acidic group in the (co) polymer of said (4), or the functional group which can be used for polymer reaction, the compound etc. which were mentioned in (2) mentioned above are mentioned. It is available.
이들의 고분자 반응을 행할 경우의 관능기의 조합의 예로서는, 예를 들면 산성기(카르복실기 등)를 갖는 공중합체와 에폭시기를 갖는 비닐 모노머의 조합, 아미노기를 갖는 공중합체와 에폭시기를 갖는 비닐 모노머의 조합, 아미노기를 갖는 공중합체와 이소시아네이트기를 갖는 비닐 모노머의 조합, 수산기를 갖는 공중합체와 이소시아네이트기를 갖는 비닐 모노머의 조합, 수산기를 갖는 공중합체와 산할라이드기를 갖는 비닐 모노머의 조합, 아미노기를 갖는 공중합체와 활성 할라이드 기를 갖는 비닐 모노머의 조합, 산무수물기를 갖는 공중합체와 수산기를 갖는 비닐 모노머의 조합, 이소시아네이트기를 갖는 공중합체와 아미노기를 갖는 비닐 모노머의 조합, 이소시아네이트기를 갖는 공중합체와 수산기를 갖는 비닐 모노머의 조합, 활성 할라이드기를 갖는 공중합체와 아미노기를 갖는 비닐 모노머의 조합 등 이 열거된다. 또한, 이들의 조합은 2종 이상을 병용해도 상관없다.Examples of the combination of functional groups in the case of performing these polymer reactions include, for example, a combination of a copolymer having an acid group (carboxyl group and the like) and a vinyl monomer having an epoxy group, a combination of a copolymer having an amino group and a vinyl monomer having an epoxy group, Combination of copolymer having amino group and vinyl monomer having isocyanate group, Combination of copolymer having hydroxyl group and vinyl monomer having isocyanate group, Combination of copolymer having hydroxyl group and vinyl monomer having acid halide group, Copolymer having amino group and active Combination of vinyl monomers having halide groups, copolymers of acid anhydride groups and vinyl monomers having hydroxyl groups, combinations of copolymers having isocyanate groups and vinyl monomers having amino groups, combinations of copolymers having isocyanate groups and vinyl monomers having hydroxyl groups Active harley The combination of such a vinyl monomer having an amino group and a copolymer having a group are exemplified. In addition, these combinations may use 2 or more types together.
<말레아미드산계 공중합체><Maleamic Acid Copolymer>
상기 말렌아미드산계 공중합체는 무수 말레인산 공중합체의 무수물기에 대하여 1급 아민 화합물을 1종 이상 반응시켜서 얻어지는 공중합체이다. 상기 공중합체는 하기 구조식(VII)으로 나타내어지는 말레인산 하프 아미드 구조를 갖는 말레아미드산 유닛 B와 상기 말레인산 하프 아미드 구조를 갖지 않는 유닛 A를 적어도 포함하는 말레아미드산계 공중합체인 것이 바람직하다.The maleic amide copolymer is a copolymer obtained by reacting at least one primary amine compound with an anhydride group of a maleic anhydride copolymer. The copolymer is preferably a maleamic acid copolymer comprising at least a maleamic acid unit B having a maleic acid half amide structure represented by the following structural formula (VII) and a unit A not having the maleic acid half amide structure.
상기 유닛 A는 1종이어도 좋고, 2종 이상이어도 좋다. 예를 들면, 상기 유닛 B가 1종이라고 하면, 상기 유닛 A가 1종일 경우에는 상기 말레아미드산계 공중합체가 2원 공중합체를 의미하는 것이 되고, 상기 유닛 A가 2종일 경우에는 상기 말레아미드산계 공중합체가 3원 공중합체를 의미하게 된다.The unit A may be one kind or two or more kinds. For example, when said unit B is 1 type, when the said unit A is 1 type, the said maleamic acid type copolymer means a binary copolymer, and when said unit A is 2 types, the said maleamic acid type is Copolymer means tertiary copolymer.
상기 유닛 A로서는 치환기를 갖고 있어도 좋은 아릴기와 후술하는 비닐 단량체로서, 상기 비닐 단량체의 호모 폴리머의 유리전이온도(Tg)가 80℃ 미만인 비닐 단량체(c)의 조합이 바람직하게 열거된다.As said unit A, the combination of the aryl group which may have a substituent and the vinyl monomer (c) whose glass transition temperature (Tg) of the homopolymer of the said vinyl monomer is less than 80 degreeC is mentioned preferably.
단, 상기 구조식(VII) 중, R3 및 R4는 수소 원자 및 저급 알킬기 중 어느 하나를 나타낸다. x 및 y는 반복단위의 몰분율을 나타내고, 예를 들면 상기 유닛 A가 1종인 경우, x는 85∼50몰%이고, y는 15∼50몰%이다.However, in said structural formula (VII), R <3> and R < 4 > represents either a hydrogen atom and a lower alkyl group. x and y represent the mole fraction of a repeating unit, for example, when the said unit A is 1 type, x is 85-50 mol% and y is 15-50 mol%.
상기 구조식(VI) 중 R1으로서는 예를 들면 (-COOR10), (-CONR11R12), 치환기를 갖고 있어도 좋은 아릴기, (-OCOR13), (-OR14), (-COR15) 등의 치환기가 열거된다. 여기서, 상기 R10∼R15는 수소 원자(-H), 치환기를 갖고 있어도 좋은 알킬기, 아릴기 및 아랄킬기 중 어느 하나를 나타낸다. 상기 알킬기, 아릴기 및 아랄킬기는 환상 구조 또는 분기 구조를 갖고 있어도 좋다.Examples of R 1 in the structural formula (VI) include (-COOR 10 ), (-CONR 11 R 12 ), an aryl group which may have a substituent, (-OCOR 13 ), (-OR 14 ), (-COR 15 Substituents such as Here, said R <10> -R <15> represents either the hydrogen atom (-H), the alkyl group which may have a substituent, an aryl group, and an aralkyl group. The alkyl group, aryl group and aralkyl group may have a cyclic structure or a branched structure.
상기 R10∼R15로서는 예를 들면, 메틸, 에틸, n-프로필, i-프로필, n-부틸, i-부틸, sec-부틸, t-부틸, 펜틸, 알릴, n-헥실, 시클로헥실, 2-에틸헥실, 도데실, 메톡시에틸, 페닐, 메틸페닐, 메톡시페닐, 벤질, 페네틸, 나프틸, 클로로페닐 등 이 열거된다.As said R <10> -R <15> , methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, pentyl, allyl, n-hexyl, cyclohexyl, 2-ethylhexyl, dodecyl, methoxyethyl, phenyl, methylphenyl, methoxyphenyl, benzyl, phenethyl, naphthyl, chlorophenyl and the like are listed.
상기 R1의 구체예로서는 예를 들면, 페닐, α-메틸페닐, 2-메틸페닐, 3-메틸페닐, 4-메틸페닐, 2,4-디메틸페닐 등의 벤젠 유도체; n-프로필옥시카르보닐, n-부틸옥시카르보닐, 펜틸옥시카르보닐, 헥실옥시카르보닐, n-부틸옥시카르보닐, n-헥실옥시카르보닐, 2-에틸헥실옥시카르보닐, 메틸옥시카르보닐 등이 열거된다.As a specific example of said R <1> , For example, benzene derivatives, such as phenyl, (alpha)-methylphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2, 4- dimethylphenyl; n-propyloxycarbonyl, n-butyloxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, n-butyloxycarbonyl, n-hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, methyl Oxycarbonyl and the like.
상기 R2로서는 치환기를 갖고 있어도 좋은 알킬기, 아릴기, 아랄킬기 등이 열거된다. 이들은 환상 구조 또는 분기 구조를 갖고 있어도 좋다. 상기 R2의 구체예로서는 예를 들면 벤질, 페네틸, 3-페닐-1-프로필, 4-페닐-1-부틸, 5-페닐-1-펜틸, 6-페닐-1-헥실, α-메틸벤질, 2-메틸벤질, 3-메틸벤질, 4-메틸벤질, 2-(p-톨릴)에틸, β-메틸페네틸, 1-메틸-3-페닐프로필, 2-클로로벤질, 3-클로로벤질, 4-클로로벤질, 2-플루오로벤질, 3-플루오로벤질, 4-플루오로벤질, 4-브로모페네틸, 2-(2-클로로페닐)에틸, 2-(3-클로로페닐)에틸, 2-(4-클로로페닐)에틸, 2-(2-플루오로페닐)에틸, 2-(3-플루오로페닐)에틸, 2-(4-플루오로페닐)에틸, 4-플루오로-α,α-디메틸 페네틸, 2-메톡시벤질, 3-메톡시벤질, 4-메톡시벤질, 2-에톡시벤질, 2-메톡시페네틸, 3-메톡시페네틸, 4-메톡시페네틸, 메틸, 에틸, 프로필, i-프로필, 부틸, t-부틸, sec-부틸, 펜틸, 헥실, 시클로헥실, 헵틸, 옥틸, 라우릴, 페닐, 1-나프틸, 메톡시메틸, 2-메톡시에틸, 2-에톡시에틸, 3-메톡시프로필, 2-부톡시에틸, 2-시클로헥실옥시에틸, 3-에톡시프로필, 3-프로폭시프로필, 3-이소프로폭시프로필아민 등이 열거된다.As said R <2> , the alkyl group, aryl group, aralkyl group etc. which may have a substituent are mentioned. These may have a cyclic structure or a branched structure. Specific examples of R 2 include benzyl, phenethyl, 3-phenyl-1-propyl, 4-phenyl-1-butyl, 5-phenyl-1-pentyl, 6-phenyl-1-hexyl, α-methylbenzyl 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2- (p-tolyl) ethyl, β-methylphenethyl, 1-methyl-3-phenylpropyl, 2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 4-bromophenethyl, 2- (2-chlorophenyl) ethyl, 2- (3-chlorophenyl) ethyl, 2 -(4-chlorophenyl) ethyl, 2- (2-fluorophenyl) ethyl, 2- (3-fluorophenyl) ethyl, 2- (4-fluorophenyl) ethyl, 4-fluoro-α, α Dimethyl phenethyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-ethoxybenzyl, 2-methoxyphenethyl, 3-methoxyphenethyl, 4-methoxyphenethyl, Methyl, ethyl, propyl, i-propyl, butyl, t-butyl, sec-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, lauryl, phenyl, 1-naphthyl, methoxymethyl, 2-methoxyethyl , 2-ethoxyethyl, 3- The ethoxypropyl, 2-ethoxypropyl-butoxyethyl, 2-cyclohexyl-oxyethyl, 3-, and 3-propoxy propyl, 3-isopropoxy-propylamine are exemplified.
상기 바인더는 특히, (a) 무수 말레인산, (b) 방향족 비닐 단량체, 및 (c) 비닐 단량체로서, 상기 비닐 단량체의 호모 폴리머의 유리전이온도(Tg)가 80℃미만인 비닐 단량체로 이루어지는 공중합체의 무수물기에 대하여 1급 아민 화합물을 반응시켜서 얻어지는 공중합체인 것이 바람직하다. 상기 (a) 성분과 상기 (b) 성분으로 이루어지는 공중합체에서는 후술하는 높은 표면 경도의 감광층을 얻을 수는 있지만, 라미네이트성의 확보가 곤란하게 되는 경우가 있다. 또한, 상기 (a) 성분과 상기 (c) 성분으로 이루어지는 공중합체에서는 라미네이트성은 확보할 수 있지만, 상기 표면 경도의 확보가 곤란하게 되는 경우가 있다.The binder is a copolymer of (a) maleic anhydride, (b) an aromatic vinyl monomer, and (c) a vinyl monomer, wherein the copolymer comprises a vinyl monomer having a glass transition temperature (Tg) of the homopolymer of the vinyl monomer of less than 80 ° C. It is preferable that it is a copolymer obtained by making a primary amine compound react with an anhydride group. In the copolymer which consists of said (a) component and said (b) component, although the photosensitive layer of the high surface hardness mentioned later can be obtained, it may become difficult to ensure lamination property. Moreover, although lamination property can be ensured in the copolymer which consists of said (a) component and said (c) component, securing of the said surface hardness may become difficult.
--(b) 방향족 비닐 단량체---(b) Aromatic Vinyl Monomers--
상기 방향족 비닐 단량체로서는, 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있지만, 본 발명의 감광성 조성물을 사용하여 형성되는 감광층의 표면 경도를 높게 할 수 있다는 점에서, 호모 폴리머의 유리전이온도(Tg)가 80℃이상인 화합물이 바람직하고, 100℃이상인 화합물이 보다 바람직하다.There is no restriction | limiting in particular as said aromatic vinyl monomer, Although it can select suitably according to the objective, Since the surface hardness of the photosensitive layer formed using the photosensitive composition of this invention can be made high, the glass transition temperature of a homopolymer ( The compound whose Tg) is 80 degreeC or more is preferable, and the compound which is 100 degreeC or more is more preferable.
상기 방향족 비닐 단량체의 구체예로서는 예를 들면, 스티렌(호모 폴리머의 Tg=100℃), α-메틸스티렌(호모 폴리머의 Tg=168℃), 2-메틸스티렌(호모 폴리머의 Tg=136℃), 3-메틸스티렌(호모 폴리머의 Tg=97℃), 4-메틸스티렌(호모 폴리머의 Tg=93℃), 2,4-디메틸스티렌(호모 폴리머의 Tg=112℃) 등의 스티렌 유도체가 바람직하게 열거된다. 이들은 1종 단독으로 사용해도 좋고, 2종 이상을 병용해도 좋다.As a specific example of the said aromatic vinyl monomer, For example, styrene (Tg = 100 degreeC of homopolymer), (alpha) -methylstyrene (Tg = 168 degreeC of homopolymer), 2-methylstyrene (Tg = 136 degreeC of homopolymer), Styrene derivatives, such as 3-methylstyrene (Tg of homopolymer = 97 degreeC), 4-methylstyrene (Tg of homopolymer Tg = 93 degreeC), and 2, 4- dimethyl styrene (Tg of homopolymer (112 degreeC)) are preferable. Listed. These may be used individually by 1 type and may use 2 or more types together.
--(c) 비닐 단량체---(c) vinyl monomers--
상기 비닐 단량체는 상기 비닐 단량체의 호모 폴리머의 유리전이온도(Tg)가 80℃미만인 것이 필요하고, 40℃이하가 바람직하고, 0℃이하가 보다 바람직하다.As for the said vinyl monomer, the glass transition temperature (Tg) of the homopolymer of the said vinyl monomer needs to be less than 80 degreeC, 40 degrees C or less is preferable, and 0 degrees C or less is more preferable.
상기 비닐 단량체로서는 예를 들면, n-프로필아크릴레이트(호모 폴리머의 Tg=-37℃), n-부틸아크릴레이트(호모 폴리머의 Tg=-54℃), 펜틸아크릴레이트 또는 헥실아크릴레이트(호모 폴리머의 Tg=-57℃), n-부틸메타크릴레이트(호모 폴리머의 Tg=-24℃), n-헥실메타크릴레이트(호모 폴리머의 Tg=-5℃) 등이 열거된다. 이들은 1종 단독으로 사용해도 좋고, 2종 이상을 병용해도 좋다.As said vinyl monomer, n-propyl acrylate (Tg = -37 degreeC of a homopolymer), n-butyl acrylate (Tg = -54 degreeC of a homopolymer), pentyl acrylate, or hexyl acrylate (homopolymer, for example) Tg = -57 ° C.), n-butyl methacrylate (Tg = -24 ° C. of homopolymer), n-hexyl methacrylate (Tg = -5 ° C. of homopolymer), and the like. These may be used individually by 1 type and may use 2 or more types together.
-1급 아민 화합물-Primary amine compound
상기 1급 아민 화합물로서는 예를 들면, 벤질아민, 페네틸아민, 3-페닐-1-프로필아민, 4-페닐-1-부틸아민, 5-페닐-1-펜틸아민, 6-페닐-1-헥실아민, α-메틸벤질아민, 2-메틸벤질아민, 3-메틸벤질아민, 4-메틸벤질아민, 2-(p-톨릴)에틸아민, β-메틸페네틸아민, 1-메틸-3-페닐프로필아민, 2-클로로벤질아민, 3-클로로벤질아민, 4-클로로벤질아민, 2-클로로벤질아민, 3-클로로벤질아민, 4-클로로벤질아민, 4-브로모페네틸아민, 2-(2-클로로페닐)에틸아민, 2-(3-클로로페닐)에틸아민, 2-(4-클로로페닐)에틸아민, 2-(2-플루오로페닐)에틸아민, 2-(3-플루오로페닐)에틸아민, 2-(4-플루오로페닐)에틸아민, 4-플루오로-α,α-디메틸페네틸아민, 2-메톡시벤질아민, 3-메톡시벤질아민, 4-메톡시벤질아민, 2-에톡시벤질아민, 2-메톡시페네틸아민, 3-메톡시페네틸아민, 4-메톡시페네틸아민, 메틸아민, 에틸아민, 프로필아민, 1-프로필아민, 부틸아민, t-부틸아민, sec-부틸아민, 펜틸아민, 헥실아민, 시클로헥실아민, 헵틸아민, 옥틸아민, 라우릴아민, 아닐린, 옥틸아닐린, 아니시딘, 4-클로로아닐린, 1-나프틸아민, 메톡시메틸아민, 2-메톡시에틸아민, 2-에톡시에틸아민, 3-메톡시프로필아민, 2-부톡시에틸아민, 2-시클로헥실옥시에틸아민, 3-에톡시프로필 아민, 3-프로폭시프로필아민, 3-이소프로폭시프로필아민 등이 열거된다. 이들 중에서도 벤질아민, 페네틸아민이 특히 바람직하다.As said primary amine compound, for example, benzylamine, phenethylamine, 3-phenyl-1-propylamine, 4-phenyl-1-butylamine, 5-phenyl-1-pentylamine, 6-phenyl-1- Hexylamine, α-methylbenzylamine, 2-methylbenzylamine, 3-methylbenzylamine, 4-methylbenzylamine, 2- (p-tolyl) ethylamine, β-methylphenethylamine, 1-methyl-3- Phenylpropylamine, 2-chlorobenzylamine, 3-chlorobenzylamine, 4-chlorobenzylamine, 2-chlorobenzylamine, 3-chlorobenzylamine, 4-chlorobenzylamine, 4-bromophenethylamine, 2- ( 2-chlorophenyl) ethylamine, 2- (3-chlorophenyl) ethylamine, 2- (4-chlorophenyl) ethylamine, 2- (2-fluorophenyl) ethylamine, 2- (3-fluorophenyl ) Ethylamine, 2- (4-fluorophenyl) ethylamine, 4-fluoro-α, α-dimethylphenethylamine, 2-methoxybenzylamine, 3-methoxybenzylamine, 4-methoxybenzylamine , 2-ethoxybenzylamine, 2-methoxyphenethylamine, 3-methoxyphenethylamine, 4-methoxyphenethylamine, methyla , Ethylamine, propylamine, 1-propylamine, butylamine, t-butylamine, sec-butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, laurylamine, aniline, octylaniline, Anicidine, 4-chloroaniline, 1-naphthylamine, methoxymethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 2-butoxyethylamine, 2-cyclo Hexyloxyethylamine, 3-ethoxypropyl amine, 3-propoxypropylamine, 3-isopropoxypropylamine and the like. Among these, benzylamine and phenethylamine are particularly preferable.
상기 1급 아민 화합물은 1종 단독으로 사용해도 좋고, 2종 이상을 병용해도 좋다.The said primary amine compound may be used individually by 1 type, and may use 2 or more types together.
상기 1급 아민 화합물의 반응량으로서는 상기 무수물기에 대하여 0.1∼1.2당량인 것이 필요하고, 0.1∼1.0당량이 바람직하다. 상기 반응량이 1.2당량을 초과하면, 상기 1급 아민 화합물을 1종 이상 반응시켰을 경우에, 용해성이 현저하게 악화되는 경우가 있다.As reaction amount of the said primary amine compound, it is necessary that it is 0.1-1.2 equivalent with respect to the said anhydride group, and 0.1-1.0 equivalent is preferable. When the said reaction amount exceeds 1.2 equivalent, when 1 or more types of said primary amine compounds are reacted, solubility may deteriorate remarkably.
상기 (a)무수 말레인산의 상기 바인더에 있어서의 함유량은 15∼50몰%가 바람직하고, 20∼45몰%가 보다 바람직하고, 20∼40몰%가 특히 바람직하다. 상기 함유량이 15몰%미만이면, 알칼리 현상성을 부여할 수 없고, 50몰%를 초과하면, 내 알칼리성이 열화하고, 또한 상기 공중합체의 합성이 곤란해져, 정상의 영구 패턴의 형성을 행할 수 없는 경우가 있다. 또한, 이 경우에 있어서의 상기 (b) 방향족 비닐 단량체 및 (c) 호모 폴리머의 유리전이온도(Tg)가 80℃미만인 비닐 단량체의 상기 바인더에 있어서의 함유량은 각각 20∼60몰%, 15∼40몰%가 바람직하다. 상기 함유량이 상기 수치 범위를 만족할 경우에는, 표면 경도 및 라미네이트성의 양립을 꾀할 수 있다.15-50 mol% is preferable, as for content in the said binder of (a) maleic anhydride, 20-45 mol% is more preferable, 20-40 mol% is especially preferable. If the content is less than 15 mol%, alkali developability cannot be imparted. If the content exceeds 50 mol%, alkali resistance deteriorates, and the synthesis of the copolymer becomes difficult, and a normal permanent pattern can be formed. There may be no. In this case, the content in the binder of the vinyl monomer in which the glass transition temperature (Tg) of the (b) aromatic vinyl monomer and (c) homopolymer in this case is less than 80 ° C is 20 to 60 mol% and 15 to 15, respectively. 40 mol% is preferable. When the said content satisfies the said numerical range, both surface hardness and lamination property can be aimed at.
상기 말레아미드산계 공중합체의 분자량은 3,000∼500,000이 바람직하고, 8,000∼150,000이 보다 바람직하다. 상기 분자량이 3,000미만이면, 후술하는 감광층의 경화후에 있어서, 막품질이 취약해져 표면 경도가 열화하는 경우가 있고, 500,000을 초과하면, 상기 감광성 조성물의 가열 적층시의 유동성이 낮아져 적절한 라미네이트성의 확보가 곤란해지는 경우가 있고, 또한 현상성이 악화하는 경우가 있다.3,000-500,000 are preferable and, as for the molecular weight of the said maleamic acid type copolymer, 8,000-150,000 are more preferable. When the said molecular weight is less than 3,000, after hardening of the photosensitive layer mentioned later, film quality may become weak and surface hardness may deteriorate, and when it exceeds 500,000, the fluidity at the time of lamination | stacking of the said photosensitive composition will become low, and ensuring appropriate lamination property May become difficult, and developability may deteriorate.
<기타 바인더><Other Binders>
상기 바인더로서는 기타 바인더를 병용해도 좋다. 상기 기타 바인더로서는 일본특허공개 평11-288087호 공보 기재의 폴리아미드(이미드) 수지, 일본특허공개 평11-282155호 공보 기재의 폴리이미드 전구체 등을 사용할 수 있다. 이들은 1종 단독으로 사용해도 좋고, 2종 이상을 혼합해서 사용해도 좋다.As said binder, you may use other binder together. As said other binder, the polyamide (imide) resin of Unexamined-Japanese-Patent No. 11-288087, the polyimide precursor of Unexamined-Japanese-Patent No. 11-282155, etc. can be used. These may be used individually by 1 type and may mix and use 2 or more types.
상기 폴리아미드(이미드) 또는 폴리이미드 전구체 등의 바인더의 분자량으로서는, 3,000∼500,000이 바람직하고, 5,000∼100,000이 보다 바람직하다. 상기 분자량이 3,000미만이면, 감광층 표면의 택성이 강하게 되는 경우가 있고, 후술하는 감광층의 경화 후에 있어서, 막품질이 취약해지거나, 또는 표면경도가 열화하는 경우가 있고, 500,000을 초과하면, 현상성이 열화하는 경우가 있다.As molecular weight of binders, such as the said polyamide (imide) or polyimide precursor, 3,000-500,000 are preferable and 5,000-100,000 are more preferable. When the said molecular weight is less than 3,000, the tackiness of the surface of a photosensitive layer may become strong, and after hardening of the photosensitive layer mentioned later, a film quality may become weak or surface hardness may deteriorate, and when it exceeds 500,000, Developability may deteriorate.
상기 바인더의 상기 감광성 조성물 고형분 중의 고형분 함유량은 5∼70질량%가 바람직하고, 10∼50질량%가 보다 바람직하다. 상기 고형분 함유량이 5질량%미만이면, 후술하는 감광층의 막강도가 약해지기 쉽고, 상기 감광층의 표면의 택성이 악화하는 경우가 있고, 70질량%을 초과하면, 노광 감도가 저하하는 경우가 있다.5-70 mass% is preferable, and, as for solid content in the photosensitive composition solid content of the said binder, 10-50 mass% is more preferable. When the solid content is less than 5% by mass, the film strength of the photosensitive layer described later tends to be weak, and the tackiness of the surface of the photosensitive layer may deteriorate. When the content exceeds 70% by mass, the exposure sensitivity may decrease. have.
[(B) 중합성 화합물][(B) Polymerizable Compound]
상기 중합성 화합물로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있지만, 분자 중에 적어도 1개의 부가 중합가능한 기를 갖고, 비점이 상압 에서 100℃이상인 화합물이 바람직하고, 예를 들면, (메타)아크릴기를 갖는 모노머로부터 선택되는 적어도 1종이 바람직하게 열거된다.There is no restriction | limiting in particular as said polymeric compound, Although it can select suitably according to the objective, The compound which has at least 1 addition polymerization group in a molecule | numerator, and whose boiling point is 100 degreeC or more at normal pressure is preferable, For example, (meth) acryl At least 1 sort (s) chosen from the monomer which has a group is mentioned preferably.
상기 (메타)아크릴기를 갖는 모노머로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있고, 예를 들면 폴리에틸렌글리콜모노(메타)아크릴레이트, 폴리프로필렌글리콜모노(메타)아크릴레이트, 페녹시에틸(메타)아크릴레이트 등의 단관능 아크릴레이트나 단관능 메타크릴레이트; 폴리에틸렌글리콜디(메타)아크릴레이트, 폴리프로필렌글리콜디(메타)아크릴레이트, 트리메틸올에탄트리아크릴레이트, 트리메틸올프로판트리아크릴레이트, 트리메틸올프로판디아크릴레이트, 네오펜틸글리콜디(메타)아크릴레이트, 펜타에리스리톨테트라(메타)아크릴레이트, 펜타에리스리톨트리(메타)아크릴레이트, 디펜타에리스리톨헥사(메타)아크릴레이트, 디펜타에리스리톨펜타(메타)아크릴레이트, 헥산디올디(메타)아크릴레이트, 트리메틸올프로판트리(아크릴로일옥시프로필)에테르, 트리(아크릴로일옥시에틸)이소시아누레이트, 트리(아크릴로일옥시에틸)시아누레이트, 글리세린트리(메타)아크릴레이트, 트리메틸올프로판이나 글리세린, 비스페놀 등의 다관능 알콜에 에틸렌옥사이드나 프로필렌옥사이드를 부가반응시킨 후에 (메타)아크릴레이트화한 것, 일본특허공고 소48-41708호, 일본특허공고 소50-6034호, 일본특허공개 소51-37193호 등의 각 공보에 기재되어 있는 우레탄 아크릴레이트류; 일본특허공개 소48-64183호, 일본특허공고 소49-43191호, 일본특허공고 소52-30490호 등의 각 공보에 기재되어 있는 폴리에스테르아크릴레이트류; 에폭시 수지와 (메타)아크릴산의 반응 생성물인 에폭시아크릴레이트류 등의 다관능 아크릴레이트나 메타크릴레이트 등이 열거된다. 이들 중에서 도 트리메틸올프로판트리(메타)아크릴레이트, 펜타에리스리톨테트라(메타)아크릴레이트, 디펜타에리스리톨헥사(메타)아크릴레이트, 디펜타에리스리톨펜타(메타)아크릴레이트가 특히 바람직하다.There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) Monofunctional acrylates and monofunctional methacrylates, such as a) acrylate; Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylol ethane triacrylate, trimethylolpropane triacrylate, trimethylolpropanediacrylate, neopentyl glycol di (meth) acrylate, Pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanedioldi (meth) acrylate, trimethylolpropane Tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, trimethylolpropane or glycerin, bisphenol (Meth) acrylate after addition reaction of ethylene oxide or propylene oxide to polyfunctional alcohols such as Urethane acrylates described in each publication such as yttrate, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, and Japanese Patent Publication No. 51-37193; Polyester acrylates described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490; Polyfunctional acrylates, methacrylates, etc., such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid, are mentioned. Among them, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate are particularly preferable.
상기 중합성 화합물의 상기 감광성 조성물 고형분 중의 고형분 함유량은 5∼50질량%가 바람직하고, 10∼40질량%가 보다 바람직하다. 상기 고형분 함유량이 5질량%미만이면, 현상성의 악화, 노광 감도의 저하 등의 문제를 일으키는 경우가 있고, 50질량%를 초과하면, 감광층의 점착성이 지나치게 강해지는 경우가 있어 바람직하지 않다.5-50 mass% is preferable, and, as for solid content in the said photosensitive composition solid content of the said polymeric compound, 10-40 mass% is more preferable. When the solid content is less than 5% by mass, problems may occur such as deterioration of developability and a decrease in exposure sensitivity, and when it exceeds 50% by mass, the adhesiveness of the photosensitive layer may be too strong, which is not preferable.
[(C) 광중합 개시제][(C) Photopolymerization Initiator]
상기 광중합 개시제로서는, 상기 중합성 화합물의 중합을 개시하는 능력을 갖는 한, 특별히 제한은 없고, 공지의 광중합 개시제 중에서 적당하게 선택할 수 있지만, 예를 들면 자외선 영역으로부터 가시 광선에 대하여 감광성을 갖는 것이 바람직하고, 광여기된 증감제와 어떠한 작용을 일으키고, 활성 라디칼을 생성하는 활성제이어도 좋고, 모노머의 종류에 따라서 양이온 중합을 개시시키는 개시제이어도 좋다.As said photoinitiator, there is no restriction | limiting in particular as long as it has the ability to start superposition | polymerization of the said polymeric compound, Although it can select suitably from well-known photoinitiators, For example, what has photosensitivity with respect to visible light from an ultraviolet range is preferable. And an activator that causes some action with the photoexcited sensitizer and generates active radicals, or may be an initiator that initiates cationic polymerization depending on the type of monomer.
또한, 상기 광중합 개시제는 약 300∼800nm(더욱 바람직하게는 330∼500nm)의 범위내에 적어도 약 50의 분자 흡광 계수를 갖는 성분을 적어도 1종 함유하고 있는 것이 바람직하다.In addition, the photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 in the range of about 300 to 800 nm (more preferably, 330 to 500 nm).
상기 광중합 개시제로서는 예를 들면, 할로겐화 탄화수소 유도체(예를 들면 트리아진 골격을 갖는 것, 옥사디아졸 골격을 갖는 것 등), 포스핀 옥사이드, 헥사 아릴 비이미다졸, 옥심 유도체, 유기 과산화물, 티오 화합물, 케톤 화합물, 방향족 오늄염, 메탈로센류 등이 열거된다.As said photoinitiator, a halogenated hydrocarbon derivative (for example, having a triazine skeleton, an oxadiazole skeleton, etc.), phosphine oxide, hexa aryl biimidazole, an oxime derivative, an organic peroxide, a thio compound , Ketone compounds, aromatic onium salts, metallocenes and the like.
상기 트리아진 골격을 갖는 할로겐화 탄화수소 화합물로서는, 예를 들면 와카바야시 등 저, Bull. Chem. Soc. Japan, 42, 2924(1969) 기재의 화합물, 영국 특허 1388492호 명세서 기재의 화합물, 일본특허공개 소53-133428호 공보 기재의 화합물, 독일국 특허 3337024호 명세서 기재의 화합물, F.C.Schaefer 등에 의한 J.0rg.Chem; 29, 1527(1964) 기재의 화합물, 일본특허공개 소62-58241호 공보 기재의 화합물, 일본특허공개 평5-281728호 공보 기재의 화합물, 일본특허공개 평5-34920호 공보 기재의 화합물, 미국특허 제4212976호 명세서에 기재되어 있는 화합물 등이 열거된다.As a halogenated hydrocarbon compound which has the said triazine skeleton, Wakabayashi et al., Bull. Chem. Soc. Compounds described in Japan, 42, 2924 (1969), compounds described in British Patent No. 1388492, compounds described in JP-A-53-133428, compounds described in JP 3337024, FCSchaefer and the like. 0rg. Chem; 29, 1527 (1964), a compound of JP-A-62-58241, a compound of JP-A-5-281728, a compound of JP-A-5-34920, United States And the compounds described in patent 4212976.
상기 와카바야시 등 저, Bull. Chem. Soc. Japan, 42, 2924(1969)기재의 화합물로서는 예를 들면, 일본특허공개 2005-258431호 공보의 [0291]에 기재되어 있는 화합물 등이 열거된다.Wakabayashi et al., Bull. Chem. Soc. As a compound of Japan, 42, 2924 (1969), the compound etc. which are described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.
상기 영국 특허 1388492호 명세서 기재의 화합물로서는, 예를 들면 일본특허공개 2005-258431호 공보의 [0292]에 기재되어 있는 화합물 등이 열거된다.As a compound of the said British patent 1388492 specification, the compound etc. which are described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.
상기 일본특허공개 소53-133428호 공보 기재의 화합물로서는 예를 들면, 일본특허공개 2005-258431호 공보의 [0293]에 기재되어 있는 화합물 등이 열거된다.As a compound of the said Unexamined-Japanese-Patent No. 53-133428, the compound etc. which were described in Unexamined-Japanese-Patent No. 2005-258431, etc. are mentioned, for example.
상기 독일국 특허 3337024호 명세서 기재의 화합물로서는, 예를 들면 일본특허공개 2005-258431호 공보의 [0294]에 기재되어 있는 화합물 등이 열거된다.As a compound of the said German patent 3337024 specification, the compound etc. which are described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.
상기 F. C. Schaefer 등에 의한 J.0rg.Chem.; 29, 1527(1964) 기재의 화합물 로서는 예를 들면, 일본특허공개 2005-258431호 공보의 [0295]에 기재되어 있는 화합물 등이 열거된다.J. 0rg. Chem. By F. C. Schaefer et al .; As a compound of 29, 1527 (1964), the compound etc. which were described in Unexamined-Japanese-Patent No. 2005-258431 are mentioned, for example.
상기 일본특허공개 소62-58241호 공보 기재의 화합물로서는 예를 들면, 일본특허공개 2005-258431호 공보의 [0296]에 기재되어 있는 화합물 등이 열거된다.As a compound of the said Unexamined-Japanese-Patent No. 62-58241, the compound etc. which were described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.
상기 일본특허공개 평5-281728호 공보 기재의 화합물로서는 예를 들면 일본특허공개 2005-258431호 공보의 [0297]에 기재되어 있는 화합물 등이 열거된다.As a compound of the said Unexamined-Japanese-Patent No. 5-281728, the compound etc. which were described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.
상기 일본특허공개 평5-34920호 공보 기재 화합물로서는 예를 들면 일본특허공개 2005-258431호 공보의 [0298]에 기재되어 있는 화합물 등이 열거된다.As said compound of Unexamined-Japanese-Patent No. 5-34920, the compound etc. which were described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.
상기 미국특허 제4212976호 명세서에 기재되어 있는 화합물로서는 예를 들면 일본특허공개 2005-258431호 공보의 [0299]에 기재되어 있는 화합물 등이 열거된다.As a compound described in the said US patent 4212976, the compound etc. which are described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.
상기 포스핀 옥사이드로서는 예를 들면 일본특허공개 2005-258431호 공보의 [0307]에 기재되어 있는 화합물 등이 열거된다.As said phosphine oxide, the compound etc. which are described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.
상기 헥사아릴비이미다졸로서는 예를 들면, 2,2'-비스(2-클로로페닐)-4,4',5,5'-테트라페닐비이미다졸, 2,2'-비스(o-플루오로페닐)-4,4',5,5'-테트라페닐비이미다졸, 2,2'-비스(2-브로모페닐)-4,4',5,5'-테트라페닐비이미다졸, 2,2'-비스(2,4-디클로로페닐)-4,4',5,5'-테트라페닐비이미다졸, 2,2'-비스(2-클로로페닐)-4,4',5,5'-테트라(3-메톡시페닐)비이미다졸, 2,2'-비스(2-클로로페닐)-4,4',5,5'-테트라(4-메톡시페닐)비이미다졸, 2,2'-비스(4-메톡시페닐)-4,4',5,5'-테트라페닐비이미다졸, 2,2'-비스(2,4-디클로로페닐)-4,4',5,5'-테트라페닐비이미다졸, 2,2'- 비스(2-니트로페닐)-4,4',5,5'-테트라페닐비이미다졸, 2,2'-비스(2-메틸페닐)-4,4',5,5'-테트라페닐비이미다졸, 2,2'-비스(2-트리플루오로메틸페닐)-4,4',5,5'-테트라페닐비이미다졸, WO00/52529호 공보에 기재된 화합물 등이 열거된다.As said hexaaryl biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (o-fluorine, for example) Rophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5 , 5'-tetra (3-methoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (4-methoxyphenyl) biimidazole , 2,2'-bis (4-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4' , 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2- Methylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-trifluoromethylphenyl) -4,4', 5,5'-tetraphenylbiimidazole, And the compounds described in WO00 / 52529.
상기 비이미다졸류는 예를 들면, Bull. Chem. Soc. Japan, 33, 565(1960) 및 J. Org. Chem, 36(16)2262(1971)에 개시되어 있는 방법에 의해 용이하게 합성할 수 있다.The biimidazoles are, for example, Bull. Chem. Soc. Japan, 33, 565 (1960) and J. Org. It can be synthesize | combined easily by the method disclosed by Chem, 36 (16) 2262 (1971).
본 발명에서 바람직하게 사용되는 상기 옥심 유도체로서는 예를 들면, 3-벤조일옥시이미노부탄-2-온, 3-아세톡시이미노부탄-2-온, 3-프로피오닐옥시이미노부탄-2-온, 2-아세톡시이미노펜탄-3-온, 2-아세톡시이미노-1-페닐프로판-1-온, 2-벤조일옥시이미노-1-페닐프로판-1-온, 3-(4-톨루엔술포닐옥시)이미노부탄-2-온 및 2-에톡시카르보닐옥시이미노-1-페닐프로판-1-온 등이 열거된다.Examples of the oxime derivatives preferably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2 -Acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) Iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, etc. are mentioned.
상기 유기 과산화물로서는 예를 들면, 3,3',4,4'-테트라(t-부틸퍼옥시카르보닐)벤조페논 등이 열거된다.As said organic peroxide, 3,3 ', 4,4'- tetra (t-butylperoxycarbonyl) benzophenone etc. are mentioned, for example.
상기 티오 화합물로서는 예를 들면, 2,4-디에틸티옥산톤, 2,4-디클로로티옥산톤, 1-클로로-4-프로폭시티옥산톤, 2-벤조일메틸렌-3-메틸나프토티아졸린 등이 열거된다.As said thio compound, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy cyoxanthone, 2-benzoylmethylene-3-methyl naphthothiazoline And the like.
상기 케톤 화합물로서는 예를 들면, 일본특허공개 2005-258431호 공보의 [0305]에 기재되어 있는 화합물 등이 열거된다.As said ketone compound, the compound etc. which are described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.
상기 방향족 오늄염으로서는 예를 들면, 디페닐요오드늄테트라플루오로보레이트, 디페닐요오드늄헥사플루오로포스포네이트, 트리페닐술포늄테트라플루오로보 레이트, 트리페닐술포늄헥사플루오로포스포네이트, 테트라페닐포스포늄-헥사플루오로포스페이트 등이 열거된다.As said aromatic onium salt, diphenyl iodonium tetrafluoro borate, diphenyl iodonium hexafluoro phosphonate, a triphenyl sulfonium tetrafluoro borate, a triphenyl sulfonium hexafluoro phosphonate, tetra, for example. Phenylphosphonium-hexafluorophosphate and the like.
상기 메탈로센류로서는 예를 들면, 비스(η5-2,4-시클로펜타디엔-1-일)-비스(2,6-디플루오로-3-(1H-피롤-1-일)-페닐)티타늄, η5-5-시클로펜타디에닐-η6-쿠메닐-아이안(1+)-헥사플루오로포스페이트(1-) 등이 열거된다.Examples of the metallocenes include bis (η 5 -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl Titanium, η 5 -5-cyclopentadienyl- η 6 -cumenyl-an (1 +)-hexafluorophosphate (1-), and the like.
또한, 상기 이외의 광중합 개시제로서, N-페닐글리신 등 폴리할로겐 화합물(예를 들면, 사브롬화탄소, 페닐트리브로모메틸술폰, 페닐트리클로로메틸케톤 등), 아민류(예를 들면, 4-디메틸아미노벤조산에틸, 4-디메틸아미노벤조산n-부틸, 4-디메틸아미노벤조산페네틸, 4-디메틸아미노벤조산2-프탈이미드에틸, 4-디메틸아미노벤조산2-메타크릴로일옥시에틸, 펜타메틸렌비스(4-디메틸아미노벤조에이트), 3-디메틸아미노벤조산의 페네틸, 펜타메틸렌에스테르, 4-디메틸아미노벤즈알데히드, 2-클로로-4-디메틸아미노벤즈알데히드, 4-디메틸아미노벤질알콜, 에틸(4-디메틸아미노벤조일)아세테이트, 4-피페리디노아세토페논, 4-디메틸아미노벤조인, N,N-디메틸-4-톨루이딘, N,N-디에틸-3-페네티딘, 트리벤질아민, 디벤질페닐아민, N-메틸-N-페닐벤질아민, 4-브롬-N,N-디메틸아닐린, 트리도데실아민, 크리스탈 바이올렛 락톤, 류코 크리스탈 바이올렛 등), 일본특허공개 소53-133428호 공보, 일본특허공고 소57-1819호 공보, 동 57-6096호 공보 및 미국특허 제3615455호 명세서에 기재된 화합물 등이 열거된다.Moreover, as a photoinitiator of that excepting the above, polyhalogen compounds, such as N-phenylglycine (for example, carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), amines (for example, 4-dimethyl) Ethyl aminobenzoate, 4-dimethylaminobenzoic acid n-butyl, 4-dimethylaminobenzoic acid phenethyl, 4-dimethylaminobenzoic acid 2-phthalimideethyl, 4-dimethylaminobenzoic acid 2-methacryloyloxyethyl, pentamethylenebis (4-dimethylaminobenzoate), phenethyl, pentamethylene ester of 3-dimethylaminobenzoic acid, 4-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-dimethyl Aminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-4-toluidine, N, N-diethyl-3-phenetidine, tribenzylamine, dibenzylphenyl Amine, N-methyl-N-phenylbenzylamine, 4-bromine-N, N-dimeth Aniline, tridodecylamine, crystal violet lactone, leuco crystal violet, etc.), Japanese Patent Laid-Open No. 53-133428, Japanese Patent Laid-Open No. 57-1819, Japanese Patent Laid-Open No. 57-6096, and US Patent No. 3615455 The compound described in the above is mentioned.
또한, 후술하는 감광층으로의 노광에 있어서의 노광 감도나 감광 파장을 조 정할 목적으로, 상기 광중합 개시제에 더해서, 증감제를 첨가하는 것이 가능하다.Moreover, in addition to the said photoinitiator, it is possible to add a sensitizer in order to adjust the exposure sensitivity and the photosensitive wavelength in exposure to the photosensitive layer mentioned later.
상기 증감제는 후술하는 광조사 수단으로서의 가시 광선이나 자외광 및 가시광선 레이저 등에 의해 적당하게 선택할 수 있다.The said sensitizer can be suitably selected with visible light, an ultraviolet light, a visible light laser, etc. as light irradiation means mentioned later.
상기 증감제는 활성 에너지선에 의해 여기 상태가 되고, 다른 물질(예를 들면, 라디칼 발생제, 산발생제 등)과 상호 작용(예를 들면, 에너지 이동, 전자 이동 등)함으로써, 라디칼이나 산 등의 유용기를 발생하는 것이 가능하다.The sensitizer is excited by an active energy ray, and interacts with other substances (e.g., radical generators, acid generators, etc.) (e.g., energy transfer, electron transfer, etc.) It is possible to generate useful groups such as these.
또한, 이들의 화합물은 감광층의 감도의 향상을 꾀할 뿐만 아니라, 광여기에 의해 상기 모노머의 중합을 개시시키는 광중합 개시제로서의 기능도 갖고 있다.In addition, these compounds not only improve the sensitivity of the photosensitive layer, but also have a function as a photopolymerization initiator that initiates polymerization of the monomers by photo-excitation.
상기 증감제로서는 특별히 제한은 없고, 공지의 증감제 중에서 적당하게 선택할 수 있지만, 예를 들면 공지의 다핵 방향족류(예를 들면, 피렌, 페릴렌, 트리페닐렌), 크산텐류(예를 들면, 플루오레세인, 에오신, 에리스로신, 로다민 B, 로즈 벵갈), 시아닌류(예를 들면, 인도카르보시아닌, 티아카르보시아닌, 옥사카르보시아닌), 멜로시아닌류(예를 들면, 멜로시아닌, 카르보멜로시아닌), 티아진류(예를 들면, 티오닌, 메틸렌블루, 톨루이딘블루), 아크리딘류(예를 들면, 아크리딘오렌지, 클로로플라빈, 아크릴플라빈), 안트라퀴논류(예를 들면, 안트라퀴논), 스쿠알륨류(예를 들면, 스쿠알륨) 등이 열거된다.There is no restriction | limiting in particular as said sensitizer, Although it can select suitably from well-known sensitizers, For example, well-known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, Fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (e.g. indocarbocyanine, thiacarbocyanine, oxacarbocyanine), melocyanines (e.g. melo Cyanine, carbomelocyanine), thiazines (e.g. thionine, methylene blue, toluidine blue), acridines (e.g. acridine orange, chloroflavin, acrylflavin), anthra Quinones (for example, anthraquinone), squariases (for example, squalarium), etc. are mentioned.
상기 증감제로서는 헤테로 축환계 화합물이 바람직하게 더 열거된다. 상기 헤테로 축환계 화합물이란, 환 중에 헤테로 원소를 갖는 다환식 화합물을 의미하고, 상기 환 중에 질소 원자를 함유하는 것이 바람직하다. 상기 헤테로 축환계 화합물로서는 예를 들면, 헤테로 축환계 케톤 화합물, 퀴놀린 화합물, 아크리딘 화합 물이 열거된다.As said sensitizer, a heterocyclic ring-type compound is further preferably listed. The heterocyclic ring compound means a polycyclic compound having a hetero element in the ring, and preferably contains a nitrogen atom in the ring. As said heterocyclic ring-type compound, a heterocyclic ring-type ketone compound, a quinoline compound, an acridine compound is mentioned, for example.
상기 헤테로 축환계 케톤 화합물로서는 구체적으로는, 예를 들면 아크리돈, 클로로 아크리돈, N-메틸아크리돈, N-부틸아크리돈, N-부틸-클로로아크리돈 등의 아크리돈 화합물; 3-(2-벤조푸로일)-7-디에틸아미노쿠마린, 3-(2-벤조푸로일)-7-(1-피롤리디닐)쿠마린, 3-벤조일-7-디에틸아미노쿠마린, 3-(2-메톡시벤조일)-7-디에틸아미노쿠마린, 3-(4-디메틸아미노벤조일)-7-디에틸아미노쿠마린, 3,3'-카르보닐 비스(5,7-디-n-프로폭시쿠마린), 3,3'-카르보닐비스(7-디에틸아미노쿠마린), 3-벤조일-7-메톡시쿠마린, 3-(2-푸로일)-7-디에틸아미노쿠마린, 3-(4-디에틸아미노신나모일)-7-디에틸아미노쿠마린, 7-메톡시-3-(3-피리딜카르보닐)쿠마린, 3-벤조일-5,7-디프로폭시쿠마린, 7-벤조트리아졸-2-일쿠마린, 7-디에틸아미노-4-메틸쿠마린, 또한, 일본특허공개 평5-19475호, 일본특허공개 평7-271028호, 일본특허공개 2002-363206호, 일본특허공개 2002-363207호, 일본특허공개 2002-363208호, 일본특허공개 2002-363209호 공보 등에 기재된 쿠마린 화합물 등의 쿠마린류; 등이 열거된다.Specific examples of the heterocyclic ring-type ketone compound include acridons such as acridon, chloro acridon, N-methyl acridon, N-butyl acridon and N-butyl-chloro acredon. compound; 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3 -(2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3'-carbonyl bis (5,7-di-n- Propoxycoumarin), 3,3'-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzo Triazole-2-ylcoumarin, 7-diethylamino-4-methylcoumarin, Japanese Patent Laid-Open No. 5-19475, Japanese Patent Laid-Open No. 7-271028, Japanese Patent Laid-Open No. 2002-363206, Japanese Patent Laid-Open Coumarins such as coumarin compounds described in 2002-363207, Japanese Patent Laid-Open No. 2002-363208, Japanese Patent Laid-Open No. 2002-363209 and the like; And the like.
상기 퀴놀린 화합물로서는 구체적으로는 예를 들면, 퀴놀린, 9-히드록시-1,2-디히드록시퀴놀린-2-온, 9-에톡시-1,2-디히드퀴놀린-2-온, 9-디부틸아미노-1,2-디히드로퀴놀린-2-온, 8-히드록시퀴놀린, 8-메르캅토퀴놀린, 퀴놀린-2-카르복실산 등이 열거된다.Specific examples of the quinoline compound include quinoline, 9-hydroxy-1,2-dihydroxyquinolin-2-one, 9-ethoxy-1,2-dihydrquinolin-2-one and 9- Dibutylamino-1,2-dihydroquinolin-2-one, 8-hydroxyquinoline, 8-mercaptoquinoline, quinoline-2-carboxylic acid and the like.
상기 아크리딘 화합물로서는 구체적으로는 예를 들면, 9-페닐아크리딘, 1,7-비스(9,9'-아크리디닐)헵탄, 아크리딘오렌지, 클로로플라빈, 아크릴플라빈 등 이 열거된다. 이들 헤테로 축환계 화합물 중에서도, 환 중에 질소 원소를 함유하는 것 이 보다 바람직하다. 상기 환내에 질소원소를 함유하는 것으로서는, 상기 아크리딘 화합물, 아미노기에 의해 치환된 쿠마린 화합물, 아크리돈 화합물 등이 바람직하게 열거된다. 이 중에서도 상기 아크리돈, 아미노기에 의해 치환된 쿠마린, 9-페닐아크리딘 등이 더욱 바람직하고, 이들 중에서도 상기 아크리돈이 특히 바람직하다.Specific examples of the acridine compound include 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane, acridine orange, chloroflavin, acrylflavin and the like. This is listed. It is more preferable to contain a nitrogen element in a ring among these heterocyclic compounds. As what contains a nitrogen element in the said ring, the said acridine compound, the coumarin compound substituted by the amino group, an acridon compound, etc. are mentioned preferably. Among these, the said acridon, the coumarin substituted by the amino group, 9-phenylacridine, etc. are more preferable, and the said acridon is especially preferable.
상기 광중합 개시제와 상기 증감제의 조합으로서는 예를 들면, 일본특허공개 2001-305734호 공보에 기재된 전자이동형 개시계[(1) 전자 공여형 개시제 및 증감색소, (2) 전자 수용형 개시제 및 증감 색소, (3) 전자 공여형 개시제, 증감 색소 및 전자 수용형 개시제(3원 개시계)] 등의 조합이 열거된다.As a combination of the said photoinitiator and the said sensitizer, the electron transfer type | system | group starter described in Unexamined-Japanese-Patent No. 2001-305734 [(1) electron donation type initiator and sensitizing dye, (2) electron accepting type initiator and a sensitizing dye, for example. , (3) electron donating type initiator, sensitizing dye, and electron accepting type initiator (three-way initiator)].
상기 증감제의 함유량으로서는, 상기 감광성 조성물 중의 전체 성분에 대하여, 0.05∼30질량%가 바람직하고, 0.1∼20질량%가 보다 바람직하고, 0.2∼10질량%가 특히 바람직하다. 상기 함유량이 0.05질량%미만이면, 활성 에너지선으로의 감도가 저하하고, 노광 프로세스에 시간이 걸리고, 생산성이 저하하는 경우가 있고, 30 질량%을 초과하면, 보존시에 상기 감광층으로부터 상기 증감제가 석출하는 경우가 있다.As content of the said sensitizer, 0.05-30 mass% is preferable with respect to the all components in the said photosensitive composition, 0.1-20 mass% is more preferable, 0.2-10 mass% is especially preferable. When the said content is less than 0.05 mass%, the sensitivity to an active energy ray falls, an exposure process may take time, productivity may fall, and when it exceeds 30 mass%, it will increase and decrease from the said photosensitive layer at the time of storage. There is a case where I settle.
상기 광중합 개시제는 1종 단독으로 사용해도 좋고, 2종 이상을 병용해도 좋다.The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
상기 광중합 개시제의 특히 바람직한 예로서는, 후술하는 노광에 있어서, 파장이 405nm인 레이저광에 대응가능한 상기 포스핀 옥사이드류, 상기α-아미노알킬케톤류, 상기 트리아진 골격을 갖는 할로겐화 탄화수소 화합물과 아민 화합물을 조합시킨 복합 광개시제, 헥사아릴 비이미다졸 화합물, 헥사아릴 비이미다졸 화합물 과 헤테로 축환계 화합물 또는 메탈로센류 등이 열거된다.As a particularly preferable example of the photopolymerization initiator, in the following exposure, a halogenated hydrocarbon compound having an phosphine oxide, the α-aminoalkyl ketone, and the triazine skeleton and an amine compound capable of responding to a laser beam having a wavelength of 405 nm are combined. Complex photoinitiators, hexaaryl biimidazole compounds, hexaaryl biimidazole compounds, heterocyclic compounds, and metallocenes.
또한, 이들의 개시제와 함께 연쇄 이동제(예를 들면, 메르캅토 화합물, 보다구체적으로는 2-메르캅토벤즈이미다졸, 2-메르캅토벤즈옥사졸, 2-메르캅토벤즈옥사졸 등)를 병용해도 좋다.Moreover, even if it uses together a chain transfer agent (for example, a mercapto compound, more specifically 2-mercapto benzimidazole, 2-mercapto benzoxazole, 2-mercaptobenzoxazole, etc.) with these initiators, good.
상기 광중합 개시제의 상기 감광성 조성물에 있어서의 함유량으로서는 0.1∼30질량%가 바람직하고, 0.5∼20질량%가 보다 바람직하며, 0.5∼15질량%가 특히 바람직하다.As content in the said photosensitive composition of the said photoinitiator, 0.1-30 mass% is preferable, 0.5-20 mass% is more preferable, 0.5-15 mass% is especially preferable.
[(D)일반식(1)∼(3)으로 나타내어지는 화합물로부터 선택되는 적어도 1종의 화합물][(D) At least 1 sort (s) of compound chosen from the compound represented by General formula (1)-(3)]
하기 일반식(1)∼(3)으로 나타내어지는 화합물은 저온 또는 상온에서는 반응을 일으키는 경우가 없고, 가열에 의해 가교반응을 개시하는 열가교제로서의 기능을 갖는다. 상기 화합물을 본 발명의 감광성 조성물에 함유시킴으로써, 상기 감광성 조성물이 저온 또는 상온에서는 반응하는 경우가 없고, 뛰어난 보존 안정성을 꾀할 수 있는 동시에, 가열 처리시에는, 상기 열처리 온도로 신속한 반응을 나타내어 경화되고, 표면 경도 및 내알칼리성 등이 우수한 경화물이 얻어진다.The compounds represented by the following general formulas (1) to (3) do not cause a reaction at low temperature or normal temperature, and have a function as a thermal crosslinking agent which initiates a crosslinking reaction by heating. By incorporating the compound into the photosensitive composition of the present invention, the photosensitive composition does not react at low or normal temperature, and excellent storage stability can be achieved, and at the time of heat treatment, it exhibits a rapid reaction at the heat treatment temperature and cures. Hardened | cured material excellent in surface hardness, alkali resistance, etc. is obtained.
단, 상기 일반식(1), (2) 및 (3) 중 P는 산소 원자, 카르보닐기, 아미드기, 우레탄기, 알킬렌 및 아릴렌 중 어느 하나를 나타낸다. Q는 붕소 원자, 질소 원자, 알킬렌, 및 아릴렌 중 어느 하나를 나타낸다. W는 2개의 X부와 결합을 갖는 나프탈렌을 나타낸다. A1∼A5은 단일 결합, 알킬렌 및 아릴렌 중 어느 하나를 나타내고, X1∼X6은 -OCONH-, -NHCOO-, -NHCO- 및 -CONH- 중 어느 하나를 나타낸다. R1∼R6은 수소 원자, 할로겐 원자, 알킬기 및 아릴기 중 어느 하나를 나타낸다.However, P in the said General formula (1), (2), and (3) represents either an oxygen atom, a carbonyl group, an amide group, a urethane group, alkylene, and arylene. Q represents any of a boron atom, a nitrogen atom, alkylene, and arylene. W represents naphthalene having a bond with two X moieties. A 1 to A 5 represent any one of a single bond, alkylene and arylene, and X 1 to X 6 represent any one of -OCONH-, -NHCOO-, -NHCO-, and -CONH-. R 1 to R 6 represent any one of a hydrogen atom, a halogen atom, an alkyl group and an aryl group.
상기 일반식(1)∼(3) 중 상기 P의 알킬렌은 무치환 알킬렌; 아릴기, 알케닐기 및 히드록실기 중 적어도 어느 하나이거나, 및 알콕시기, 시아노기 및 할로겐 원자 중 적어도 어느 하나로 치환되어 있는 치환기 함유 알킬렌을 나타낸다.In the general formulas (1) to (3), the alkylene of P is unsubstituted alkylene; At least one of an aryl group, an alkenyl group, and a hydroxyl group, and the substituent containing alkylene substituted by at least any one of an alkoxy group, a cyano group, and a halogen atom are shown.
상기 무치환 알킬렌으로서는 분기를 갖고 있어도 좋고, 2중 결합, 3중 결합을 갖고 있어도 좋고, 총탄소수는 1∼20개인 것이 바람직하고, 1∼8개가 특히 바람직하다. 이러한 알킬렌으로서는 에틸렌, 프로필렌, i-프로필렌, 부틸렌, i-부틸렌, 시클로헥실렌 등이 열거된다.As said unsubstituted alkylene, you may have a branch, you may have a double bond and a triple bond, It is preferable that total carbon number is 1-20, and 1-8 are especially preferable. Examples of such alkylene include ethylene, propylene, i-propylene, butylene, i-butylene, cyclohexylene and the like.
상기 치환기 함유 알킬렌 중의 아릴 치환기로서는, 총탄소수 6∼30개인 것이 바람직하고, 6∼15개가 특히 바람직하고, 상기 치환기로서, 예를 들면 페닐기, 나프틸기, 안트라세닐기, 메톡시페닐기, 클로로페닐기 등이 열거된다.As an aryl substituent in the said substituent containing alkylene, it is preferable that it is 6-30 total carbons, 6-15 are especially preferable, As a substituent, for example, a phenyl group, a naphthyl group, anthracenyl group, a methoxyphenyl group, a chlorophenyl group And the like.
상기 치환기 함유 알킬렌 중의 알케닐 치환기로서는 총탄소수 2∼10개가 바람직하고, 2∼6개가 특히 바람직하고, 치환기로서, 예를 들면 에티닐기, 프로페닐기, 부티릴기 등이 열거된다.As an alkenyl substituent in the said substituent containing alkylene, 2-10 total carbons are preferable, 2-6 are especially preferable, As a substituent, an ethynyl group, a propenyl group, butyryl group etc. are mentioned, for example.
상기 치환기 함유 알킬렌 중의 알콕시 치환기로서는 분기를 갖고 있어도 좋고, 총탄소수 1∼10개가 바람직하고, 1∼5개가 특히 바람직하고, 상기 치환기로서, 예를 들면 메톡시기, 에톡시기, 프로필옥시기, 2-메틸프로필옥시기, 부톡시기 등이 열거된다.As an alkoxy substituent in the said substituent containing alkylene, you may have a branch, 1-10 total carbons are preferable, 1-5 are especially preferable, As a substituent, a methoxy group, an ethoxy group, a propyloxy group, 2 -Methylpropyloxy group, butoxy group, etc. are mentioned.
이러한 치환기 함유 알킬렌으로서는 분기를 갖고 있어도 좋고, 2중 결합, 3중 결합을 갖고 있어도 좋고, 총탄소수 2∼40개가 바람직하고, 2∼25개가 특히 바람직하다. 이러한 치환 함유 알킬렌으로서는, 예를 들면, 2-에틸헥실기, 클로로부틸기, 벤질기, 2-에티닐프로필기, 페닐에틸기, 시아노프로필기, 메톡시에틸기 등이 열거된다. As such a substituent containing alkylene, you may have a branch, you may have a double bond and a triple bond, 2-40 carbon atoms are preferable, and 2-25 are especially preferable. Examples of such substituted-containing alkylene include 2-ethylhexyl group, chlorobutyl group, benzyl group, 2-ethynylpropyl group, phenylethyl group, cyanopropyl group, methoxyethyl group and the like.
상기 P의 아릴렌으로서는 후술하는 A1∼A5의 아릴렌과 동일한 의미이다.Examples of the arylene group P is as defined and arylene, which is described later A 1 ~A 5.
상기 일반식(1)∼(3) 중, 상기 Q의 알킬렌으로서는, 상기 무치환 알킬렌이 열거되고, 상기 무치환 알킬렌으로서는 분기를 갖고 있어도 좋고, 2중 결합, 3중 결합을 갖고 있어도 좋고, 총탄소수는 2∼30개의 것이 바람직하다. 이러한 알킬렌으로서는 에틸렌, 프로필렌, i-프로필렌, 부틸렌, i-부틸렌, 시클로헥실렌 등이 열거된다.In the general formulas (1) to (3), as the alkylene of Q, the unsubstituted alkylene may be cited, and as the unsubstituted alkylene may have a branch, and may have a double bond or a triple bond. The total carbon number is preferably 2 to 30. Examples of such alkylene include ethylene, propylene, i-propylene, butylene, i-butylene, cyclohexylene and the like.
상기 Q의 아릴렌으로서는 후술하는 A1∼A5의 아릴렌과 동일한 의미이다.As the arylene and Q is as defined and arylene, which is described later A 1 ~A 5.
상기 일반식(1)∼(3) 중, 상기 W의 X부와의 결합 부위는 1, 2위치, 1, 3위치, 1, 5위치, 1, 6위치, 1, 7위치, 1, 8위치, 2, 3위치, 2, 4위치, 2, 5위치, 2, 7위치이고, 상기 W로서는 알킬기, 아릴기, 알콕시기, 할로겐 원자 중 어느 하나로 치환 되어 있어도 좋다.In said general formula (1)-(3), the coupling | bonding site | part with the X part of said W is 1, 2 position, 1, 3 position, 1, 5 position, 1, 6 position, 1, 7 position, 1, 8 It is a position, 2, 3 position, 2, 4 position, 2, 5 position, 2, 7 position, and W may be substituted by any of an alkyl group, an aryl group, an alkoxy group, and a halogen atom.
상기 일반식(1)∼(3) 중, 상기 A1∼A5의 아릴렌이란, 벤젠환 및 알킬기, 아릴기, 알케닐기, 알콕시기, 시아노기 및 할로겐 원자 중 적어도 어느 하나로 치환되어 있는 치환기 함유 아릴렌을 나타낸다.In the general formulas (1) to (3), the arylene of A 1 to A 5 is a substituent substituted with at least one of a benzene ring and an alkyl group, an aryl group, an alkenyl group, an alkoxy group, a cyano group, and a halogen atom. Containing arylene is shown.
상기 치환기 함유 아릴렌 중의 알킬기로서는 분기를 갖고 있어도 좋고, 2중 결합, 3중 결합을 갖고 있어도 좋고, 총탄소수는 1∼20개의 것이 바람직하고, 1∼10개가 특히 바람직하다. 이러한 알킬기로서는 메틸기, 에틸기, 프로필기, 이소프로필기, 부틸기, s-부틸기, t-부틸기, 부티릴기, 시클로헥실기, 시클로헥세닐기 등 이 열거된다.As an alkyl group in the said substituent containing arylene, you may have a branch, you may have a double bond, and a triple bond, 1-20 pieces are preferable, and, as for total carbon number, 1-10 pieces are especially preferable. Examples of such alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group, butyryl group, cyclohexyl group and cyclohexenyl group.
상기 치환기 함유 아릴렌 중의 아릴 치환기로서는 총탄소수 6∼30개의 것이 바람직하고, 6∼15개가 특히 바람직하고, 상기 치환기로서는 예를 들면, 페닐기, 나프틸기, 안트라세닐기, 메톡시페닐기, 클로로 페닐기 등이 열거된다.The aryl substituent in the substituent-containing arylene is preferably 6 to 30 carbon atoms, particularly preferably 6 to 15 carbon atoms. Examples of the substituent include a phenyl group, naphthyl group, anthracenyl group, methoxyphenyl group, chlorophenyl group, and the like. This is listed.
상기 치환기 함유 아릴렌 중의 알킬기로서는 분기를 갖고 있어도 좋고, 2중 결합, 3중 결합을 갖고 있어도 좋고, 총탄소수는 1∼20개의 것이 바람직하고, 1∼10개가 특히 바람직하다. 이러한 알킬기로서는 메틸기, 에틸기, 에티닐기, 프로필기, 이소프로필기, 부틸기, s-부틸기, t-부틸기, 부티릴기, 시클로헥실기, 시클로헥세닐기 등이 열거된다.As an alkyl group in the said substituent containing arylene, you may have a branch, you may have a double bond, and a triple bond, 1-20 pieces are preferable, and, as for total carbon number, 1-10 pieces are especially preferable. Examples of such alkyl groups include methyl, ethyl, ethynyl, propyl, isopropyl, butyl, s-butyl, t-butyl, butyryl, cyclohexyl and cyclohexenyl groups.
치환기 함유 아릴렌 중의 알케닐 치환기로서는, 총탄소수 2∼10개가 바람직하고, 2∼6개가 특히 바람직하고, 상기 치환기로서는 예를 들면, 에티닐기, 프로페닐기, 부티릴기 등이 열거된다.As an alkenyl substituent in a substituent containing arylene, 2-10 total carbons are preferable, 2-6 are especially preferable, For example, an ethynyl group, a propenyl group, butyryl group etc. are mentioned as said substituent.
치환기 함유 아릴렌 중의 알콕시 치환기로서는 분기를 갖고 있어도 좋고, 총탄소수 1∼10개가 바람직하고, 1∼5개가 특히 바람직하고, 상기 치환기로서는 예를 들면, 메톡시기, 에톡시기, 프로필옥시기, 2-메틸프로필옥시기, 부톡시기 등이 열거된다.As an alkoxy substituent in a substituent containing arylene, it may have a branch, 1-10 total carbons are preferable, 1-5 are especially preferable, As a substituent, a methoxy group, an ethoxy group, a propyloxy group, 2- Methylpropyloxy group, butoxy group, etc. are mentioned.
이러한 치환기 함유 아릴렌으로서는 분기를 갖고 있어도 좋고, 2중 결합, 3중 결합을 갖고 있어도 좋고, 총탄소수 2∼40개가 바람직하고, 2∼25개가 특히 바람직하다.Such substituent-containing arylene may have a branch, may have a double bond, or a triple bond, 2-40 total carbon atoms are preferable, and 2-25 are especially preferable.
이러한 치환기 함유 아릴렌으로서는 예를 들면, 메틸페닐환, 디메틸페닐환, 디부틸페닐환, 메톡시페닐환, 시클로헥실페닐환, 비페닐 구조, 디클로로페닐환, 트리브로모페닐환, 클로로시아노페닐환 등이 열거된다.As such substituent-containing arylene, for example, methylphenyl ring, dimethylphenyl ring, dibutylphenyl ring, methoxyphenyl ring, cyclohexylphenyl ring, biphenyl structure, dichlorophenyl ring, tribromophenyl ring, chlorocyanophenyl Rings and the like.
또한, 상기 A1∼A5의 알킬렌은 상기 P의 알킬렌과 동일한 의미이다.In addition, the alkylene of said A <1> -A <5> is synonymous with the alkylene of said P.
상기 일반식(1)∼(3) 중 상기 X1∼X6은 상기한 바와 같이, -OCONH-, -NHCOO-, -NHCO- 및 -CONH- 중 어느 하나를 나타낸다.In said general formula (1)-(3), said X <1> -X <6> represents either -OCONH-, -NHCOO-, -NHCO-, and -CONH- as mentioned above.
상기 일반식(1)∼(3) 중 상기 R1∼R6의 알킬기란, 무치환 알킬기; 아릴기, 알케닐기 및 히드록실기 중 적어도 어느 하나, 및 알콕시기, 시아노기 및 할로겐 원자 중 적어도 어느 하나로 치환되어 있고, 산소 원자, 황 원자, 카르보닐기, 아미드기, 우레탄기 및 우레아기 중 적어도 어느 하나, 및 에스테르기의 2가의 기 중 어느 하나를 갖고 있어도 좋은 치환기 함유 알킬기를 나타낸다.In the general formulas (1) to (3), the alkyl group of R 1 to R 6 is an unsubstituted alkyl group; At least one of an aryl group, an alkenyl group and a hydroxyl group, and at least one of an alkoxy group, cyano group and a halogen atom, and at least any one of an oxygen atom, a sulfur atom, a carbonyl group, an amide group, a urethane group and a urea group The substituent containing alkyl group which may have either of the divalent groups of one and an ester group is shown.
상기 무치환 알킬기로서는 분기를 갖고 있어도 좋고, 2중 결합, 3중 결합을 갖고 있어도 좋고, 총탄소수는 1∼20개의 것이 바람직하고, 1∼10개가 특히 바람직하다. 이러한 알킬기로서는 메틸기, 에틸기, 에티닐기, 프로필기, 이소프로필기, 부틸기, s-부틸기, t-부틸기, 부티릴기, 시클로헥실기, 시클로헥세닐기 등이 열거된다.As said unsubstituted alkyl group, you may have a branch, you may have a double bond, and a triple bond, 1-20 pieces are preferable, and 1-10 pieces are especially preferable. Examples of such alkyl groups include methyl, ethyl, ethynyl, propyl, isopropyl, butyl, s-butyl, t-butyl, butyryl, cyclohexyl and cyclohexenyl groups.
상기 치환기 함유 알킬기 중의 아릴 치환기로서는, 총탄소수 6∼30개의 것이 바람직하고, 6∼15개가 특히 바람직하고, 상기 치환기로서는 예를 들면, 페닐기, 나프틸기, 안트라세닐기, 메톡시페닐기, 클로로 페닐기 등이 열거된다.As an aryl substituent in the said substituent containing alkyl group, the thing of 6-30 total carbons is preferable, 6-15 are especially preferable, As said substituent, a phenyl group, a naphthyl group, anthracenyl group, a methoxyphenyl group, chloro phenyl group, etc. are mentioned, for example. This is listed.
상기 치환기 함유 알킬기 중의 알케닐 치환기로서는 총탄소수 2∼10개가 바람직하고, 2∼6개가 특히 바람직하고, 상기 치환기로서는 예를 들면 에티닐기, 프로페닐기, 부티릴기 등이 열거된다.As an alkenyl substituent in the said substituent containing alkyl group, 2-10 total carbons are preferable, 2-6 are especially preferable, As said substituent, an ethynyl group, a propenyl group, butyryl group etc. are mentioned, for example.
상기 치환기 함유 알킬기 중의 알콕시 치환기로서는 분기를 갖고 있어도 좋 고, 총탄소수 1∼10개가 바람직하고, 1∼5개가 특히 바람직하고, 상기 치환기로서는 예를 들면, 메톡시기, 에톡시기, 프로필옥시기, 2-메틸프로필옥시기, 부톡시기 등이 열거된다.As an alkoxy substituent in the said substituent containing alkyl group, you may have a branch, 1-10 total carbons are preferable, 1-5 are especially preferable, As a substituent, a methoxy group, an ethoxy group, a propyloxy group, 2 -Methylpropyloxy group, butoxy group, etc. are mentioned.
이러한 치환기 함유 알킬기는 분기를 갖고 있어도 좋고, 2중 결합, 3중 결합을 갖고 있어도 좋고, 총탄소수 2∼40개가 바람직하고, 2∼25개가 특히 바람직하다. 이러한 치환기 함유 알킬기로서는 예를 들면, 2-에틸헥실기, 클로로부틸기, 벤질기, 2-에티닐프로필기, 페닐에틸기, 시아노프로필기, 메톡시에틸기 등이 열거된다.Such a substituent-containing alkyl group may have a branch, and may have a double bond and a triple bond, 2-40 carbon atoms are preferable, and 2-25 are especially preferable. Examples of such substituent-containing alkyl group include 2-ethylhexyl group, chlorobutyl group, benzyl group, 2-ethynylpropyl group, phenylethyl group, cyanopropyl group, methoxyethyl group and the like.
상기 일반식(1)로 나타내지는 화합물로서는 구체적으로는, 하기 구조식(1)∼(10)으로 나타내어지는 화합물 등이 열거되지만, 이들의 화합물에 한정되는 것은 아니다.Specific examples of the compound represented by the general formula (1) include compounds represented by the following structural formulas (1) to (10), but are not limited to these compounds.
상기 구조식(1)∼(10)으로 나타내어지는 화합물 중에서도 상기 구조식(1), (2), (4)∼(7) 및 (9)로 나타내어지는 화합물이 특히 바람직하다.Among the compounds represented by the structural formulas (1) to (10), the compounds represented by the structural formulas (1), (2), (4) to (7) and (9) are particularly preferable.
상기 일반식(1)∼(3)으로 나타내어지는 화합물은 옥시란환 부위에 치환기를 갖는 옥시란환을 1분자 중에 2개 이상 갖는 화합물이고, 이들의 화합물이 감광성 조성물 중에 함유되는 것은 1H-NMR 스펙트럼을 측정해서 동정할 수 있다.The compounds represented by the general formulas (1) to (3) are compounds having two or more oxirane rings in one molecule having a substituent in the oxirane ring moiety, and it is 1 H- that these compounds are contained in the photosensitive composition. The NMR spectrum can be measured and identified.
[병용하는 열가교제][Combination of thermal crosslinking agent]
상기 열가교제로서 기능하는 일반식(1)∼(3)으로 나타내어지는 화합물 이외에도 종래 공지의 기타 열가교제를 더 병용해도 좋다.In addition to the compounds represented by General Formulas (1) to (3) which function as the heat crosslinking agent, other conventionally known heat crosslinking agents may be further used in combination.
상기 기타 열가교제로서는, 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있고, 상기 감광성 조성물을 사용하여 형성되는 감광층의 경화 후의 막강도를 개량하기 위해서, 현상성 등에 악영향을 주지 않는 범위에서, 예를 들면, 1분자내에 적어도 2개의 옥시란기를 갖는 에폭시 화합물, 1분자내에 적어도 2개의 옥세타닐기를 갖는 옥세탄 화합물을 사용할 수 있다.There is no restriction | limiting in particular as said other thermal crosslinking agent, According to the objective, in order to improve the film strength after hardening of the photosensitive layer formed using the said photosensitive composition, in the range which does not adversely affect developability etc., For example, an epoxy compound having at least two oxirane groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule can be used.
상기 1분자 중에 적어도 2개의 옥시란기를 갖는 에폭시 화합물로서는, 예를 들면, 비크실레놀형 또는 비페놀형 에폭시 수지(「YX4000 재팬에폭시레진사 제작」등) 또는 이들 혼합물, 이소시아누레이트 골격 등을 갖는 복소환식 에폭시 수지(「TEPIC; 닛산화학공업사 제작」, 「아랄다이트 PT810; 치바·스페셜티·케미컬즈사 제작」등), 비스페놀 A형 에폭시 수지, 노볼락형 에폭시 수지, 비스페놀 F형 에폭시 수지, 수소 첨가 비스페놀 A형 에폭시 수지, 비스페놀 S형 에폭시 수지, 페놀노볼락형 에폭시 수지, 크레졸 노볼락형 에폭시 수지, 할로겐화 에폭시 수지(예를 들면, 저브롬화 에폭시 수지, 고할로겐화 에폭시 수지, 브롬화 페놀 노볼락형 에폭시 수지 등), 알릴기 함유 비스페놀 A형 에폭시 수지, 트리스 페놀메탄형 에폭시 수지, 디페닐디메탄올형 에폭시 수지, 페놀비페닐렌형 에폭시 수지, 디시클로펜타디엔형 에폭시 수지(「HP-7200, HP-7200H; 다이니폰잉크화학공업사 제작」등), 글리시딜아민형 에폭시 수지(디아미노디페닐메탄형 에폭시 수지, 디글리시딜아닐린, 트리글리시딜아미노페놀 등), 글리시딜에스테르형 에폭시 수지(프탈산 디글리시딜에스테르, 아디프산 디글리시딜에스테르, 헥사히드로프탈산 디글리시딜에스테르, 다이머산 디글리시딜에스테르 등)히단토인형 에폭시 수지, 지환식 에폭시 수지(3,4-에폭시시클로헥실메틸-3',4'-에폭시시클로헥산카르복시레이트, 비스(3,4-에폭시시클로헥실메틸)아디페이트, 디시클로펜타디엔디에폭시드,「GT-300, GT-400, ZEHPE3150; 다이셀화학공업 제작」등), 이미드형 지환식 에폭시 수지, 트리히드록시페닐메탄형 에폭시 수지, 비스페놀A 노볼락형 에폭시 수지, 테트라페닐올에탄형 에폭시 수지, 글리시딜프탈레이트 수지, 테트라글리시딜크실레노일에탄 수지, 나프탈렌기 함유 에폭시 수지(나프톨아랄킬형 에폭시 수지, 나프톨노볼락형 에폭시 수지, 4관능 나프탈렌형 에폭시 수지, 시판품으로서는 「ESN-190, ESN-360; 신일본제철화학사 제작」, 「HP-4032, EXA-4750, EXA-4700; 다이니폰잉크화학공업사 제작」등), 페놀 화합물과 디비닐벤젠이나 디시클로펜타디엔 등의 디올레핀 화합물의 부가 반응에 의하여 얻어지는 폴리페놀 화합물과, 에피클로로히드린의 반응물, 4-비닐시크로헥센-1-옥사이드의 개환 중합물을 과아세트산 등으로 에폭시화한 것, 선상 인함유 구조를 갖는 에폭시 수지, 환상 인함유 구조를 갖는 에폭시 수지, α-메틸스틸벤형 액정 에폭시 수지, 디벤조일옥시벤젠형 액정 에폭시 수지, 아조 페닐형 액정 에폭시 수지, 아조메틴페닐형 액정 에폭시 수지, 비나프틸형 액정 에폭시 수지, 아진형 에폭시 수지, 글리시딜 메타아크릴레이트 공중합계 에폭시 수지(「CP-50S, CP-50M; 일본 유지사 제작」등), 시클로헥실 말레이미드와 글리시딜메타아크릴레이트의 공중합 에폭시 수지, 비스(글리시딜옥시페닐)플루오렌형 에폭시 수지, 비스(글리시딜옥시페닐)아다만탄형 에폭시 수지 등이 열거되지만, 이들에 한정되는 것은 아니다. 이들의 에폭시 수지는 1종 단독으로 사용해도 좋고, 2종 이상을 병용해도 좋다.As an epoxy compound which has at least two oxirane groups in the said 1 molecule, For example, a bixylenol type or a biphenol type epoxy resin ("YX4000 Japan epoxy resin company make", etc.), these mixtures, an isocyanurate skeleton etc. are mentioned. Heterocyclic cyclic epoxy resin ("TEPIC; Nissan Chemical Co., Ltd.", "Araldite PT810; Chiba Specialty Chemicals Co., Ltd."), bisphenol A type epoxy resin, novolak type epoxy resin, bisphenol F type epoxy resin, Hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin, brominated phenol novolak) Epoxy resin, etc.), allyl group-containing bisphenol A epoxy resin, tris phenol methane epoxy resin, diphenyl dimethanol epoxy G, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin ("HP-7200, HP-7200H; Dainippon Ink and Chemicals", etc.), glycidylamine type epoxy resin (diaminodiphenylmethane type) Epoxy resin, diglycidyl aniline, triglycidylaminophenol, etc., glycidyl ester type epoxy resin (phthalic acid diglycidyl ester, adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, Hydantoin type epoxy resin, alicyclic epoxy resin (3, 4- epoxycyclohexyl methyl-3 ', 4'- epoxycyclohexane carboxylate, bis (3, 4- epoxy cyclohexyl) Methyl) adipate, dicyclopentadiene diepoxide, `` GT-300, GT-400, ZEHPE3150; manufactured by Daicel Chemical Industry, '' etc.), imide alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A Novolak epoxy resin, te Laphenylol ethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group containing epoxy resin (naphthol aralkyl type epoxy resin, naphthol novolak type epoxy resin, tetrafunctional naphthalene type epoxy resin, commercial item Examples include "ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.", "HP-4032, EXA-4750, EXA-4700; Dainippon Ink and Chemicals Co., Ltd. "), a polyphenol compound obtained by addition reaction of a phenol compound and diolefin compounds such as divinylbenzene and dicyclopentadiene, and a reaction product of epichlorohydrin, 4-vinylcyclohexene Epoxidized ring-opening polymer of -1-oxide with peracetic acid or the like, epoxy resin having linear phosphorus containing structure, epoxy resin having cyclic phosphorus containing structure, α-methylstilbene type liquid crystal epoxy resin, dibenzoyloxybenzene type liquid crystal Epoxy resin, azo phenyl type liquid crystal epoxy resin, azomethine phenyl type liquid crystal epoxy resin, binaphthyl type liquid crystal epoxy resin, azine type epoxy resin, glycidyl methacrylate copolymer type epoxy resin ("CP-50S, CP-50M; Japanese fats and oils production ", etc., the copolymerization epoxy resin of cyclohexyl maleimide and glycidyl methacrylate, bis (glycidyl oxyphenyl) fluorene type Although a foxy resin, bis (glycidyl oxyphenyl) adamantane type epoxy resin, etc. are mentioned, It is not limited to these. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.
상기 옥세탄 화합물로서는 예를 들면, 비스[(3-메틸-3-옥세타닐메톡시)메틸]에테르, 비스[(3-에틸-3-옥세타닐메톡시)메틸]에테르, 1,4-비스[(3-메틸-3-옥세타닐메톡시)메틸]벤젠, 1,4-비스[(3-에틸-3-옥세타닐메톡시)메틸]벤젠, (3-메틸-3-옥세타닐)메틸아크릴레이트, (3-에틸-3-옥세타닐)메틸아크릴레이트, (3-메틸-3-옥세타닐)메틸메타크릴레이트, (3-에틸-3-옥세타닐)메틸메타크릴레이트 또는 이들 올리고머 또는 공중합체 등의 다관능 옥세탄류 이외에, 옥세탄기를 갖는 화합물과 노볼락 수지, 폴리(p-히드록시스티렌), 카르도형 비스페놀류, 칼릭사렌류, 칼릭스레조르신아렌류, 실세스퀴옥산 등의 수산기를 갖는 수지 등의 에테르 화합물이 열거되고, 이 밖에, 옥세탄환을 갖는 불포화 모노머와 알킬(메타)아크릴레이트의 공중합체 등도 열거된다.Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether and 1,4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) Methylacrylate, (3-ethyl-3-oxetanyl) methylacrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate Or a compound having an oxetane group, a novolak resin, a poly (p-hydroxy styrene), a cardo-type bisphenol, a kalisarene, a calix resorcinarene, in addition to polyfunctional oxetanes such as these oligomers or copolymers, Ether compounds, such as resin which has hydroxyl groups, such as a silsesquioxane, are mentioned, In addition, the copolymer etc. of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate are mentioned.
또한, 상기 에폭시 화합물이나 상기 옥세탄 화합물의 열경화를 촉진하기 위해서, 예를 들면 디시안디아미드, 벤질디메틸아민, 4-(디메틸아미노)-N,N-디메틸벤질아민, 4-메톡시-N,N-디메틸벤질아민, 4-메틸-N,N-디메틸벤질아민 등의 아민 화합 물; 트리에틸벤질암모늄클로라이드 등의 4급 암모늄염 화합물; 디메틸아민 등의 블록 이소시아네이트 화합물; 이미다졸, 2-메틸이미다졸, 2-에틸이미다졸, 2-에틸-4-메틸이미다졸, 2-페닐이미다졸, 4-페닐이미다졸, 1-시아노에틸-2-페닐이미다졸, 1-(2-시아노에틸)-2-에틸-4-메틸이미다졸 등의 이미다졸 유도체 2환식 아미딘 화합물 및 그 염; 트리페닐포스핀 등의 인화합물; 멜라민, 구아나민, 아세토구아나민, 벤조구아나민 등의 구아나민 화합물; 2,4-디아미노-6-메타크릴로일옥시에틸-S-트리아진, 2-비닐-2,4-디아미노-S-트리아진, 2-비닐-4,6-디아미노-S-트리아진·이소시아누르산 부가물, 2,4-디아미노-6-메타크릴로일옥시에틸-S-트리아진·이소시아누르산부가물 등의 S-트리아진 유도체; 등을 사용할 수 있다. 이들은 1종 단독으로 사용해도 좋고, 2종 이상을 병용해도 좋다. 또한, 상기 에폭시 화합물이나 상기 옥세탄 화합물의 경화 촉매 또는 이들과 카르복실기의 반응을 촉진할 수 있는 것이면, 특별히 제한은 없고, 상기 이외의 열경화를 촉진 가능한 화합물을 사용해도 좋다.In addition, in order to promote thermosetting of the epoxy compound or the oxetane compound, for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N Amine compounds such as, N-dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; Quaternary ammonium salt compounds such as triethylbenzyl ammonium chloride; Block isocyanate compounds such as dimethylamine; Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2- Imidazole derivative bicyclic amidine compounds such as phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole and salts thereof; Phosphorus compounds such as triphenylphosphine; Guanamine compounds, such as melamine, guanamine, acetoguanamine and benzoguanamine; 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S- S-triazine derivatives, such as a triazine isocyanuric acid adduct and a 2, 4- diamino-6-methacryloyloxyethyl-S-triazine and an isocyanuric acid adduct; Etc. can be used. These may be used individually by 1 type and may use 2 or more types together. In addition, as long as it can accelerate | stimulate reaction of the hardening catalyst of the said epoxy compound, the said oxetane compound, or these, and a carboxyl group, there is no restriction | limiting in particular, You may use the compound which can promote the thermosetting of that excepting the above.
상기 에폭시 화합물, 상기 옥세탄 화합물 및 이들과 카르복실산의 열경화를 촉진 가능한 화합물의 상기 감광성 조성물 고형분 중의 고형분 함유량으로서는 통상 0.01∼15질량%이다.As content of solid content in the said photosensitive composition solid content of the said epoxy compound, the said oxetane compound, and the compound which can promote thermosetting of these and a carboxylic acid, it is 0.01-15 mass% normally.
또한, 상기 열가교제로서는 일본특허공개 평5-9407호 공보 기재의 폴리 이소시아네이트 화합물을 사용할 수 있고, 상기 폴리 이소시아네이트 화합물은 적어도 2개의 이소시아네이트기를 함유하는 지방족, 환식 지방족 또는 방향족기 치환 지방족 화합물로부터 유도되어 있어도 좋다. 구체적으로는, 2관능 이소시아네이트(예를 들면, 1,3-페닐렌디이소시아네이트와 1,4-페닐렌디이소시아네이트의 혼합물, 2,4- 및 2,6-톨루엔디이소시아네이트, 1,3- 및 1,4-크실릴렌 디이소시아네이트, 비스(4-이소시아네이트페닐)메탄, 비스(4-이소시아네이트시클로헥실)메탄, 이소포론디이소시아네이트, 헥사메틸렌디이소시아네이트, 트리메틸헥사메틸렌디이소시아네이트 등), 상기 2관능 이소시아네이트와 트리메틸올프로판, 펜타에리스톨, 글리세린 등의 다관능 알콜; 상기 다관능 알콜의 알킬렌 옥사이드 부가체와 상기 2관능 이소시아네이트의 부가체; 헥사메틸렌디이소시아네이트, 헥사메틸렌-1,6-디이소시아네이트 및 그 유도체 등의 환식 3량체나 뷰렛체; 노르보르난 디이소시아네이트; 등이 열거된다.As the thermal crosslinking agent, a polyisocyanate compound described in Japanese Patent Application Laid-Open No. 5-9407 can be used, and the polyisocyanate compound is derived from an aliphatic, cyclic aliphatic or aromatic group-substituted aliphatic compound containing at least two isocyanate groups. You may be. Specifically, difunctional isocyanate (for example, a mixture of 1,3-phenylenediisocyanate and 1,4-phenylenediisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1, 4-xylylene diisocyanate, bis (4-isocyanatephenyl) methane, bis (4-isocyanatecyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc.), the bifunctional isocyanate and Polyfunctional alcohols such as trimethylolpropane, pentaerythritol and glycerin; An adduct of an alkylene oxide adduct of the polyfunctional alcohol and the difunctional isocyanate; Cyclic trimers and biuret bodies such as hexamethylene diisocyanate, hexamethylene-1,6-diisocyanate and derivatives thereof; Norbornane diisocyanate; And the like.
또한, 본 발명의 감광성 조성물 및 후술의 감광성 필름의 보존성을 향상시키는 것을 목적으로서, 상기 폴리이소시아네이트 및 그 유도체의 이소시아네이트기에 블록제를 반응시켜서 얻어지는 화합물을 사용해도 좋다.Moreover, you may use the compound obtained by making a blocking agent react with the isocyanate group of the said polyisocyanate and its derivative (s) for the purpose of improving the storage property of the photosensitive composition of this invention and the photosensitive film mentioned later.
상기 이소시아네이트기 블록제로서는 알콜류(예를 들면, 이소프로판올, tert-부탄올 등), 락탐류(예를 들면,ε-카프로락탐 등), 페놀류(예를 들면, 페놀, 크레졸, p-tert-부틸페놀, p-sec-부틸페놀, p-sec-아밀페놀, p-옥틸페놀, p-노닐페놀 등), 복소환식 히드록실 화합물(예를 들면, 3-히드록시피리딘, 8-히드록시퀴놀린 등), 활성 메틸렌 화합물(예를 들면, 디알킬말로네이트, 메틸에칠케톡심, 아세틸아세톤, 알킬아세토아세테이트옥심, 아세토옥심, 시클로헥사논옥심 등) 등이 열거된다. 이 밖에, 일본특허공개 평6-295060호 공보 기재의 분자내에 적어도 1개의 중합가능한 2중 결합 및 적어도 1개의 블록 이소시아네이트기 중 어느 하나를 갖는 화합물 등을 사용할 수 있다.As said isocyanate group blocking agent, alcohols (for example, isopropanol, tert-butanol, etc.), lactams (for example, (epsilon) -caprolactam, etc.), phenols (for example, phenol, cresol, p-tert- butylphenol , p-sec-butylphenol, p-sec-amylphenol, p-octylphenol, p-nonylphenol, etc.), heterocyclic hydroxyl compounds (for example, 3-hydroxypyridine, 8-hydroxyquinoline, etc.) And active methylene compounds (e.g., dialkylmalonate, methylethylketoxime, acetylacetone, alkylacetoacetate oxime, acetooxime, cyclohexanone oxime, etc.). In addition, the compound etc. which have any one of at least 1 polymerizable double bond and at least 1 block isocyanate group in the molecule | numerator of Unexamined-Japanese-Patent No. 6-295060 can be used.
또한, 상기 열가교제로서, 멜라민 유도체를 사용할 수 있다. 상기 멜라민 유도체로서는, 예를 들면 메틸올멜라민, 알킬화 메틸올멜라민(메틸올기를 메틸, 에틸, 부틸 등으로 에테르화한 화합물) 등이 열거된다. 이들은 1종 단독으로 사용해도 좋고, 2종 이상을 병용해도 좋다. 이들 중에서도 보존 안정성이 양호하고, 감광층의 표면경도 또는 경화막의 막강도 자체의 향상에 유효한 점에서, 알킬화 메틸올 멜라민이 바람직하고, 헥사메틸화 메틸올멜라민이 특히 바람직하다.In addition, a melamine derivative may be used as the thermal crosslinking agent. Examples of the melamine derivatives include methylolmelamine, alkylated methylolmelamine (compounds obtained by etherification of methylol with methyl, ethyl, butyl, etc.) and the like. These may be used individually by 1 type and may use 2 or more types together. Among them, alkylated methylol melamine is preferred, and hexamethylated methylol melamine is particularly preferable because of its good storage stability, and the effect of improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.
또한, 그 밖의 열가교제로서, 멜라민 이외의 알데히드 축합 생성물, 수지 전구체 등을 사용할 수 있다. 구체적으로는, N,N'-디메틸올우레아, N,N'-디메틸올말론아미드, N,N'-디메틸올숙신이미드, 1,3-N,N'-디메틸올테레프탈아미드, 2,4,6-트리메틸올페놀, 2,6-디메틸올-4-메틸올아니솔, 1,3-디메틸올-4,6-디이소프로필벤젠 등이 열거된다. 또한, 이들의 메틸올 화합물 대신에, 대응하는 에틸 또는 부틸에테르, 또는 아세트산 또는 프로피온산의 에스테르를 사용해도 좋다.Moreover, as other heat crosslinking agents, aldehyde condensation products other than melamine, resin precursors, etc. can be used. Specifically, N, N'- dimethylol urea, N, N'- dimethylol malonamide, N, N'- dimethylol succinimide, 1, 3-N, N'- dimethylol terephthalamide, 2, 4,6-trimethylolphenol, 2,6-dimethylol-4-methylolanisole, 1,3-dimethylol-4,6-diisopropylbenzene, and the like. Instead of these methylol compounds, corresponding ethyl or butyl ethers or esters of acetic acid or propionic acid may be used.
상기 일반식(1)∼(3)으로 나타어내지는 화합물 및 그 밖의 열가교제의 감광성 조성물 고형분 중에 있어서의 고형분 함유량으로서는 1∼50질량%가 바람직하고, 3∼30질량%가 보다 바람직하다. 상기 함유량이 1질량%미만이면, 가열 처리시의 반응이 저하되고, 경화막의 막강도의 향상이 도모될 수 없는 경우가 있고, 50질량%를 초과하면, 현상성, 노광 감도의 저하, 및 경화막의 막경도의 저하를 일으키는 경우가 있다.As solid content in the photosensitive composition solid content of the compound represented by the said General formula (1)-(3), and other heat crosslinking agent, 1-50 mass% is preferable, and 3-30 mass% is more preferable. When the said content is less than 1 mass%, reaction at the time of heat processing may fall, the improvement of the film strength of a cured film may not be planable, and when it exceeds 50 mass%, developability, the fall of exposure sensitivity, and hardening The film hardness of the film may be lowered in some cases.
-열경화 촉진제-Thermosetting accelerator
상기 바인더 중의 에폭시아크릴레이트 화합물의 열경화를 촉진시키기 위해 서, 종래 공지의 열경화 촉진제를 배합할 수 있다. 상기 열경화 촉진제로서는, 예를 들면, 디시안디아미드, 벤질디메틸아민, 4-(디메틸아미노)-N,N-디메틸벤질아민, 4-메톡시-N,N-디메틸벤질아민, 4-메틸-N,N-디메틸벤질아민 등의 아민 화합물; 트리에틸벤질암모늄클로라이드 등의 4급 암모늄 염화합물; 디메틸아민 등으로 블록된 블록 이소시아네이트 화합물; 이미다졸, 2-메틸이미다졸, 2-에틸이미다졸, 2-에틸-4-메틸이미다졸, 2-페닐이미다졸, 4-페닐이미다졸, 1-시아노에틸-2-페닐이미다졸, 1-(2-시아노에틸)-2-에틸-4-메틸이미다졸 등의 이미다졸 유도체 2환식 아미딘 화합물 및 그 염; 트리페닐포스핀 등의 인 화합물; 멜라민, 구아나민, 아세토구아나민, 벤조구아나민 등의 구아나민 화합물; 2,4-디아미노-6-메타크릴로일옥시에틸-S-트리아진, 2-비닐-2,4-디아미노-S-트리아진, 2-비닐-4,6-디아미노-S-트리아진·이소시아누르산 부가물, 2,4-디아미노-6-메타크릴로일 옥시에틸-S-트리아진·이소시아누르산 부가물 등의 S-트리아진 유도체; 등을 사용할 수 있다. 이들은 1종 단독으로 사용해도 좋고, 2종 이상을 병용해도 좋다.In order to promote thermosetting of the epoxy acrylate compound in the binder, a conventionally known thermosetting accelerator can be blended. As said thermosetting accelerator, for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl- Amine compounds such as N, N-dimethylbenzylamine; Quaternary ammonium salt compounds such as triethylbenzyl ammonium chloride; Block isocyanate compounds blocked with dimethylamine or the like; Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2- Imidazole derivative bicyclic amidine compounds such as phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole and salts thereof; Phosphorus compounds such as triphenylphosphine; Guanamine compounds, such as melamine, guanamine, acetoguanamine and benzoguanamine; 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S- S-triazine derivatives, such as a triazine isocyanuric acid adduct and a 2, 4- diamino-6-methacryloyl oxyethyl-S-triazine and an isocyanuric acid adduct; Etc. can be used. These may be used individually by 1 type and may use 2 or more types together.
또한, 상기 열경화 촉진제로서는, 상기 에폭시아크릴레이트 화합물의 열경화를 촉진할 수 있는 것이면, 특별히 제한은 없고, 상기 이외의 열경화를 촉진가능한 화합물을 사용해도 좋다.The thermosetting accelerator is not particularly limited as long as it can promote thermosetting of the epoxy acrylate compound, and a compound capable of promoting thermosetting other than the above may be used.
상기 열경화 촉진제의 상기 감광성 조성물 고형분 중의 고형분 함유량은 0.01~15질량%인 것이 바람직하다.It is preferable that solid content in the said photosensitive composition solid content of the said thermosetting accelerator is 0.01-15 mass%.
[기타 성분][Other Ingredients]
상기 기타 성분으로서는 예를 들면, 열중합 금지제, 가소제, 착색제(착색 안 료 또는 염료), 체질 안료 등이 열거되고, 또한 기재 표면으로의 밀착 촉진제 및 그 밖의 조제류(예를 들면, 도전성 입자, 충전제, 소포제, 난연제, 레벨링제, 박리촉진제, 산화방지제, 향료, 표면장력 조정제, 연쇄이동제 등)를 병용해도 좋다. 이들의 성분을 적당하게 함유시킴으로써, 목적으로 하는 감광성 조성물 또는 감광성 필름의 안정성, 사진성, 막물성 등의 성질을 조정할 수 있다.As said other components, a thermal polymerization inhibitor, a plasticizer, a coloring agent (coloring pigment or dye), a sieving pigment, etc. are mentioned, for example, Adhesion promoter to a surface of a base material, and other preparations (for example, electroconductive particle) , Fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, and the like. By containing these components suitably, properties, such as stability, a photographic property, film | membrane property, etc. of the target photosensitive composition or photosensitive film, can be adjusted.
-열중합 금지제-Thermal polymerization inhibitor
상기 열중합 금지제는 상기 중합성 화합물의 열적인 중합 또는 경시적인 중합을 방지하기 위해서 첨가해도 좋다.The thermal polymerization inhibitor may be added in order to prevent thermal polymerization or polymerization with time of the polymerizable compound.
상기 열중합 금지제로서는 예를 들면, 4-메톡시페놀, 하이드로퀴논, 알킬 또는 아릴 치환 하이드로퀴논, t-부틸카테콜, 피로갈롤, 2-히드록시벤조페논, 4-메톡시-2-히드록시 벤조페논, 염화 제일동, 페노티아진, 클로라닐, 나프틸아민, β-나프톨, 2,6-디-t-부틸-4-크레졸, 2,2'-메틸렌비스(4-메틸-6-t-부틸페놀), 피리딘, 니트로벤젠, 디니트로벤젠, 피크린산, 4-톨루이딘, 메틸렌블루, 동과 유기 크실레이트제 반응물, 살리실산 메틸, 및 페노티아진, 니트로소 화합물, 니트로소 화합물과 A1과의 킬레이트 등이 열거된다.Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone and 4-methoxy-2-hydride. Roxy benzophenone, first copper chloride, phenothiazine, chloranyl, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2,2'-methylenebis (4-methyl-6 t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic xylates reactant, methyl salicylate, and phenothiazine, nitroso compound, nitroso compound and A1 And chelates with.
상기 열중합 금지제의 함유량으로서는 상기 중합성 화합물에 대하여 0.001∼5질량%가 바람직하게, 0.005∼2질량%가 보다 바람직하며, 0.01∼1질량%가 특히 바람직하다. 상기 함유량이 0.001질량%미만이면, 보존시의 안정성이 저하하는 경우가 있고, 5질량%를 초과하면, 활성 에너지선에 대한 감도가 저하하는 경우가 있다.As content of the said thermal polymerization inhibitor, 0.001-5 mass% is preferable with respect to the said polymeric compound, 0.005-2 mass% is more preferable, 0.01-1 mass% is especially preferable. When the said content is less than 0.001 mass%, stability at the time of storage may fall, and when it exceeds 5 mass%, the sensitivity with respect to an active energy ray may fall.
-착색 안료--Pigmentation Pigment-
상기 착색 안료로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있고, 예를 들면 빅토리아·퓨어 블루 BO(C.I.42595), 오라민(C.I.41000), 팻·블랙 HB(C.I.26150), 모노 라이트·옐로우 GT(C.I.피그먼트·옐로우 12), 퍼머넌트·옐로우 GR(C.I.피그먼트·옐로우 17), 퍼머넌트·옐로우 HR(C.I.피그먼트·옐로우 83), 퍼머넌트·카민 FBB(C.I.피그먼트·레드 146), 호스타밤레드 ESB(C.I.피그먼트·바이올렛 19), 퍼머넌트·루비 FBH(C.I. 피그먼트·레드 11), 파스텔·핑크 B 스푸라(C.I.피그먼트·레드 81)모나스트랄·퍼스트·블루(C.I.피그먼트·블루 15), 모노라이트·퍼스트·블랙 B(C.I.피그먼트·블랙 1), 카본, C.I.피그먼트·레드97, C.I.피그먼트·레드 122, C.I. 피그먼트·레드 149, C.I. 피그먼트·레드 168, C.I.피그먼트·레드 177, C.I.피그먼트·레드 180, C.I.피그먼트·레드 192, C.I.피그먼트·레 드215, C.I.피그먼트·그린 7, C.I.피그먼트·그린 36, C.I.피그먼트·블루 15:1, C.I.피그먼트·블루 15:4, C.I.피그먼트·블루 15:6, C.I.피그먼트·블루 22, C.I. 피그먼트·블루 60, C.I.피그먼트·블루 64 등이 열거된다. 이들은 1종 단독으로 사용해도 좋고, 2종 이상을 병용해도 좋다.There is no restriction | limiting in particular as said coloring pigment, According to the objective, it can select suitably, For example, Victoria pure blue BO (CI42595), Oramine (CI41000), Fat black HB (CI26150), Mono light, Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Host star red ESB (CI pigment violet 19), permanent ruby FBH (CI pigment red 11), pastel pink B spura (CI pigment red 81) monastral first blue (CI pig) Blue 15), monolight first black B (CI pigment black 1), carbon, CI pigment red 97, CI pigment red 122, CI Pigment Red 149, C.I. Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI Pigment Green 36, CI Pigment blue 15: 1, CI pigment blue 15: 4, CI pigment blue 15: 6, CI pigment blue 22, CI Pigment blue 60, C.I. pigment blue 64, and the like. These may be used individually by 1 type and may use 2 or more types together.
상기 착색 안료의 상기 감광성 조성물 고형분 중의 고형분 함유량은, 영구 패턴 형성 시의 감광층의 노광 감도, 해상성 등을 고려해서 정할 수 있고, 상기 착색 안료의 종류에 의해 달라지지만, 일반적으로는 0.01∼10질량%가 바람직하고, 0.05∼5질량%가 보다 바람직하다.Solid content content in the said photosensitive composition solid content of the said coloring pigment can be determined in consideration of exposure sensitivity, resolution, etc. of the photosensitive layer at the time of permanent pattern formation, and it changes with kinds of the said coloring pigment, but is generally 0.01-10 Mass% is preferable and 0.05-5 mass% is more preferable.
-체질 안료-Constitution Pigment
상기 감광성 조성물에는 필요에 따라서, 영구 패턴의 표면 경도의 향상, 또 는 선팽창 계수를 낮게 억제하는 것, 또는 경화막 자체의 유전율이나 유전 정접을 낮게 억제하는 것을 목적으로서, 무기 안료나 유기 미립자를 첨가할 수 있다.If necessary, inorganic pigments and organic fine particles are added to the photosensitive composition for the purpose of improving the surface hardness of the permanent pattern, or suppressing the coefficient of linear expansion low, or reducing the dielectric constant and dielectric loss tangent of the cured film itself. can do.
상기 무기 안료로서는 특별히 제한은 없고, 공지의 것 중에서 적당하게 선택할 수 있고, 예를 들면 카올린, 황산 바륨, 티탄산 바륨, 산화 규소분, 미분상 산화 규소, 기상법 실리카, 무정형 실리카, 결정성 실리카, 용융 실리카, 구상 실리카, 탈크, 클레이, 탄산 마그네슘, 탄산 칼슘, 산화 알류미늄, 수산화 알루미늄, 마이카 등 이 열거된다.There is no restriction | limiting in particular as said inorganic pigment, It can select from a well-known thing suitably, For example, kaolin, barium sulfate, barium titanate, silicon oxide powder, fine powder silicon oxide, vapor phase silica, amorphous silica, crystalline silica, melting Silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica and the like.
상기 무기 안료의 평균 입경은 10㎛미만이 바람직하고, 3㎛이하가 보다 바람직하다. 상기 평균 입경이 10㎛이상이면, 광착란에 의해 해상도가 열화하는 경우가 있다.Less than 10 micrometers is preferable and, as for the average particle diameter of the said inorganic pigment, 3 micrometers or less are more preferable. When the said average particle diameter is 10 micrometers or more, resolution may deteriorate by optical confusion.
상기 유기 미립자로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있고, 예를 들면 멜라민 수지, 벤조구아나민 수지, 가교 폴리스티렌 수지 등 이 열거된다. 또한, 평균 입경 1∼5㎛, 흡유량 100∼200m2/g정도의 실리카, 가교 수지로 이루어지는 구상 다공질 미립자 등을 사용할 수 있다.There is no restriction | limiting in particular as said organic microparticles | fine-particles, According to the objective, it can select suitably, For example, a melamine resin, benzoguanamine resin, crosslinked polystyrene resin, etc. are mentioned. Moreover, the spherical porous fine particles which consist of silica of about 1-5 micrometers of average particle diameters, oil absorption amount of about 100-200m <2> / g, crosslinking resin, etc. can be used.
상기 체질 안료의 첨가량은 5∼60질량%가 바람직하다. 상기 첨가량이 5질량%미만이면, 충분하게 선팽창 계수를 저하시킬 수 없는 경우가 있고, 60질량%를 초과하면, 감광층 표면에 경화막을 형성했을 경우에, 상기 경화막의 막품질이 취약해져, 영구 패턴을 이용하여 배선을 형성할 경우에 있어서, 배선의 보호막으로서의 기능이 손상되는 경우가 있다.As for the addition amount of the said extender pigment, 5-60 mass% is preferable. If the addition amount is less than 5% by mass, the coefficient of linear expansion may not be sufficiently lowered. If the amount exceeds 60% by mass, when the cured film is formed on the surface of the photosensitive layer, the film quality of the cured film becomes weak and permanent. When wiring is formed using a pattern, the function as a protective film of wiring may be impaired.
-밀착 촉진제-Adhesion Promoter
각 층간의 밀착성, 또는 감광층과 기재의 밀착성을 향상시키기 위해서, 각 층에 공지의 소위, 밀착 촉진제라 하는 것을 사용할 수 있다.In order to improve the adhesiveness between each layer, or the adhesiveness of a photosensitive layer and a base material, what is called a well-known so called adhesion promoter can be used for each layer.
상기 밀착 촉진제로서는 예를 들면, 일본특허공개 평5-11439호 공보, 일본특허공개 평5-341532호 공보 및 일본특허공개 평6-43638호 공보 등에 기재된 밀착 촉진제가 바람직하게 열거된다. 구체적으로는 벤즈이미다졸, 벤즈옥사졸, 벤즈티아졸, 2-메르캅토벤즈이미다졸, 2-메르캅토벤즈옥사졸, 2-메르캅토벤즈티아졸, 3-몰포리노메틸-1-페닐-트리아졸-2-티온, 3-몰포리노메틸-5-페닐-옥사디아졸-2-티온, 5-아미노-3-몰포리노메틸-티아졸-2-티온 및 2-메르캅토-5-메틸티오-티아디아졸, 트리아졸, 테트라졸, 벤조트리아졸, 카르복시벤조트리아졸, 아미노기 함유 벤조트리아졸, 실란커플링제 등이 열거된다.As said adhesion promoter, the adhesion promoter described in Unexamined-Japanese-Patent No. 5-11439, Unexamined-Japanese-Patent No. 5-341532, Unexamined-Japanese-Patent No. 6-43638, etc. is mentioned preferably, for example. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-tria Sol-2-thione, 3-morpholinomethyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione and 2-mercapto-5-methylthio -Thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent and the like.
상기 밀착 촉진제의 함유량으로서는, 상기 감광성 조성물 중의 전체 성분에 대하여 0.001질량%∼20질량%가 바람직하고, 0.01∼10질량%가 보다 바람직하고, 0.1질량%∼5질량%가 특히 바람직하다.As content of the said adhesion promoter, 0.001 mass%-20 mass% are preferable with respect to the all components in the said photosensitive composition, 0.01-10 mass% is more preferable, 0.1 mass%-5 mass% are especially preferable.
본 발명의 감광성 조성물은 UV노광에 의해 화상 형성 가능하고, 표면의 택성이 작고, 라미네이트성 및 취급성이 양호하고, 보존시의 상온 하에서는 반응을 일으키지 않고, 보존 안정성이 우수하고, 고감도로 현상성도 우수하고, 현상 후 우수한 내약품성, 표면경도, 내열성, 유전 특성, 전기절연성 등을 발현한다. 이 때문에, 프린트 배선판(다층 배선 기판, 빌드업 배선 기판 등)의 보호막, 층간 절연막,및 솔더 레지스트 패턴, 컬러 필터나 골재, 리브재, 스페이서, 격벽 등의 디스플레 이용 부재, 홀로그램, 마이크로머신, 프루프 등의 영구 패턴 형성용으로서 널리 사용할 수 있고, 특히 본 발명의 감광성 필름, 영구 패턴 및 그 형성방법에 바람직하게 사용할 수 있다.The photosensitive composition of the present invention can be image-formed by UV exposure, has low surface tack, good lamination and handling properties, does not cause a reaction at room temperature at the time of storage, is excellent in storage stability, and develops with high sensitivity. It shows excellent chemical resistance, surface hardness, heat resistance, dielectric properties, electrical insulation after development. For this reason, protective films of printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), interlayer insulating films, and solder resist patterns, color filters and aggregates, rib members, spacers, partitions, display members, such as partition walls, holograms, micromachines, and proofs. It can be widely used for permanent pattern formation, such as these, and can especially use for the photosensitive film of this invention, a permanent pattern, and its formation method.
(감광성 필름)(Photosensitive film)
본 발명의 감광성 필름은 적어도 지지체와 감광층을 포함하여 이루어지고, 바람직하게는 보호 필름을 포함하여 이루어지고, 또한 필요에 따라서, 쿠션층, 산소 차단층(PC층) 등의 그 밖의 층을 포함하여 이루어진다.The photosensitive film of the present invention comprises at least a support and a photosensitive layer, preferably a protective film, and, if necessary, includes other layers such as a cushion layer, an oxygen barrier layer (PC layer), and the like. It is done by
상기 감광성 필름의 형태로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있고, 예를 들면, 상기 지지체 상에, 상기 감광층, 상기 보호막 필름을 이 순서로 포함하여 이루어지는 형태, 상기 지지체 상에, 상기 PC층, 상기 감광층, 상기 보호 필름을 이 순서로 포함하여 이루어지는 형태, 상기 지지체 상에 상기 쿠션층, 상기 PC층, 상기 감광층, 상기 보호 필름을 이 순서로 포함하여 이루어지는 형태등이 열거된다. 또한, 상기 감광층은 단층이어도 좋고, 복수층이어도 좋다.There is no restriction | limiting in particular as a form of the said photosensitive film, According to the objective, it can select suitably, For example, on the said support body, the form which contains the said photosensitive layer and the said protective film film in this order, on the said support body, The form which comprises the said PC layer, the said photosensitive layer, and the said protective film in this order, the form which includes the said cushion layer, the said PC layer, the said photosensitive layer, and the said protective film in this order on the said support body, etc. are enumerated. do. The photosensitive layer may be a single layer or a plurality of layers.
[감광층][Photosensitive layer]
상기 감광층은 본 발명의 상기 감광성 조성물에 의해 형성된다.The photosensitive layer is formed by the photosensitive composition of the present invention.
상기 감광층의 상기 감광성 필름에 있어서 형성되는 개소로서는, 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있지만, 통상, 상기 지지체 상에 적층된다.There is no restriction | limiting in particular as a location formed in the said photosensitive film of the said photosensitive layer, Although it can select suitably according to the objective, Usually, it is laminated | stacked on the said support body.
상기 감광층은 후술하는 노광 공정에 있어서, 광조사 수단으로부터의 광을 수광하여 출사하는 묘소부를 n개 갖는 광변조 수단에 의해, 상기 광조사 수단으로부터의 광을 변조시킨 후, 상기 묘소부에 있어서의 출사면의 변형에 의한 수차를 보정 가능한 비구면을 갖는 마이크로 렌즈를 배열한 마이크로 렌즈 어레이를 통한 광으로, 노광되는 것이 바람직하다.The photosensitive layer is modulated with light from the light irradiation means by the light modulating means having n drawing portions that receive and emit light from the light irradiation means in the exposure step to be described later. It is preferable to be exposed to light through a microlens array in which a microlens having an aspherical surface capable of correcting aberration due to deformation of the exit face of? Is arranged.
상기 감광층을 노광하여 현상하는 경우에 있어서, 상기 감광층의 노광하는 부분의 두께를, 상기 노광 및 현상 후에 있어서 변화시키지 않는 상기 노광에 사용하는 광의 최소 에너지는 0.1∼100(mJ/cm2)인 것이 바람직하고, 1∼80mJ/cm2인 것이 보다 바람직하다. 상기 노광에 사용하는 광의 최소 에너지가 0.1mJ/cm2미만이면, 가공 마진이 좁아지는 경우가 있고, 100mJ/cm2을 초과하면, 택트 시간이 길어지기 때문에 바람직하지 않다.When exposing and developing the said photosensitive layer, the minimum energy of the light used for the said exposure which does not change the thickness of the part which exposes the said photosensitive layer after the said exposure and image development is 0.1-100 (mJ / cm <2> ). It is preferable that it is and it is more preferable that it is 1-80mJ / cm <2> . If the minimum energy of light used for the exposure is less than 0.1mJ / cm 2, and if the machining margin is narrowed, if it exceeds 100mJ / cm 2, it is not preferable since a long tact time.
여기서, 「상기 감광층의 노광하는 부분의 두께를, 상기 노광 및 현상 후에 있어서 변화시키지 않는 상기 노광에 사용하는 광의 최소 에너지 」란, 소위 현상 감도이고, 예를 들면 상기 감광층을 노광했을 때의 상기 노광에 사용한 광의 에너지량(노광량)과 상기 노광에 연속된 상기 현상 처리에 의해 생성된 상기 경화층의 두께의 관계를 나타내는 그래프(감도 곡선)로부터 구할 수 있다.Here, "the minimum energy of the light used for the said exposure which does not change the thickness of the part which exposes the said photosensitive layer after the said exposure and image development" is what is called image development sensitivity, for example, when the said photosensitive layer is exposed, It can obtain | require from the graph (sensitivity curve) which shows the relationship between the energy amount (exposure amount) of the light used for the said exposure, and the thickness of the said hardened layer produced | generated by the said developing process continued to the said exposure.
상기 경화층의 두께는 상기 노광량이 증가하는데 따라서 증가해 가고, 그 후에 상기 노광전의 상기 감광층의 두께와 대략 동일하면서 일정하게 된다. 상기 현상 감도는 상기 경화층의 두께가 대략 일정하게 되었을 때의 최소 노광량을 판독함으로써 구해지는 값이다.The thickness of the cured layer increases as the exposure amount increases, and then becomes constant while being substantially equal to the thickness of the photosensitive layer before the exposure. The said developing sensitivity is a value calculated | required by reading the minimum exposure amount when the thickness of the said hardened layer becomes substantially constant.
여기서, 상기 경화층의 두께와 상기 노광전의 상기 감광층의 두께의 차가 ±1㎛이내일 때, 상기 경화층의 두께가 노광 및 현상에 의해 변화되지 않고 있다고 간주한다.Here, when the difference between the thickness of the cured layer and the thickness of the photosensitive layer before the exposure is within ± 1 μm, it is considered that the thickness of the cured layer is not changed by exposure and development.
상기 경화층 및 상기 노광전의 상기 감광층의 두께의 측정 방법으로서는, 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있지만, 막두께 측정 장치, 표면 조도 측정기(예를 들면, 서프컴 1400D(도쿄정밀사 제작)) 등을 사용하여 측정하는 방법이 열거된다.There is no restriction | limiting in particular as a measuring method of the thickness of the said hardened layer and the said photosensitive layer before the exposure, Although it can select suitably according to the objective, A film thickness measuring apparatus and a surface roughness measuring instrument (for example, Surfcom 1400D (Tokyo Precision) The method of measurement using the company make) is mentioned.
상기 감광층의 두께로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있지만, 예를 들면 3∼100㎛가 바람직하고, 5∼70㎛가 보다 바람직하다.There is no restriction | limiting in particular as thickness of the said photosensitive layer, Although it can select suitably according to the objective, For example, 3-100 micrometers is preferable and 5-70 micrometers is more preferable.
상기 감광층의 형성 방법으로서는 상기 지지체 상에, 본 발명의 상기 감광성 조성물을 물 또는 용제에 용해, 유화 또는 분산시켜 감광성 조성물 용액을 조제하고, 상기 용액을 직접 도포하고, 건조시킴으로써 적층하는 방법이 열거된다.As a formation method of the said photosensitive layer, the method of laminating | stacking by preparing the photosensitive composition solution by dissolving, emulsifying, or disperse | distributing the said photosensitive composition of this invention in water or a solvent on the said support body, apply | coating the said solution directly, and enumerating are listed do.
상기 감광성 조성물 용액의 용제로서는, 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있고, 예를 들면 메탄올, 에탄올, n-프로판올, 이소프로판올, n-부탄올, sec-부탄올, n-헥사놀 등의 알콜류; 아세톤, 메틸에틸케톤, 메틸이소부틸케톤, 시클로헥사논, 디이소부틸케톤 등의 케톤류; 아세트산 에틸, 아세트산 부틸, 아세트산-n-아밀, 황산 메틸, 프로피온산 에틸, 프탈산 디메틸, 벤조산 에틸 및 메톡시프로필아세테이트 등의 에스테르류; 톨루엔, 크실렌, 벤젠, 에틸벤젠 등의 방향족 탄화수소류; 사염화탄소, 트리클로로에틸렌, 클로로포름, 1,1,1-트리클로로에탄, 염화메틸렌, 모노클로로벤젠 등의 할로겐화 탄화수소류; 테트라히드로푸 란, 디에틸에테르, 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 1-메톡시-2-프로판올 등의 에테르류; 디메틸포름아미드, 디메틸아세트아미드, 디메틸술포옥시드, 술포란 등이 열거된다. 이들은 1종 단독으로 사용해도 좋고, 2종 이상을 병용해도 좋다. 또한, 공지의 계면활성제를 첨가해도 좋다.There is no restriction | limiting in particular as a solvent of the said photosensitive composition solution, According to the objective, it can select suitably, For example, alcohol, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol ; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and diisobutyl ketone; Esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate and methoxypropyl acetate; Aromatic hydrocarbons such as toluene, xylene, benzene and ethylbenzene; Halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride and monochlorobenzene; Ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and 1-methoxy-2-propanol; Dimethylformamide, dimethylacetamide, dimethylsulfooxide, sulfolane and the like. These may be used individually by 1 type and may use 2 or more types together. Moreover, you may add a well-known surfactant.
상기 도포의 방법으로서는, 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있고, 예를 들면, 스핀 코터, 슬릿 스핀 코터, 롤 코터, 다이 코터, 커튼 코터 등을 사용하여, 상기 지지체에 직접 도포하는 방법이 열거된다.There is no restriction | limiting in particular as said coating method, According to the objective, it can select suitably, For example, apply | coating directly to the said support body using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, etc. The method is listed.
상기 건조의 조건으로서는 각 성분, 용매의 종류, 사용 비율 등에 의해서도 달라지지만, 통상 60∼110℃의 온도에서 30초간∼15분간정도이다.As said drying conditions, although it changes also with each component, a kind of solvent, a use ratio, etc., it is about 30 to 15 minutes normally at the temperature of 60-110 degreeC.
[지지체][Support]
상기 지지체로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있지만, 상기 감광층을 박리가능하고, 또한 광의 투과성이 양호한 것이 바람직하고, 또한 표면의 평활성이 양호한 것이 보다 바람직하다.There is no restriction | limiting in particular as said support body, Although it can select suitably according to the objective, it is preferable that the said photosensitive layer is peelable, and that light transmittance is favorable, and that surface smoothness is more preferable.
상기 지지체는 합성 수지제이고, 또한 투명한 것이 바람직하고, 예를 들면 폴리에틸렌테레프탈레이트, 폴리에틸렌나프탈레이트, 폴리프로필렌, 폴리에틸렌, 3아세트산 셀룰로오스, 2아세트산 셀룰로오스, 폴리(메타)아크릴산 알킬에스테르, 폴리(메타)아크릴산 에스테르 공중합체, 폴리염화비닐, 폴리비닐알콜, 폴리카보네이트, 폴리스티렌, 셀로판, 폴리염화비닐리덴 공중합체, 폴리아미드, 폴리이미드, 염화비닐·아세트산 비닐공중합체, 폴리테트라플루오로에틸렌, 폴리트리플루오로에틸렌, 셀룰로오스계 필름, 나일론 필름 등의 각종의 플라스틱 필름이 열거되고, 이 들 중에서도 폴리에틸렌테레프탈레이트가 특히 바람직하다. 이들은 1종 단독으로 사용해도 좋고, 2종 이상을 병용해도 좋다.The support is made of synthetic resin and is preferably transparent. For example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly (meth) Acrylic ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoro Various plastic films, such as a low ethylene, a cellulose film, and a nylon film, are mentioned, Among these, polyethylene terephthalate is especially preferable. These may be used individually by 1 type and may use 2 or more types together.
또한, 상기 지지체로서는 예를 들면, 일본특허공개 평4-208940호 공보, 일본특허공개 평5-80503호 공보, 일본특허공개 평5-173320호 공보, 일본특허공개 평5-72724호 공보 등에 기재된 지지체를 사용할 수 있다.Moreover, as said support body, it is described, for example in Unexamined-Japanese-Patent No. 4-208940, Unexamined-Japanese-Patent No. 5-80503, Unexamined-Japanese-Patent No. 5-173320, Unexamined-Japanese-Patent No. 5-72724, etc., for example. Supports can be used.
상기 지지체의 두께로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있지만, 예를 들면 4∼300㎛가 바람직하고, 5∼175㎛가 보다 바람직하다.There is no restriction | limiting in particular as thickness of the said support body, Although it can select suitably according to the objective, For example, 4-300 micrometers is preferable and 5-175 micrometers is more preferable.
상기 지지체의 형상으로서는, 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있지만, 장척상이 바람직하다. 상기 장척상의 지지체의 길이로서는, 특별히 제한은 없고, 예를 들면 10m∼20,000m의 길이의 것이 열거된다.There is no restriction | limiting in particular as a shape of the said support body, Although it can select suitably according to the objective, the elongate phase is preferable. There is no restriction | limiting in particular as length of the said elongate support body, For example, the thing of length 10m-20,000m is mentioned.
[보호 필름][Protective film]
상기 보호 필름은 상기 감광층의 오염이나 손상을 방지하고, 보호하는 기능을 갖는다.The protective film has a function of preventing and protecting contamination or damage of the photosensitive layer.
상기 보호 필름의 상기 감광성 필름에 있어서 형성되는 개소로서는 특별하게 한정은 없고, 목적에 따라서 적당하게 선택할 수 있지만, 통상 상기 감광층상에 형성된다.There is no restriction | limiting in particular as a location formed in the said photosensitive film of the said protective film, Although it can select suitably according to the objective, it is normally formed on the said photosensitive layer.
상기 보호 필름으로서는 예를 들면, 상기 지지체에 사용되는 것, 실리콘 종이, 폴리에틸렌, 폴리프로필렌이 라미네이트된 종이, 폴리올레핀 또는 폴리테트라플루오로에틸렌 시트 등이 열거되고, 이들 중에서도 폴리에틸렌 필름, 폴리프로필렌 필름이 바람직하다.As said protective film, what is used for the said support | support, for example, the silicone paper, polyethylene, the paper laminated with polypropylene, a polyolefin or a polytetrafluoroethylene sheet, etc. are mentioned, Among these, a polyethylene film and a polypropylene film are preferable. Do.
상기 보호 필름의 두께로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있지만, 예를 들면 5∼100㎛가 바람직하고, 8∼30㎛가 보다 바람직하다.There is no restriction | limiting in particular as thickness of the said protective film, Although it can select suitably according to the objective, For example, 5-100 micrometers is preferable and 8-30 micrometers is more preferable.
상기 보호 필름을 사용할 경우, 상기 감광층 및 상기 지지체의 접착력 A와 상기 감광층 및 보호 필름의 접착력 B가 접착력 A > 접착력 B의 관계인 것이 바람직하다.When using the said protective film, it is preferable that the adhesive force A of the said photosensitive layer and said support body, and the adhesive force B of the said photosensitive layer and protective film are the relationship of adhesive force A> adhesive force B.
상기 지지체와 보호 필름의 조합(지지체/보호 필름)으로서는 예를 들면, 폴리에틸렌테레프탈레이트/폴리프로필렌, 폴리에틸렌테레프탈레이트/폴리에틸렌, 폴리염화비닐/셀로판, 폴리이미드/폴리프로필렌, 폴리에틸렌테레프탈레이트/폴리에틸렌테레프탈레이트 등이 열거된다. 또한, 지지체 및 보호 필름 중 적어도 어느 하나를 표면 처리함으로써, 상술한 바와 같은 접착력의 관계를 만족시킬 수 있다. 상기 지지체의 표면처리는 상기 감광층과의 접착력을 높이기 위해서 실시되어도 좋고, 예를 들면 언더코트층의 도포, 코로나 방전 처리, 화염 처리, 자외선 조사 처리, 고주파 조사 처리, 글로우 방전 조사 처리, 활성 플라즈마 조사 처리, 레이저 광선조사 처리 등을 들 수 있다.As a combination (support / protective film) of the said support body and a protective film, it is polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, for example. And the like. In addition, by surface-treating at least any one of a support body and a protective film, the relationship of the adhesive force mentioned above can be satisfied. The surface treatment of the support may be carried out in order to increase the adhesion with the photosensitive layer, and for example, application of an undercoat layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow discharge irradiation treatment, active plasma Irradiation treatment, laser beam irradiation treatment, and the like.
또한, 상기 지지체와 상기 보호 필름의 정마찰 계수로서는 0.3∼1.4가 바람직하고, 0.5∼1.2가 보다 바람직하다.Moreover, as a static friction coefficient of the said support body and the said protective film, 0.3-1.4 are preferable and 0.5-1.2 are more preferable.
상기 정마찰 계수가 0.3미만이면, 지나치게 미끄럽기 때문에, 롤상으로 했을 경우에 권취 어긋남이 발생하는 경우가 있고, 1.4을 초과하면, 양호한 롤상으로 권취하는 것이 곤란하게 되는 경우가 있다.When the said static friction coefficient is less than 0.3, it is too slippery, and when it makes into a roll shape, winding shift may generate | occur | produce, and when it exceeds 1.4, it may become difficult to wind up to a favorable roll shape.
상기 감광성 필름은 예를 들면, 원통상의 권심에 권취하고, 장척상으로 롤상 으로 권취되어 보관되는 것이 바람직하다. 상기 장척상의 감광성 필름의 길이로서는, 특별히 제한은 없고, 예를 들면 10∼20,000m의 범위로부터 적당하게 선택할 수 있다. 또한, 유저가 사용하기 쉽도록 슬릿 가공하고, 100∼1,000m의 범위의 장척체를 롤상으로 하여도 좋다. 또, 이 경우에는 상기 지지체가 가장 외측이 되도록 권취하는 것이 바람직하다. 또한, 상기 롤상의 감광성 필름을 시트상으로 슬릿해도 좋다. 보관 시, 가장자리면의 보호, 엣지 퓨전(fusion)을 방지하는 관점으로부터, 가장자리면에는 세퍼레이터(특히, 방습성의 것, 건조제 함유의 것)를 설치하는 것이 바람직하고, 또 곤포는 투습성이 낮은 소재를 사용하는 것이 바람직하다.It is preferable that the said photosensitive film is wound by the cylindrical core, for example, is wound up in the shape of a roll in the shape of a long picture, and is stored. There is no restriction | limiting in particular as length of the said elongate photosensitive film, For example, it can select suitably from the range of 10-20,000m. Moreover, you may slit process so that a user may use it, and you may make the elongate body of the range of 100-1,000m into roll shape. Moreover, in this case, it is preferable to wind up so that the said support body may become outermost. Moreover, you may slit the said roll-shaped photosensitive film in a sheet form. In storage, it is preferable to install a separator (especially moisture-proof and desiccant-containing) on the edge surface from the viewpoint of protecting the edge surface and preventing edge fusion. It is preferable to use.
상기 보호 필름은 상기 보호 필름과 상기 감광층의 접착성을 조정하기 위해서 표면 처리해도 좋다. 상기 표면 처리는 예를 들면, 상기 보호 필름의 표면에 폴리오르가노실록산, 불소화 폴리올레핀, 폴리플루오로에틸렌, 폴리비닐알콜 등의 폴리머로 이루어지는 언더코트층을 형성한다. 상기 언더코트의 형성은 상기 폴리머의 도포액을 상기 보호 필름의 표면에 도포한 후, 30∼150℃(특히, 50∼120℃)에서 1∼30분간 건조시킴으로써 형성할 수 있다.You may surface-treat the said protective film in order to adjust the adhesiveness of the said protective film and the said photosensitive layer. The said surface treatment forms the undercoat layer which consists of polymers, such as a polyorganosiloxane, a fluorinated polyolefin, polyfluoroethylene, polyvinyl alcohol, on the surface of the said protective film, for example. The undercoat can be formed by applying the polymer coating liquid to the surface of the protective film and then drying at 30 to 150 ° C (in particular, 50 to 120 ° C) for 1 to 30 minutes.
또한, 상기 감광층, 상기 지지체, 상기 보호 필름 이외에, 쿠션층, 산소 차단층(PC층), 박리층, 접착층, 광흡수층, 표면 보호층 등의 층을 가져도 좋다.Moreover, in addition to the said photosensitive layer, the said support body, and the said protective film, you may have layers, such as a cushion layer, an oxygen barrier layer (PC layer), a peeling layer, an adhesive layer, a light absorption layer, and a surface protective layer.
상기 쿠션층은 상온에서는 택성이 없고, 진공 및 가열 조건에서 적층했을 경우에 용융하고, 유동하는 층이다.The cushion layer is a layer which does not have tackiness at normal temperature and melts and flows when laminated under vacuum and heating conditions.
상기 PC층은 통상, 폴리비닐알콜을 주성분으로 하여 형성된 0.5∼5㎛정도의 피막이다.The said PC layer is a film of about 0.5-5 micrometers normally formed using polyvinyl alcohol as a main component.
본 발명의 감광성 필름은 표면의 택성이 작고, 라미네이트성 및 취급성이 양호하고, 보존 안정성이 우수하고, 고감도이며 현상성도 우수하고, 현상 후에 우수한 내약품성, 표면 경도, 내열성, 유전 특성 등을 발현하는 감광성 조성물이 적층된 감광층을 포함하여 이루어진다. 이 때문에, 프린트 배선판, 컬러 필터나 골재, 리브재, 스페이서, 격벽 등의 디스플레이용 부재, 홀로그램, 마이크로 머신, 프루프 등의 영구 패턴 형성용으로서 널리 사용할 수 있고, 본 발명의 영구 패턴 및 그 형성 방법에 바람직하게 사용할 수 있다.The photosensitive film of the present invention has small surface tack, good lamination and handling properties, excellent storage stability, high sensitivity and developability, and exhibits excellent chemical resistance, surface hardness, heat resistance, dielectric properties, and the like after development. It comprises a photosensitive layer in which the photosensitive composition is laminated. For this reason, it can be widely used for forming permanent patterns, such as a printed wiring board, a color filter, aggregate, a rib material, a spacer, a partition, a display member, a hologram, a micromachine, a proof, etc., The permanent pattern of this invention, and its formation method It can be used preferably.
특히, 본 발명의 감광성 필름은 상기 필름의 두께가 균일하기 때문에, 영구 패턴의 형성시에, 기재로의 적층이 보다 세밀하게 행하여진다.In particular, in the photosensitive film of the present invention, since the thickness of the film is uniform, lamination to the substrate is performed more precisely at the time of forming the permanent pattern.
(영구 패턴 및 영구 패턴 형성 방법)(Permanent pattern and permanent pattern formation method)
본 발명의 영구 패턴은 본 발명의 영구 패턴 형성 방법에 의해 얻어진다.The permanent pattern of this invention is obtained by the permanent pattern formation method of this invention.
본 발명의 영구 패턴 형성 방법은 제 1 형태로서, 본 발명의 감광성 조성물을 기재의 표면에 도포하고, 건조하여 감광층을 형성한 후, 노광하고, 현상하고, 가열한다.The permanent pattern formation method of this invention is a 1st aspect, apply | coats the photosensitive composition of this invention to the surface of a base material, and after drying and forming a photosensitive layer, it exposes, develops, and heats.
또한, 본 발명의 영구 패턴 형성 방법은 제 2 형태로서, 본 발명의 감광성 필름을 가열 및 가압 중 적어도 어느 하나의 하에 있어서 기재의 표면에 적층한 후, 노광하고, 현상하고, 가열한다.Moreover, the permanent pattern formation method of this invention is a 2nd aspect, after laminating | stacking the photosensitive film of this invention on the surface of a base material under at least one of heating and pressurization, it exposes, develops, and heats.
이하, 본 발명의 영구 패턴 형성 방법의 설명을 통해서, 본 발명의 영구 패턴의 상세도 명백하게 된다.Hereinafter, the detail of the permanent pattern of this invention becomes clear through description of the permanent pattern formation method of this invention.
[기재][materials]
상기 기재로서는 특별히 제한은 없고, 공지의 재료 중에서 표면 평활성이 높은 것으로부터 요철이 있는 표면을 갖는 것까지 적당하게 선택할 수 있고, 판상의 기재(기판)가 바람직하고, 구체적으로는 공지의 프린트 배선판 형성용 기판(예를 들면, 동장 적층판), 유리판(예를 들면, 소다 유리판 등), 합성 수지성의 필름, 종이, 금속판 등이 열거되지만, 이들 중에서도 프린트 배선판 형성용 기판이 바람직하고, 다층배선기판이나 빌드업 배선기판 등으로의 반도체 등의 고밀도 실장화가 가능해 지는 점에서, 상기 프린트 배선판 형성용 기판이 배선 형성 완료인 것이 특히 바람직하다.There is no restriction | limiting in particular as said base material, From a well-known material, it can select suitably from the thing with high surface smoothness to the surface with an unevenness, A plate-shaped base material (substrate) is preferable, Specifically, well-known printed wiring board formation Substrates for use (e.g. copper clad laminates), glass plates (e.g., soda glass plates, etc.), synthetic resin films, papers, metal plates and the like are listed. Among these, printed wiring board forming substrates are preferred, and multilayer wiring boards are preferred. It is particularly preferable that the printed wiring board forming substrate is complete with wiring in that high density mounting of a semiconductor or the like into a buildup wiring board or the like becomes possible.
상기 기재는 상기 제 1 형태로서, 상기 기재 상에 상기 감광성 조성물에 의한 감광층이 형성되어서 이루어지는 적층체, 또는 상기 제 2 형태로서, 상기 감광성 필름에 있어서의 감광층이 중첩되도록 하여 적층되어 이루어지는 적층체를 형성해서 사용할 수 있다. 즉, 상기 적층체에 있어서의 상기 감광층에 대하여 후술하는, 노광함으로써 노광한 영역을 경화시켜, 후술하는 현상에 의해 영구 패턴을 형성할 수 있다.The said base material is a laminated body by which the photosensitive layer by the said photosensitive composition is formed on the said base material as said 1st form, or laminated | stacked by laminating | stacking so that the photosensitive layer in the said photosensitive film may overlap as said 2nd aspect. A sieve can be formed and used. That is, the exposed area which is mentioned later with respect to the said photosensitive layer in the said laminated body can be hardened | cured, and a permanent pattern can be formed by the phenomenon mentioned later.
-적층체-Laminate
상기 제 1 형태의 적층체의 형성 방법으로서는, 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있지만, 상기 기재 상에 상기 감광성 조성물을 도포 및 건조해서 형성한 감광층을 적층하는 것이 바람직하다.There is no restriction | limiting in particular as a formation method of the said 1st aspect, Although it can select suitably according to the objective, It is preferable to laminate | stack the photosensitive layer formed by apply | coating and drying the said photosensitive composition on the said base material.
상기 도포 및 건조의 방법으로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있고, 예를 들면, 상기 감광성 필름에 있어서의 감광층을 형성할 때에 행하여지는 상기 감광성 조성물 용액의 도포 및 건조와 동일한 방법으로 행할 수 있고, 예를 들면, 상기 감광성 조성물 용액을 스핀 코터, 슬릿 스핀 코터, 롤 코터, 다이 코터, 커튼 코터 등을 이용하여 도포하는 방법이 열거된다.There is no restriction | limiting in particular as said coating and drying method, According to the objective, it can select suitably, For example, the method similar to the coating and drying of the said photosensitive composition solution performed when forming the photosensitive layer in the said photosensitive film. The method of apply | coating the said photosensitive composition solution using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, etc. is mentioned, for example.
상기 제 2 형태의 적층체의 형성 방법으로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있지만, 상기 기재 상에 상기 감광성 필름을 가열 및 가압 중 적어도 어느 하나를 행하면서 적층하는 것이 바람직하다. 또, 상기 감광성 필름이 상기 보호 필름을 가질 경우에는, 상기 보호 필름을 박리하고, 상기 기재에 상기 감광층이 중첩되도록 하여 적층하는 것이 바람직하다.There is no restriction | limiting in particular as a formation method of the said 2nd aspect, Although it can select suitably according to the objective, It is preferable to laminate | stack the said photosensitive film on the said base material, performing at least any one of heating and pressurization. Moreover, when the said photosensitive film has the said protective film, it is preferable to peel off the said protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base material.
상기 가열 온도로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있지만, 예를 들면 70∼130℃가 바람직하게, 80∼110℃가 보다 바람직하다.There is no restriction | limiting in particular as said heating temperature, Although it can select suitably according to the objective, For example, 70-130 degreeC is preferable and 80-110 degreeC is more preferable.
상기 가압의 압력으로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있지만, 예를 들면, 0.01∼1.0MPa가 바람직하고, 0.05∼1.0MPa가 보다 바람직하다.There is no restriction | limiting in particular as a pressure of the said pressurization, Although it can select suitably according to the objective, For example, 0.01-1.0 MPa is preferable and 0.05-1.0 MPa is more preferable.
상기 가열 및 가압 중 적어도 어느 하나를 행하는 장치로서는, 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있고, 예를 들면 히트 프레스, 히트 롤 라미네이터(예를 들면, 대성 라미네이터사 제작, VP-II), 진공 라미네이터(예를 들면, 명기제작소 제작, MVLP 500) 등이 적합하게 열거된다.There is no restriction | limiting in particular as an apparatus which performs at least any of the said heating and pressurization, According to the objective, it can select suitably, For example, a heat press and a heat roll laminator (for example, Daesung Laminator Co., VP-II) , Vacuum laminators (eg, MKLP, MVLP 500) and the like are suitable.
[노광 공정]Exposure process
상기 노광 공정은 상기 감광층에 대하여, 노광을 행하는 공정이다.The exposure step is a step of exposing the photosensitive layer.
상기 노광의 대상으로서는 감광층을 갖는 재료인 한, 특별한 제한은 없고, 목적에 따라서 적당하게 선택할 수 있지만, 예를 들면, 기재 상에 상기 감광성 조성물 또는 상기 감광성 필름이 형성되어서 이루어지는 상기 적층체에 대하여 행하여지는 것이 바람직하다.As long as it is a material which has a photosensitive layer as an object of the said exposure, there is no restriction | limiting in particular and it can select suitably according to the objective, For example, with respect to the said laminated body in which the said photosensitive composition or the said photosensitive film is formed on a base material, It is preferable to be done.
상기 적층체로의 노광으로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있고, 예를 들면, 상기 지지체, 쿠션층 및 PC층을 통하여 상기 감광층을 노광해도 좋고, 상기 지지체를 박리한 후, 상기 쿠션층 및 PC층을 통하여 상기 감광층을 노광해도 좋고, 상기 지지체 및 쿠션층을 박리한 후, 상기 PC층을 통하여 상기 감광층을 노광해도 좋고, 상기 지지체, 쿠션층 및 PC층을 박리한 후, 상기 감광층을 노광해도 좋다.There is no restriction | limiting in particular as exposure to the said laminated body, According to the objective, it can select suitably, For example, you may expose the said photosensitive layer through the said support body, a cushion layer, and a PC layer, and after peeling the said support body, After exposing the said photosensitive layer through a cushion layer and a PC layer, after peeling the said support body and a cushion layer, you may expose the said photosensitive layer through the said PC layer, after peeling the said support body, a cushion layer, and a PC layer You may expose the said photosensitive layer.
상기 노광으로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있고, 디지털 노광, 아날로그 노광 등이 열거되지만, 이들 중에서도 디지털 노광이 바람직하다.There is no restriction | limiting in particular as said exposure, According to the objective, it can select suitably, Digital exposure, analog exposure, etc. are enumerated, Among these, digital exposure is preferable.
상기 디지털 노광으로서는, 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있지만, 예를 들면, 형성하는 패턴 형성 정보에 기초하여 제어 신호를 생성하고, 상기 제어 신호에 따라 변조시킨 광을 사용하여 행하는 것이 바람직하다.There is no restriction | limiting in particular as said digital exposure, Although it can select suitably according to the objective, For example, to generate a control signal based on the pattern formation information to form, and to perform it using the light modulated according to the said control signal desirable.
상기 디지털 노광의 수단으로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있고, 예를 들면 광을 조사하는 광조사 수단, 형성하는 패턴 정보 에 기초하여 상기 광조사 수단으로부터 조사되는 광을 변조시키는 광변조 수단 등이 열거된다.There is no restriction | limiting in particular as said means of digital exposure, According to the objective, it can select suitably, For example, the light which modulates the light irradiated from the said light irradiation means based on pattern information to form, Modulation means and the like.
<광변조 수단><Optical Modulation Means>
상기 광변조 수단으로서는 광을 변조할 수 있는 한, 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있지만, 예를 들면 n개의 묘소부를 갖는 것이 바람직하다.There is no restriction | limiting in particular as long as it can modulate light as said optical modulation means, Although it can select suitably according to the objective, For example, it is preferable to have n drawing parts.
상기 n개의 묘소부를 갖는 광변조 수단으로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있지만, 예를 들면 공간 광변조 소자가 바람직하다.There is no restriction | limiting in particular as an optical modulation means which has the said n drawing parts, Although it can select suitably according to the objective, For example, a spatial light modulation element is preferable.
상기 공간 광변조 소자로서는 예를 들면, 디지털·마이크로 미러·디바이스(DMD), MEMS(Micro Electro Mechanical Systems) 타입의 공간 광변조 소자(SLM; Special Light Modulator), 전기 광학 효과에 의해 투과광을 변조하는 광학 소자(PLZT 소자), 액정광 셔터(FLC) 등이 열거되고, 이들 중에서도 DMD가 바람직하게 열거된다.Examples of the spatial light modulator include digital micro mirror devices (DMD), MEMS (Micro Electro Mechanical Systems) type spatial light modulators (SLM; Special Light Modulator), and modulated transmitted light by electro-optic effects. Optical element (PLZT element), liquid crystal light shutter (FLC), etc. are mentioned, DMD is mentioned preferably among these.
또한, 상기 광변조 수단은 형성하는 패턴 정보에 기초하여 제어 신호를 생성하는 패턴 신호 생성 수단을 갖는 것이 바람직하다. 이 경우, 상기 광변조 수단은 상기 패턴 신호 생성 수단이 생성한 제어 신호에 따라 광을 변조시킨다.It is also preferable that the light modulating means has a pattern signal generating means for generating a control signal based on the pattern information to be formed. In this case, the light modulating means modulates light according to the control signal generated by the pattern signal generating means.
상기 제어 신호로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있고, 예를 들면 디지털 신호가 바람직하게 열거된다.There is no restriction | limiting in particular as said control signal, According to the objective, it can select suitably, For example, a digital signal is mentioned preferably.
상기 광변조 수단의 구체예로서는 일본특허공개 2005-258431호 공보의 [0016]∼[0047]에 기재되어 있는 수단 등이 열거된다.As a specific example of the said optical modulation means, the means etc. which are described in [0016]-[0047] of Unexamined-Japanese-Patent No. 2005-258431 are mentioned.
-광조사 수단-Light irradiation means
상기 광조사 수단으로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있고, 예를 들면 (초)고압 수은 등, 크세논 등, 카본 아크 등, 할로겐 램 프, 복사기용 등의 형광관, LED, 반도체 레이저 등의 공지의 광원 또는 2개 이상의 광을 합성해서 조사 가능한 수단이 열거되고, 이들 중에서도 2개 이상의 광을 합성해서 조사 가능한 수단이 바람직하다.There is no restriction | limiting in particular as said light irradiation means, According to the objective, it can select suitably, For example, (super) high pressure mercury, xenon, etc., carbon arcs, halogen lamps, copiers, fluorescent tubes, LED, a semiconductor, etc. Known light sources, such as a laser, or the means which can irradiate by combining 2 or more lights are mentioned, Among these, the means which can irradiate by combining 2 or more lights are preferable.
상기 광조사 수단으로부터 조사되는 광으로서는 예를 들면, 지지체를 통하여 광조사를 행할 경우에는, 상기 지지체를 투과하고, 또한 사용되는 광중합 개시제나 증감제를 활성화하는 전자파, 자외로부터 가시 광선, 전자선, X선, 레이저광 등이 열거되고, 이들 중에서도 레이저광이 바람직하고, 2개 이상의 광을 합성한 레이저광(이하, 「합파 레이저광」이라고 하는 경우가 있음)이 보다 바람직하다. 또, 지지체를 박리하고나서 광조사를 행하는 경우에도, 동일한 광을 사용할 수 있다.As the light irradiated from the light irradiation means, for example, when light irradiation is carried out through a support, electromagnetic waves that transmit the support and activate the photopolymerization initiator and the sensitizer used, visible light from the ultraviolet ray, electron beam, X A line, a laser beam, etc. are enumerated, Among these, a laser beam is preferable and the laser beam which synthesize | combined two or more lights (henceforth "mold wave laser beam") is more preferable. Moreover, even when light irradiation is performed after peeling a support body, the same light can be used.
상기 자외로부터 가시 광선의 파장으로서는 예를 들면, 300∼1,500nm가 바람직하고, 320∼800nm가 보다 바람직하고, 330nm∼650nm가 특히 바람직하다.As said ultraviolet-ray wavelength of visible light, 300-1500 nm is preferable, 320-800 nm is more preferable, 330 nm-650 nm are especially preferable.
상기 레이저광의 파장으로서는 예를 들면, 200∼1,500nm이 바람직하고, 300∼800nm가 보다 바람직하고, 330nm∼500nm가 더욱 바람직하고, 395nm∼415nm가 특히 바람직하다.As a wavelength of the said laser beam, 200-1,500 nm is preferable, 300-800 nm is more preferable, 330 nm-500 nm are still more preferable, 395 nm-415 nm are especially preferable.
상기 합파 레이저광을 조사 가능한 수단으로서는 예를 들면, 복수의 레이저와 멀티 모드 광파이버와 상기 복수의 레이저로부터 각각 조사된 레이저광을 수광하여 상기 멀티 모드 광파이버에 결합시키는 집합 광학계를 갖는 수단이 바람직하다.As means capable of irradiating the haptic laser light, for example, a means having a plurality of lasers, a multi-mode optical fiber, and a collective optical system for receiving the laser light irradiated from the plurality of lasers and coupling the multi-mode optical fiber to the multi-mode optical fiber is preferable.
상기 합파 레이저를 조사가능한 수단(파이버 어레이 광원)로서는 예를 들면, 일본특허공개 2005-316431호 공보의 단락번호[0130]∼[0177]에 기재되어 있는 수단 등이 열거된다.As a means (fiber array light source) which can irradiate the said haptic laser, the means described in Paragraph No. [0130]-[0177] of Unexamined-Japanese-Patent No. 2005-316431, etc. are mentioned, for example.
<마이크로렌즈 어레이><Microlens Array>
또한, 상기 노광은 상기 변조시킨 광을 마이크로렌즈 어레이를 통하여 행하는 것이 바람직하고, 또한 애퍼쳐 어레이, 결상 광학계 등을 통하여 행해도 좋다.The exposure is preferably performed through the microlens array and may be performed through an aperture array, an imaging optical system, or the like.
상기 마이크로렌즈 어레이로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있지만, 예를 들면 상기 묘소부에 있어서의 출사면의 변형에 의한 수차를 보정 가능한 비구면을 갖는 마이크로 렌즈를 배열한 것이 바람직하게 열거된다.There is no restriction | limiting in particular as said microlens array, Although it can select suitably according to the objective, For example, what arrange | positioned the microlens which has an aspherical surface which can correct the aberration by the deformation of the exit surface in the said drawing part is preferable. do.
상기 비구면으로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있지만, 예를 들면 토릭면이 바람직하다.There is no restriction | limiting in particular as said aspherical surface, Although it can select suitably according to the objective, For example, a toric surface is preferable.
또한, 상기 마이크로렌즈 어레이, 상기 애퍼쳐 어레이, 및 상기 결상 광학계 등으로서는 예를 들면, 일본특허공개 2005-258431호 공보의 단락번호 [0051]∼[0063], 단락번호 [0065], 단락번호 [0070]∼[0073] 및 단락번호 [0083]∼[0088]에 기재되어 있는 수단 등이 열거된다.Further, as the microlens array, the aperture array, and the imaging optical system, for example, paragraph numbers [0051] to [0063], paragraph numbers [0065] of [Patent No. 2005-258431], and [ The means described in 0070]-[0073], paragraph numbers [0083]-[0088], etc. are mentioned.
<기타 광학계><Other optical system>
본 발명의 영구 패턴 형성 방법에서는 공지의 광학계 중에서 적당하게 선택된 기타 광학계와 병용해도 좋고, 예를 들면, 1대의 조합 렌즈로 이루어지는 광량 분포 보정 광학계 등이 열거된다.In the permanent pattern formation method of this invention, you may use together with the other optical system suitably selected from well-known optical systems, For example, the light quantity distribution correction optical system which consists of one combination lens, etc. are mentioned.
상기 광량 분포 보정 광학계로서는 구체적으로는 예를 들면, 일본특허공개2005-258431호 공보의 단락번호[0090]∼[0105]에 기재되어 있는 수단 등이 열거된 다.Specific examples of the light amount distribution correcting optical system include means described in, for example, paragraphs [0090] to [0105] of JP-A-2005-258431.
[현상 공정][Developing process]
상기 현상 공정은 상기 노광 공정에 의해 상기 감광층을 노광하고, 상기 감광층의 노광된 영역을 경화시킨 후, 미경화 영역을 제거함으로써 현상하여 영구 패턴을 형성하는 공정이다.The said developing process is a process of exposing the said photosensitive layer by the said exposure process, hardening the exposed area | region of the said photosensitive layer, and developing by removing a non-hardened area | region, and forming a permanent pattern.
상기 미경화 영역의 제거 방법으로서는, 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있고, 예를 들면, 현상액을 이용하여 제거하는 방법 등이 열거된다.There is no restriction | limiting in particular as a removal method of the said unhardened area | region, According to the objective, it can select suitably, For example, the method of removing using a developing solution, etc. are mentioned.
상기 현상액으로서는 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있지만, 예를 들면, 알칼리 금속 또는 알칼리 토류 금속의 수산화물, 또는 탄산염, 탄산수소염, 암모니아수, 4급 암모늄염의 수용액 등이 바람직하게 열거된다. 이들 중에서도, 탄산나트륨 수용액이 특히 바람직하다.There is no restriction | limiting in particular as said developing solution, Although it can select suitably according to the objective, For example, the hydroxide of alkali metal or alkaline-earth metal, or the carbonate, hydrogencarbonate, aqueous ammonia, the quaternary ammonium salt, etc. are mentioned preferably. Among these, an aqueous sodium carbonate solution is particularly preferable.
상기 현상액은 계면활성제, 소포제, 유기 염기(예를 들면, 벤질 아민, 에틸렌디아민, 에탄올아민, 테트라메틸암모늄 하이드록사이드, 디에틸렌트리아민, 트리 에틸렌펜타민, 몰포린, 트리에탄올아민 등)나, 현상을 촉진시키기 위해서 유기용제(예를 들면, 알콜류, 케톤류, 에스테르류, 에테르류, 아미드류, 락톤류 등)등과 병용해도 좋다. 또한, 상기 현상액은 물 또는 알칼리 수용액과 유기 용제를 혼합한 수계 현상액이라도 좋고, 유기 용제 단독이어도 좋다.The developing solution may be a surfactant, an antifoaming agent, an organic base (eg, benzyl amine, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.), In order to promote development, you may use together with an organic solvent (for example, alcohol, ketones, ester, ether, amide, lactone, etc.). The developer may be an aqueous developer in which water or an alkali aqueous solution and an organic solvent are mixed, or may be an organic solvent alone.
[경화 처리 공정]Curing Treatment Process
본 발명의 영구 패턴 형성 방법은 또한 경화 처리 공정으로서, 가열 처리를 포함하고, 또한 필요에 따라 전체면 노광 처리를 포함한다.The permanent pattern formation method of this invention also contains a heat processing as a hardening process process, and also includes a whole surface exposure process as needed.
상기 경화 처리 공정은 상기 현상 공정이 행하여진 후, 형성된 영구 패턴에 있어서의 감광층에 대하여 경화 처리를 행하는 공정이다.The said hardening process process is a process of performing hardening process with respect to the photosensitive layer in the permanent pattern formed after the said image development process is performed.
-가열 처리-Heating treatment
상기 가열 열처리는, 본 발명의 감광성 조성물에 함유되는 상기 일반식(1)∼(3)으로 나타내어지는 화합물의 열가교 효과에 의한 막경도의 충분한 향상을 꾀하기 위해서 행하는 것이다. 상기 가열 처리로서는 전체면 가열 처리이어도 좋고, 패턴상으로 가열 처리를 행하는 것이어도 좋고, 이 중에서도 전체면 가열 처리가 바람직하다.The said heat processing is performed in order to achieve sufficient improvement of the film hardness by the thermal crosslinking effect of the compound represented by the said General Formula (1)-(3) contained in the photosensitive composition of this invention. As said heat processing, whole surface heat processing may be sufficient, heat processing may be performed in a pattern form, and the whole surface heat processing is especially preferable.
전체면 가열 처리의 방법으로서는, 상기 현상 공정 후에, 상기 영구 패턴이 형성된 상기 적층체상의 전체면을 가열하는 방법이 열거된다. 상기 전체면 가열에 의해 상기 일반식(1)∼(3)으로 나타내어지는 화합물의 가교 반응이 촉진되고, 상기 영구 패턴의 표면의 막강도가 높아진다.As a method of whole surface heat processing, the method of heating the whole surface on the said laminated body in which the said permanent pattern was formed after the said image development process is mentioned. By whole surface heating, the crosslinking reaction of the compound represented by the said General formula (1)-(3) is accelerated | stimulated, and the film strength of the surface of the said permanent pattern becomes high.
상기 전체면 가열에 있어서의 가열 온도로서는 120∼250℃가 바람직하고, 120∼200℃가 보다 바람직하다. 상기 가열 온도가 120℃미만이면, 상기 일반식(1)∼(3)으로 나타내어지는 화합물에 의한 감광성 조성물 중의 수지의 가교 반응성이 저하하고, 가열 처리에 의한 막강도의 향상이 얻어지지 않는 경우가 있고, 250℃를 초과하면, 상기 감광성 조성물 중의 수지의 분해가 발생하고, 막품질이 약하여 무르게 되는 경우가 있다.As heating temperature in the said whole surface heating, 120-250 degreeC is preferable and 120-200 degreeC is more preferable. When the said heating temperature is less than 120 degreeC, the crosslinking reactivity of resin in the photosensitive composition by the compound represented by the said General formula (1)-(3) falls, and the improvement of the film strength by heat processing may not be obtained. When it exceeds 250 degreeC, decomposition | disassembly of resin in the said photosensitive composition generate | occur | produces, film quality may be weak, and it may become soft.
상기 전체면 가열에 있어서의 가열 시간으로서는 10∼120분이 바람직하고, 15∼60분이 보다 바람직하다.As heating time in the said whole surface heating, 10 to 120 minutes are preferable, and 15 to 60 minutes are more preferable.
상기 전체면 가열을 행하는 장치로서는 특별히 제한은 없고, 공지의 장치 중에서 목적에 따라서 적당하게 선택할 수 있고, 예를 들면, 드라이 오븐, 핫플레이트, IR히터 등이 열거된다.There is no restriction | limiting in particular as an apparatus which performs said whole surface heating, According to the objective, it can select suitably from a well-known apparatus, For example, a dry oven, a hotplate, an IR heater, etc. are mentioned.
-전체면 노광 처리-Full surface exposure treatment
상기 전면 노광 처리의 방법으로서는 예를 들면, 상기 현상 공정 후에, 상기영구 패턴이 형성된 상기 적층체상의 전체면을 노광하는 방법이 열거된다. 상기 전체면 노광에 의해, 상기 감광층을 형성하는 감광성 조성물 중의 수지의 경화가 촉진되어, 상기 영구 패턴의 표면이 경화된다.As a method of the said front surface exposure process, the method of exposing the whole surface on the said laminated body in which the said permanent pattern was formed after the said image development process is mentioned, for example. By said whole surface exposure, hardening of resin in the photosensitive composition which forms the said photosensitive layer is accelerated | stimulated, and the surface of the said permanent pattern is hardened.
상기 전체면 노광을 행하는 장치로서는, 특별히 제한은 없고, 목적에 따라서 적당하게 선택할 수 있지만, 예를 들면 초고압 수은등 등의 UV노광기가 바람직하게 열거된다.There is no restriction | limiting in particular as an apparatus which performs said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned preferably.
또, 상기 기재가 다층 배선 기판 등의 프린트 배선판일 경우에는, 상기 프린트 배선판 상에 본 발명의 영구 패턴을 형성하고, 또한 이하와 같이 납땜을 행할 수 있다.Moreover, when the said base material is a printed wiring board, such as a multilayer wiring board, the permanent pattern of this invention can be formed on the said printed wiring board, and can be soldered as follows.
즉, 상기 현상 공정에 의해, 상기 영구 패턴인 경화층이 형성되고, 상기 프린트 배선판의 표면에 금속층이 노출된다. 상기 프린트 배선판의 표면에 노출된 금속층의 부위에 대하여 금도금을 행한 후, 납땜을 행한다. 그리고, 납땜을 행한 부위에, 반도체나 부품 등을 실장한다. 이 때, 상기 경화층에 의한 영구 패턴이 보호막 또는 절연막(층간 절연막)으로서의 기능을 발휘하고, 외부로부터의 충격이나 이 웃끼리의 전극의 도통이 방지된다.That is, by the said developing process, the hardened layer which is the said permanent pattern is formed, and a metal layer is exposed on the surface of the said printed wiring board. After plating with gold on the site | part of the metal layer exposed to the surface of the said printed wiring board, soldering is performed. And a semiconductor, a component, etc. are mounted in the soldered part. At this time, the permanent pattern by the said hardened layer functions as a protective film or an insulating film (interlayer insulation film), and the impact from the outside and the conduction of the electrodes of these neighbors are prevented.
본 발명의 영구 패턴 형성 방법에 있어서는 보호막, 층간 절연막 및 솔더 레지스트 패턴 중 적어도 어느 하나를 형성하는 것이 바람직하다. 상기 영구 패턴 형성 방법에 의해 형성되는 영구 패턴이 상기 보호막 또는 상기 층간 절연막이면, 배선을 외부로부터의 충격이나 구부러짐으로부터 보호될 수 있고, 특히, 상기 층간 절연막일 경우에는, 예를 들면 다층 배선 기판이나 빌드업 배선 기판 등으로의 반도체 부품의 고밀도 실장에 유용하다.In the permanent pattern formation method of this invention, it is preferable to form at least any one of a protective film, an interlayer insulation film, and a soldering resist pattern. If the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film, the wiring can be protected from impact or bending from the outside. In particular, in the case of the interlayer insulating film, for example, a multilayer wiring board It is useful for high-density mounting of semiconductor components to build-up wiring boards and the like.
본 발명의 영구 패턴 형성 방법은 고속으로 패턴 형성이 가능하기 때문에, 각종 패턴의 형성에 널리 사용할 수 있고, 특히 배선 패턴의 형성에 바람직하게 사용할 수 있다.Since the pattern formation method of the present invention can form a pattern at high speed, it can be widely used for formation of various patterns, and especially can be used for formation of a wiring pattern.
또한, 본 발명의 영구 패턴 형성 방법에 의해 형성되는 영구 패턴은 우수한 표면 경도, 절연성, 내열성 등을 갖고, 보호막, 층간 절연막 및 솔더 레지스트 패턴으로서 바람직하게 사용할 수 있다.Moreover, the permanent pattern formed by the permanent pattern formation method of this invention has the outstanding surface hardness, insulation, heat resistance, etc., and can be used suitably as a protective film, an interlayer insulation film, and a soldering resist pattern.
(실시예)(Example)
이하, 본 발명의 실시예에 관하여 설명하지만, 본 발명은 하기 실시예에 하등 한정되지 않는다.Hereinafter, although the Example of this invention is described, this invention is not limited to a following example at all.
(실시예 1) (Example 1)
-감광성 조성물의 조제-Preparation of Photosensitive Composition
하기 조성에 기초하여 감광성 조성물을 조제했다. 또, 분산 용매로서 메틸에틸케톤을 사용하고, 고형분 농도를 55질량%하여 조제했다. 분산은 비즈밀을 사용하 여 행하고, 얻어진 분산액은 입자 게이지에 의해 응집이 없는 것을 확인했다.The photosensitive composition was prepared based on the following composition. Moreover, methyl ethyl ketone was used as a dispersion solvent, and 55 mass% of solid content concentration was prepared. Dispersion was carried out using a bead mill, and it was confirmed that the obtained dispersion was free of aggregation by a particle gauge.
[감광성 조성물 용액의 조성][Composition of Photosensitive Composition Solution]
·황산 바륨(사카이 화학 공업사 제작, B30) 33.4질량부33.4 parts by mass of barium sulfate (manufactured by Sakai Chemical Co., Ltd., B30)
·하기 구조식(46)으로 나타내어지는 바인더 40.0질량부40.0 parts by mass of a binder represented by the following structural formula (46)
·상기 구조식(1)로 나타내어지는 화합물(열가교제) 15.7질량부15.7 parts by mass of the compound (thermal crosslinking agent) represented by the above structural formula (1)
·디펜타에리스톨헥사아크릴레이트 16.0질량부Dipentaerythritol hexaacrylate 16.0 parts by mass
·IRGACURE 819(치바·스페셜티·케미컬즈 제작) 5.8질량부IRGACURE 819 (Chiba Specialty Chemicals) 5.8 parts by mass
·하이드로퀴논 모노메틸에테르 0.056질량부0.056 parts by mass of hydroquinone monomethyl ether
·디시안디아미드 0.77질량부0.77 parts by mass of dicyandiamide
·2MAOK*1 0.47질량부2MAOK * 1 0.47 parts by mass
*1: 2MAOK는 하기 구조식(47)로 나타내어지는 2,4-디아미노-6-[2'-메틸이미다졸릴-(1')]-에틸-s-트리아진의 이소시아누르산 부가물(시코쿠화성공업(주) 제작)이다.* 1: 2MAOK is an isocyanuric acid adduct of 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine represented by the following structural formula (47): (Manufactured by Shikoku Kasei Kogyo Co., Ltd.).
-구조식(1)로 나타내어지는 화합물의 합성-Synthesis of Compound Represented by Structural Formula (1)
또한, 상기 구조식(1)로 나타내지는 화합물은 다음과 같이 하여 합성했다.In addition, the compound represented by the said Formula (1) was synthesize | combined as follows.
4-히드록시벤질알콜 50질량부와 에피클로로히드린 83.7질량부를 반응 가마에 넣어, 80℃에서 가열했다. 반응 가마에 48% 수산화 나트륨 수용액 31.6질량부를 3시간 걸쳐서 적하했다. 그 후 3시간 반응시켰다. 방냉 후, 아세트산 에틸 100질량부로 추출하고, 포화 식염수로 분액하여 유기상을 황산 마그네슘으로 건조했다. 유기상의 용매를 증류 제거하고, 실리카겔 크로마토그래피(전개 용매: 헥산/아세트산 에틸=3/7)로 정제하고, 제 1 중간 생성물 59질량부(수율 84%)를 얻었다.50 mass parts of 4-hydroxybenzyl alcohol and 83.7 mass parts of epichlorohydrin were put into the reaction kiln, and it heated at 80 degreeC. 31.6 mass parts of 48% sodium hydroxide aqueous solution was dripped at the reaction kiln over 3 hours. The reaction was then carried out for 3 hours. After cooling, the mixture was extracted with 100 parts by mass of ethyl acetate, separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the organic phase was distilled off, and it refine | purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 3/7), and 59 mass parts (yield 84%) of 1st intermediate products were obtained.
다음에, m-크실릴렌 디이소시아네이트 4.84질량부와 상기 제 1 중간 생성물 10질량부와 아세트산 에틸 14질량부를 반응 가마에 넣고, 90℃에서 가열했다. 반응 가마에 스타녹트(요시토미제약사 제작)을 0.02질량부 가했다. 그 후, 2시간 반응시켰다. 방냉 후, 반응 용액을 여과하고, 여액의 용매를 증류 제거하고, 아세트산 에틸에서 재결정함으로써 백색고체 12.5질량부(수율 84%)를 얻었다.Next, 4.84 mass parts of m-xylylene diisocyanate, 10 mass parts of said 1st intermediate products, and 14 mass parts of ethyl acetate were put into the reaction kiln, and it heated at 90 degreeC. 0.02 mass part of stannock (made by Yoshitomi Pharmaceutical Co., Ltd.) was added to the reaction kettle. Then, it was reacted for 2 hours. After allowing to cool, the reaction solution was filtered, the solvent of the filtrate was distilled off and recrystallized from ethyl acetate to obtain 12.5 parts by mass of a white solid (yield 84%).
또, 생성물은 1H-NMR(300MHz:CDCl3)로 동정했다. 스펙트럼의 각 피크는 7.67(t, 2H), 7.28-7.08(m, 8H), 6.88(d, 4H), 4.28(d, 2H), 4.12(q, 8H), 3.79(q, 2H), 2.85-2.77(m, 8H), 2.70(q,2H)이었다.In addition, the product was identified by 1 H-NMR (300 MHz: CDCl 3 ). Each peak in the spectrum is 7.67 (t, 2H), 7.28-7.08 (m, 8H), 6.88 (d, 4H), 4.28 (d, 2H), 4.12 (q, 8H), 3.79 (q, 2H), 2.85 -2.77 (m, 8H), 2.70 (q, 2H).
또한, 상기 구조식(1)로 나타내어지는 화합물의 감광성 조성물 중의 함유량은 14질량%이다.In addition, content in the photosensitive composition of the compound represented by the said Formula (1) is 14 mass%.
-감광성 필름의 제조-Production of Photosensitive Film
얻어진 감광성 조성물을 상기 지지체로서의 두께 20㎛의 PET(폴리에틸렌테레프탈레이트)필름 상에, 도포하고, 건조시켜서, 막두께 30㎛의 감광층을 형성했다.이어서, 상기 감광층 상에 상기 보호 필름으로서 12㎛두께의 폴리프로필렌 필름을 라미네이트로 적층하고, 감광성 필름을 제조했다.The obtained photosensitive composition was applied onto a PET (polyethylene terephthalate) film having a thickness of 20 µm as the support, and dried to form a photosensitive layer having a thickness of 30 µm. A polypropylene film having a thickness of µm was laminated with a laminate to prepare a photosensitive film.
-영구 패턴의 형성-Formation of permanent patterns
--적층체의 조제----Preparation of Laminates--
다음에 상기 기재로서, 배선 형성 완료의 동장 적층판(스루홀 없슴, 동두께12㎛)의 표면에 화학 연마 처리를 실시해서 조제했다. 상기 동장 적층판 상에, 상기 감광성 필름의 감광층이 상기 동장 적층판에 접하도록 해서 상기 감광성 필름에 있어서의 보호 필름을 박리하면서, 진공 라미네이터(니치고모톤(주)사 제작, VP130)를 이용하여 적층시키고, 상기 동장 적층판과 상기 감광층과 상기 폴리에틸렌테레프탈레이트 필름(지지체)이 이 순서로 적층된 적층체를 조제했다.Next, as the base material, a chemical polishing treatment was performed on the surface of the copper-clad laminate (no through hole, 12 µm thick) for wiring formation to prepare. On the said copper clad laminated board, it laminates using a vacuum laminator (Nichigo Motor Co., Ltd. make, VP130), peeling the protective film in the said photosensitive film so that the photosensitive layer of the said photosensitive film may contact the said copper clad laminated board. The laminated body by which the said copper clad laminated board, the said photosensitive layer, and the said polyethylene terephthalate film (support) were laminated | stacked in this order was prepared.
압착 조건은 진공 처리의 시간 40초간, 압착 온도 70℃, 압착 압력 0.2MPa, 가압 시간 10초간으로 했다.The crimping conditions were 40 seconds of the time of vacuum processing, 70 degreeC of crimping temperature, 0.2MPa of crimping pressure, and 10 second of pressurization time.
<택성의 평가><Evaluation of Tajik>
상기한 바와 같이 해서 얻어진 적층체에 있어서의 감광층의 표면의 택성에 대해서, 하기 기준에 기초하여 평가했다. 상기 실시예 1의 감광성 필름에 있어서의 보호 필름을 박리시킨 시점에서는 상기 감광층의 표면에 강한 택성이 없고, 박리 자체도 용이하게 행할 수 있었다. 결과를 표 3에 나타낸다.The tackiness of the surface of the photosensitive layer in the laminated body obtained as mentioned above was evaluated based on the following criteria. When the protective film in the photosensitive film of the said Example 1 was peeled off, there was no strong tackiness on the surface of the said photosensitive layer, and peeling itself could also be easily performed. The results are shown in Table 3.
[평가 기준][Evaluation standard]
○: 감광층의 표면에 강한 택성이 확인되지 않았다. (Circle): Strong tackiness was not confirmed on the surface of the photosensitive layer.
△:감광층의 표면에 약한 택성이 확인되었다. (Triangle | delta): Weak weakness was confirmed to the surface of the photosensitive layer.
×:감광층의 표면에 강한 택성이 확인되었다.X: Strong tackiness was confirmed on the surface of the photosensitive layer.
--노광 공정--Exposure Process
상기 조제한 적층체에 있어서의 감광층에 대하여, 폴리에틸렌테레프탈레이트 필름(지지체)측으로부터, 레이저 노광 장치를 사용하여 405nm의 레이저광을 직경이 다른 구멍부가 형성되는 패턴이 얻어지도록 조사해서 노광하여 상기 감광층의 일부의 영역을 경화시켰다.The photosensitive layer in the prepared laminate is irradiated with a laser light of 405 nm from a polyethylene terephthalate film (support) side so as to obtain a pattern in which holes having different diameters are formed, and then exposed, thereby exposing the photosensitive layer. The area of part of the layer was cured.
--현상 공정--Development Process
실온에서 10분간 정치한 후, 상기 적층체로부터 폴리에틸렌테레프탈레이트 필름(지지체)을 박리하고, 동장 적층판상의 감광층의 전체면에 알칼리 현상액으로서, 1질량% 탄산 소다 수용액을 사용하고, 스프레이 압력 0.2MPa, 30℃에서 60초간 샤워 현상하고, 미경화의 영역을 용해 제거했다. 그 후, 수세 하고, 건조시켜, 영구 패턴을 형성했다.After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled from the laminate, and a 1% by mass aqueous solution of soda carbonate was used as an alkali developer to the entire surface of the photosensitive layer on the copper clad laminate, and the spray pressure was 0.2 MPa. The shower development was carried out at 30 ° C. for 60 seconds, and the uncured area was dissolved and removed. Thereafter, the mixture was washed with water and dried to form a permanent pattern.
--경화 처리 공정----Hardening Process--
상기 영구 패턴이 형성된 적층체의 전체면에 대하여, 160℃에서 60분간, 가열 처리를 실시하고, 영구 패턴의 표면을 경화하고, 막강도를 높였다. 상기 영구 패턴을 육안으로 관찰하였더니, 영구 패턴의 표면에 기포는 확인되지 않았다.The whole surface of the laminated body in which the said permanent pattern was formed was heat-processed at 160 degreeC for 60 minutes, the surface of the permanent pattern was hardened, and the film strength was raised. When the permanent pattern was visually observed, no bubble was observed on the surface of the permanent pattern.
상기 제조한 감광성 필름에 대해서, 노광 감도, 해상도, 노광 속도 및 보존 안정성의 평가를 행하고, 상기 형성된 영구 패턴에 대해서 연필 경도 및 유전 특성의 평가를 행했다. 결과를 표 3에 나타낸다.Exposure sensitivity, resolution, exposure speed, and storage stability were evaluated about the produced photosensitive film, and pencil hardness and dielectric properties were evaluated about the formed permanent pattern. The results are shown in Table 3.
<노광 감도><Exposure Sensitivity>
얻어진 상기 영구 패턴에 있어서, 남은 상기 감광층의 경화 영역의 두께를 측정했다. 이어서, 레이저광의 조사량과 경화층의 두께의 관계를 플롯해서 감도곡선을 얻는다. 이렇게 해서 얻은 감도 곡선으로부터 배선상의 경화 영역의 두께가 15㎛가 되고, 경화 영역의 표면이 광택면일 때의 광 에너지량을 감광층을 경화시키기 위해서 필요한 광 에너지량으로 했다.In the obtained permanent pattern, the thickness of the hardened region of the remaining photosensitive layer was measured. Next, the relationship between the irradiation amount of laser light and the thickness of the cured layer is plotted to obtain a sensitivity curve. From the sensitivity curve thus obtained, the thickness of the cured region on the wiring became 15 µm, and the amount of light energy when the surface of the cured region was a glossy surface was used as the amount of light energy required for curing the photosensitive layer.
그 결과, 상기 감광층을 경화시키기 위해서 필요한 광 에너지량은 30mJ/cm2이었다.As a result, the amount of light energy required to cure the photosensitive layer was 30 mJ / cm 2 .
<해상도><Resolution>
얻어진 상기 영구 패턴 형성 완료의 프린트 배선 기판의 표면을 광학 현미경으로 관찰하고, 경화층 패턴의 구멍부에 잔막이 없는 최소의 구멍 직경을 측정하고, 이것을 해상도로 했다. 상기 해상도는 수치가 작을수록 양호하다. 그 결과, 해상도는 70㎛이었다.The surface of the obtained printed wiring board of the permanent pattern formation completed was observed with an optical microscope, the minimum hole diameter without a residual film was measured and this was made into the resolution. The smaller the numerical value, the better. As a result, the resolution was 70 µm.
<노광 속도><Exposure Speed>
405nm 레이저 노광 장치를 사용하고, 노광광과 상기 감광층을 상대적으로 이동시키는 속도를 변경하여, 영구 패턴이 형성되는 속도를 구했다. 노광은 상기 조제한 적층체에 있어서의 감광층에 대하여, 폴리에틸렌테레프탈레이트 필름(지지체) 측으로부터 행했다. 또, 이 설정 속도가 빠를수록 효율적인 영구 패턴 형성이 가능해진다. 또, 상기 405nm 레이저 노광 장치는 상기 DMD로 이루어지는 광변조 수단을 갖고, 노광 속도는 13mm/sec이었다.Using a 405 nm laser exposure apparatus, the speed of moving the exposure light and the photosensitive layer relative to each other was changed to determine the speed at which the permanent pattern was formed. Exposure was performed from the polyethylene terephthalate film (support) side with respect to the photosensitive layer in the prepared laminated body. In addition, the faster the setting speed, the more efficient the permanent pattern formation becomes possible. Moreover, the said 405 nm laser exposure apparatus had the light modulation means which consists of said DMD, and the exposure speed was 13 mm / sec.
<보존 안정성><Storage stability>
상기 제조한 감광성 필름을 40℃에서 3일간의 강제 경시 후, 미노광막의 현상 시간을 측정했다.The developing time of the unexposed film | membrane was measured after 3 days of forced aging of the photosensitive film produced above at 40 degreeC.
<연필 경도><Pencil hardness>
상기 영구 패턴 형성 완료의 프린트 배선기판에 대하여, 통상의 방법을 따라 금도금을 행한 후, 수용성 플럭스 처리를 행했다. 이어서, 260℃로 설정된 땜납조에 5초간에 걸쳐, 3회 침지하고, 플럭스를 수세로 제거했다. 그리고, 상기 플럭스 제거 후의 영구 패턴에 대해서, JIS K-5400에 기초하여 연필 경도를 측정했다.After the gold plating was performed on the printed wiring board of the permanent pattern formation completed according to a conventional method, water soluble flux treatment was performed. Subsequently, it was immersed three times in the solder bath set to 260 degreeC over 5 second, and the flux was removed by water washing. And about the permanent pattern after the said flux removal, pencil hardness was measured based on JISK-5400.
그 결과, 연필 경도는 5H이었다. 또한, 육안 관찰을 행한 바, 상기 영구 패턴에 있어서의 경화막의 박리, 팽윤, 변색은 확인되지 않았다.As a result, the pencil hardness was 5H. Moreover, when visual observation was performed, peeling, swelling, and discoloration of the cured film in the said permanent pattern were not confirmed.
<유전 특성의 측정><Measurement of dielectric properties>
막두께 500㎛의 경화막의 유전 특성을 아지덴트·테크놀로지사 제작 LCR 미터와 4291A형 고체 전극을 사용하여 25℃에서 측정한 결과, 1GHz에서의 유전율은 3.3이고, 유전 정접은 0.013이었다.The dielectric properties of the cured film having a film thickness of 500 µm were measured at 25 ° C using an LCR meter manufactured by Azident Technology Co., Ltd. and a 4291A type solid electrode. As a result, the dielectric constant at 1 GHz was 3.3 and the dielectric tangent was 0.013.
(실시예 2)(Example 2)
하기 조성에 기초하여 감광성 조성물을 조제하고, 실시예 1과 동일한 방법으로 감광성 필름 및 적층체를 조제하고, 영구 패턴을 형성했다.The photosensitive composition was prepared based on the following composition, the photosensitive film and the laminated body were prepared by the method similar to Example 1, and the permanent pattern was formed.
또한, 실시예 1과 동일하게 하여 상기 제조한 감광성 조성물 및 감광성 필름에 대해서, 택성, 노광 감도, 해상도, 노광 속도 및 보존 안정성의 평가를 행하고, 상기 형성한 영구 패턴에 대해서 연필 경도 및 유전 특성의 평가를 행했다. 그 결과, 노광 감도는 30mJ/cm2, 해상도는 70㎛, 노광 속도는 13mJ/cm2이었다. 그 밖의 결과를 표 3에 나타낸다.In addition, the photosensitive composition and the photosensitive film produced in the same manner as in Example 1 were evaluated for tackiness, exposure sensitivity, resolution, exposure speed, and storage stability. Evaluation was performed. As a result, the exposure sensitivity was 30 mJ / cm 2 , the resolution was 70 μm, and the exposure speed was 13 mJ / cm 2 . Other results are shown in Table 3.
[감광성 조성물 용액의 조성][Composition of Photosensitive Composition Solution]
·황산 바륨 33.4질량부Barium sulfate 33.4 parts by mass
·스티렌/무수 말레인산/부틸 아크릴레이트 공중합체(몰비 40/32/28)와 벤질 아민(상기 공중합체의 무수물기에 대하여 1.0당량)의 부가 반응물*2 40.0질량부Addition reaction product of styrene / maleic anhydride / butyl acrylate copolymer (molar ratio 40/32/28) and benzyl amine (1.0 equivalent to the anhydride group of the copolymer) * 2 40.0 parts by mass
·상기 구조식(1)로 나타내어지는 화합물(열가교제) 15.7질량부15.7 parts by mass of the compound (thermal crosslinking agent) represented by the above structural formula (1)
·디펜타에리스리톨헥사아크릴레이트 16.0질량부Dipentaerythritol hexaacrylate 16.0 parts by mass
·IRGACURE 819(치바·스페셜티·케미컬즈 제작) 5.8질량부IRGACURE 819 (Chiba Specialty Chemicals) 5.8 parts by mass
·하이드로퀴논모노메틸에테르 0.056질량부0.056 parts by mass of hydroquinone monomethyl ether
·디시안디아미드 0.77질량부0.77 parts by mass of dicyandiamide
·2MAOK 0.47질량부2MAOK 0.47 parts by mass
*2:하기 구조식(VII)으로 나타내어지는 유닛 A 및 유닛 B를 갖는 말레아미드산계 공중합체이다. 상기 유닛 A는 2종의 구성 단위로 이루어지고, 그 중의 하나의 구성단위에 있어서의 R1은 페닐이고, 다른 구성 단위에 있어서의 R1은 부틸옥시카르 보닐, R3 및 R4는 수소 원자이다. 상기 유닛 B에 있어서의 R2는 벤질이다. 상기 유닛 A에 있어서의 반복 단위의 몰분율 x는 상기 1의 구성단위에 관해서는 40몰%이고, 상기 이외의 구성 단위에 관해서는 28몰%이고, 상기 유닛 B에 있어서의 반복 단위의 몰분율 y는 32몰%이다. 또한 상기 스티렌/무수 말레인산/부틸아크릴레이트 공중합체의 무수물기에 대한 상기 벤질 아민의 반응량은 1.0당량이다.* 2: a maleamic acid copolymer having unit A and unit B represented by the following structural formula (VII). The unit A is composed of a structural unit of two, and R 1 is phenyl in one of the structural units of which, R 1 in the other constituent unit is butyloxycarbonyl, R 3 and R 4 are hydrogen atoms to be. R 2 in the unit B is benzyl. The mole fraction x of the repeating unit in the said unit A is 40 mol% with respect to the structural unit of said 1, 28 mol% with respect to the structural unit other than the above, and the mole fraction y of the repeating unit in the said unit B is 32 mol%. In addition, the reaction amount of the benzyl amine to the anhydride group of the styrene / maleic anhydride / butyl acrylate copolymer is 1.0 equivalent.
상기 비닐 단량체인 부틸아크릴레이트의 호모 폴리머의 유리 전이 온도(Tg)는 -54℃이다.The glass transition temperature (Tg) of the homopolymer of butylacrylate which is the said vinyl monomer is -54 degreeC.
실시예 2에 있어서의 상기 구조식(1)로 나타내어지는 에폭시 수지 화합물의 감광성 조성물 중의 함유량은 14질량%이다.Content in the photosensitive composition of the epoxy resin compound represented by the said Structural formula (1) in Example 2 is 14 mass%.
(실시예 3)(Example 3)
실시예 1에 있어서, 감광성 조성물 중의 상기 구조식(1)로 나타내어지는 에폭시 수지 화합물의 첨가량을 0.8질량부로 하고, 구조식(1)로 나타내어지는 에폭시 수지 화합물의 감광성 조성물 중의 함유량을 0.8질량%(1질량% 미만)으로 한 것 이외는 실시예 1과 같은 방법으로 감광성 조성물을 조제하고, 실시예 1과 같은 방법 으로 감광성 필름 및 적층체를 조제하고, 영구 패턴을 형성했다.In Example 1, the addition amount of the epoxy resin compound represented by the structural formula (1) in the photosensitive composition is 0.8 parts by mass, and the content in the photosensitive composition of the epoxy resin compound represented by the structural formula (1) is 0.8 mass% (1 mass) A photosensitive composition was prepared in the same manner as in Example 1 except that the composition was less than%), a photosensitive film and a laminate were prepared in the same manner as in Example 1, and a permanent pattern was formed.
또한, 실시예 1과 같은 방법으로 상기 제조한 감광성 필름에 대해서, 택성, 노광 감도, 해상도, 노광 속도, 및 보존 안정성의 평가를 행하고, 상기 형성한 영구 패턴에 대해서 연필 경도 및 유전 특성의 평가를 행했다. 그 결과, 노광 감도는 30mJ/cm2, 해상도는 70㎛, 노광 속도는 13mJ/cm2이었다. 그 밖의 결과를 표 3에 나타낸다.Moreover, about the photosensitive film manufactured by the method similar to Example 1, evaluation of tackiness, exposure sensitivity, resolution, exposure speed, and storage stability is performed, and evaluation of pencil hardness and dielectric property is performed about the formed permanent pattern. Done. As a result, the exposure sensitivity was 30 mJ / cm 2 , the resolution was 70 μm, and the exposure speed was 13 mJ / cm 2 . Other results are shown in Table 3.
(실시예 4)(Example 4)
실시예 1에 있어서, 감광성 조성물 중의 상기 구조식(1)로 나타내어지는 에폭시 수지 화합물의 첨가량을 100질량부로 하고, 구조식(1)로 나타내어지는 에폭시 수지 화합물의 감광성 조성물 중의 함유량을 51질량%(50질량%초과)로 한 것 이외는 실시예 1과 동일한 방법으로 감광성 조성물을 조제하고, 실시예 1과 동일한 방법으로 감광성 필름 및 적층체를 조제하고, 영구 패턴을 형성했다.In Example 1, the addition amount of the epoxy resin compound represented by the structural formula (1) in the photosensitive composition is 100 parts by mass, and the content in the photosensitive composition of the epoxy resin compound represented by the structural formula (1) is 51% by mass (50 masses). A photosensitive composition was prepared in the same manner as in Example 1 except that the concentration was greater than%), a photosensitive film and a laminate were prepared in the same manner as in Example 1, and a permanent pattern was formed.
또한, 실시예 1과 동일한 방법으로 상기 제조한 감광성 필름에 대해서, 택성, 노광 감도, 해상도, 노광 속도, 및 보존 안정성의 평가를 행하고, 상기 형성한 영구 패턴에 대해서 연필 경도 및 유전 특성의 평가를 행했다. 그 결과, 노광 감도는 30mJ/cm2, 해상도는 70㎛, 노광 속도는 13mJ/cm2이었다. 그 밖의 결과를 표 3에 나타낸다.Moreover, about the photosensitive film manufactured above by the method similar to Example 1, evaluation of tackiness, exposure sensitivity, resolution, exposure speed, and storage stability is performed, and evaluation of pencil hardness and dielectric property is performed about the formed permanent pattern. Done. As a result, the exposure sensitivity was 30 mJ / cm 2 , the resolution was 70 μm, and the exposure speed was 13 mJ / cm 2 . Other results are shown in Table 3.
(실시예 5∼13)(Examples 5 to 13)
실시예 1에 있어서, 감광성 조성물 중의 상기 구조식(1)로 나타내어지는 화 합물을 표 3에 나타낸 상기 구조식(2)∼(10)으로 나타내어지는 화합물로 변경한 것 이외는 실시예 1과 같은 방법으로 감광성 조성물을 조제하고, 실시예 1과 같은 방법으로 감광성 필름 및 적층체를 조제하고, 영구 패턴을 형성했다.In Example 1, the method similar to Example 1 except having changed the compound represented by the said Formula (1) in the photosensitive composition into the compound represented by the said Formula (2)-(10) shown in Table 3 is carried out. The photosensitive composition was prepared, the photosensitive film and the laminated body were prepared by the method similar to Example 1, and the permanent pattern was formed.
또한, 실시예 1과 같은 방법으로 상기 제조한 감광성 필름에 대해서, 택성, 노광 감도, 해상도, 노광 속도, 및 보존 안정성의 평가를 행하고, 상기 형성한 영구 패턴에 대해서 연필 경도 및 유전 특성의 평가를 행했다. 그 결과, 실시예 5∼13에서는, 모두 노광 감도가 30mJ/cm2, 해상도가 70㎛, 노광 속도가 13mJ/cm2이었다. 각 실시예의 그 밖의 결과를 표 3에 나타낸다.Moreover, about the photosensitive film manufactured by the method similar to Example 1, evaluation of tackiness, exposure sensitivity, resolution, exposure speed, and storage stability is performed, and evaluation of pencil hardness and dielectric property is performed about the formed permanent pattern. Done. As a result, in Examples 5 to 13, the exposure sensitivity was 30 mJ / cm 2 , the resolution was 70 μm, and the exposure speed was 13 mJ / cm 2 . Other results of each example are shown in Table 3.
또한, 상기 구조식(2)∼(10)으로 나타내어지는 화합물(열가교제)은 하기와 같이 하여 합성했다.In addition, the compound (thermal crosslinking agent) represented by said structural formula (2)-(10) was synthesize | combined as follows.
-구조식(2)로 나타내어지는 화합물의 합성-Synthesis of Compound Represented by Structural Formula (2)
상기 실시예 1에서 얻은 제 1 중간 생성물 10.9질량부와 헥사메틸렌 디이소시아네이트 4.71질량부와 아세트산 에틸 14질량부를 반응 가마에 넣고, 90℃에서 가열했다. 반응 가마에 스타녹트(요시토미제약사 제작)를 0.02질량부 가했다. 그 후, 2시간 반응시켰다. 방냉 후, 반응 용액을 여과하고, 여액의 용매를 증류 제거하고, 아세트산 에틸로 재결정함으로써 백색고체 13.2질량부(수율 85%)를 얻었다.10.9 mass parts of the 1st intermediate products obtained in the said Example 1, 4.71 mass parts of hexamethylene diisocyanate, and 14 mass parts of ethyl acetate were put into the reaction kiln, and it heated at 90 degreeC. 0.02 mass part of stannock (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was added to the reaction kettle. Then, it was reacted for 2 hours. After cooling, the reaction solution was filtered, the solvent of the filtrate was distilled off, and recrystallized from ethyl acetate to obtain 13.2 parts by mass of a white solid (yield 85%).
또, 생성물은 1H-NMR(300MHz: CDCl3)로 동정했다. 스펙트럼의 각 피크는 7.13(d, 4H), 6.86(d, 4H), 4.69(br, 2H), 4.25-4.17(m, 6H), 3.94(q, 2H), 3.37-3.33(m, 2H), 3.14(d, 4H), 2.75(q, 2H), 1.47(m, 4H), 1.31(m, 4H)이었다.In addition, the product was identified by 1 H-NMR (300 MHz: CDCl 3 ). Each peak in the spectrum is 7.13 (d, 4H), 6.86 (d, 4H), 4.69 (br, 2H), 4.25-4.17 (m, 6H), 3.94 (q, 2H), 3.37-3.33 (m, 2H) , 3.14 (d, 4H), 2.75 (q, 2H), 1.47 (m, 4H), and 1.31 (m, 4H).
-구조식(3)으로 나타내어지는 화합물의 합성-Synthesis of Compound Represented by Structural Formula (3)
톨릴렌디이소시아네이트 20질량부와 3-메틸-3부텐-1-올 21.8질량부와 아세트산 에틸 80질량부를 반응 가마에 넣고, 55℃에서 가열했다. 상기 반응 가마에 스타녹트(요시토미제약사 제작) 0.05질량부 가했다. 그 후 6시간 반응시켰다. 방냉 후, 상기 반응물로부터 용매를 증류 제거하고, 실리카겔 크로마토그래피(전개 용매: 헥산/아세트산 에틸=7/3)로 정제하여 중간 생성물 32질량부(수율 80%)를 얻었다.20 mass parts of tolylene diisocyanate, 21.8 mass parts of 3-methyl-3 butene-1-ols, and 80 mass parts of ethyl acetate were put into the reaction kiln, and it heated at 55 degreeC. 0.05 mass part of stannock (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was added to the reaction kettle. The reaction was then carried out for 6 hours. After cooling, the solvent was distilled off from the reaction product and purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 7/3) to obtain 32 parts by mass of the intermediate product (yield 80%).
다음에, 상기 중간 생성물 28질량부, 아세트산 에틸 250질량부, 탄산 수소나트륨 68질량부, 물 200질량부, 및 아세톤 98질량부를 반응 가마에 넣었다. 상기 반응 가마에 OXONE115 질량부를 물 400질량부에 용해시킨 수용액을 1시간 걸쳐서 적하했다. 그 후 7시간 반응시켰다. 상기 반응 가마에 10% 티오황산 나트륨 수용액을 300질량부 가하여 1시간 교반하고, 포화 식염수에서 분액하여 유기상을 황산마그네슘으로 건조했다. 상기 유기상의 용매를 증류제거하고, 실리카겔 크로마토그래피(전개 용매: 헥산/아세트산 에틸=6/4)로 정제하고, 유상 물질 19.5질량부(수율 64%)을 얻었다.Next, 28 mass parts of said intermediate products, 250 mass parts of ethyl acetate, 68 mass parts of sodium hydrogencarbonate, 200 mass parts of water, and 98 mass parts of acetone were put into the reaction kiln. The aqueous solution which melt | dissolved OXONE115 mass part in 400 mass parts of water was dripped at the said reaction kiln over 1 hour. The reaction was then carried out for 7 hours. 300 mass parts of 10% sodium thiosulfate aqueous solution was added to the said reaction kiln, it stirred for 1 hour, liquid-separated in saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the said organic phase was distilled off, and it refine | purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 6/4), and obtained 19.5 mass parts (yield 64%) of oily substances.
또, 생성물은 1H-NMR(300MHz: CDCl3)로 동정했다. 스펙트럼의 각 피크는 7.79(s, 1H), 7.22(d, 1H), 7.09(d, 1H), 6.68(s, 1H), 6.41(s, 1H), 4.37-4.02(m, 4H), 2.63(d, 4H), 2.20(s, 3H), 2.03-1.86(m, 4H), 1.39(s, 6H)이었다.In addition, the product was identified by 1 H-NMR (300 MHz: CDCl 3 ). Each peak in the spectrum is 7.79 (s, 1H), 7.22 (d, 1H), 7.09 (d, 1H), 6.68 (s, 1H), 6.41 (s, 1H), 4.37-4.02 (m, 4H), 2.63 (d, 4H), 2.20 (s, 3H), 2.03-1.86 (m, 4H), and 1.39 (s, 6H).
-구조식(4)로 나타내어지는 화합물의 합성-Synthesis of Compound Represented by Structural Formula (4)
상기 실시예 1로 얻어진 제 1 중간 생성물 7.56질량부와 메틸렌비스페닐이소 시아네이트 4.87질량부와 아세트산 에틸 12질량부를 반응 가마에 넣고, 90℃에서 가열했다. 반응 가마에 스타녹트(요시토미제약사 제작)를 0.02질량부 가했다. 그 후에 2시간 반응시켰다. 방냉 후, 반응 용액을 여과하고, 여액의 용매를 증류 제거하고, 아세트산 에틸로 재결정함으로써 백색 고체 9.6질량부(수율 77%)를 얻었다.7.56 parts by mass of the first intermediate product obtained in Example 1, 4.87 parts by mass of methylenebisphenylisocyanate and 12 parts by mass of ethyl acetate were placed in a reaction kettle, and heated at 90 ° C. 0.02 mass part of stannock (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was added to the reaction kettle. The reaction was then carried out for 2 hours. After allowing to cool, the reaction solution was filtered, the solvent of the filtrate was distilled off, and recrystallized with ethyl acetate to obtain 9.6 parts by mass (yield 77%) of a white solid.
또한, 생성물은 1H-NMR(300MHz: CDCl3)로 동정했다. 스펙트럼의 각 피크는 9.50(s, 2H), 7.34(d, 4H), 7.20(d, 4H), 7.08(d, 4H), 6.90(d, 4H), 4.30-4.21(m, 4H), 3.84(q, 4H), 3.32(s, 2H), 2.89-2.82(m, 4H), 2.70(t, 2H), 2.50(s, 4H)이었다.The product was also identified by 1 H-NMR (300 MHz: CDCl 3 ). Each peak in the spectrum is 9.50 (s, 2H), 7.34 (d, 4H), 7.20 (d, 4H), 7.08 (d, 4H), 6.90 (d, 4H), 4.30-4.21 (m, 4H), 3.84 (q, 4H), 3.32 (s, 2H), 2.89-2.82 (m, 4H), 2.70 (t, 2H), and 2.50 (s, 4H).
-구조식(5)로 나타내어지는 화합물의 합성-Synthesis of Compound Represented by Structural Formula (5)
상기 실시예 1로 얻어진 제일 중간 생성물 7.56질량부와 1,3-비스(1-이소시아네이트-1-메틸에틸)벤젠 5.66질량부와 아세트산 에틸 15질량부를 반응 가마에 넣고, 90℃에서 가열했다. 반응 가마에 스타녹트(요시토미제약사 제작)를 0.02질량부 가했다. 그 후에 2시간 반응시켰다. 방냉 후, 아세트산 에틸 50질량부로 추출하고, 포화 식염수로 분액하고, 유기상을 황산 마그네슘으로 건조했다. 유기상의 용매를 증류 제거하고, 실리카겔 크로마토그래피(전개 용매: 헥산/아세트산 에틸=5/5)로 정제하고, 화합물 5.4질량부(수율 37%)를 얻었다.7.56 parts by mass of the first intermediate product obtained in Example 1, 5.66 parts by mass of 1,3-bis (1-isocyanate-1-methylethyl) benzene, and 15 parts by mass of ethyl acetate were placed in a reaction kiln, and heated at 90 ° C. 0.02 mass part of stannock (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was added to the reaction kettle. The reaction was then carried out for 2 hours. After cooling, the mixture was extracted with 50 parts by mass of ethyl acetate, separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the organic phase was distilled off, and it refine | purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 5/5), and obtained 5.4 mass parts (yield 37%) of compounds.
또한, 생성물은 1H-NMR(300MHz:CDCl3)로 동정했다. 스펙트럼의 각 피크는 7.47(s, 2H), 7.29(s, 4H), 7.12(s, 2H), 6.86(d, 4H), 5.06(s, 2H), 4.22-4.16(m, 6H), 3.94(q, 2H), 3.34(m, 2H), 2.92-2.74(m, 4H), 1.71(s, 12H)이었다.In addition, the product was identified by 1 H-NMR (300 MHz: CDCl 3 ). Each peak in the spectrum is 7.47 (s, 2H), 7.29 (s, 4H), 7.12 (s, 2H), 6.86 (d, 4H), 5.06 (s, 2H), 4.22-4.16 (m, 6H), 3.94 (q, 2H), 3.34 (m, 2H), 2.92-2.74 (m, 4H), and 1.71 (s, 12H).
-구조식(6)으로 나타내어지는 화합물의 합성-Synthesis of Compound Represented by Structural Formula (6)
톨릴렌디이소시아네이트 20질량부, 2-메틸-2-프로펜-1-올 16.1질량부, 및 아세트산 에틸 80질량부를 반응 가마에 넣고, 55℃에 가열했다. 상기 반응 가마에 스타녹트(요시토미제약사 제작)를 0.05질량부 가했다. 그 후 6시간 반응시켰다. 방냉 후 반응 용액을 여과했다. 상기 여액의 용매를 증류 제거하고, 헥산/아세트산 에틸=1/1 용액으로 재결정함으로써 중간 생성물 21질량부(수율 60%)를 얻었다.20 mass parts of tolylene diisocyanate, 16.1 mass part of 2-methyl-2-propene-1-ols, and 80 mass parts of ethyl acetate were put into the reaction kettle, and it heated at 55 degreeC. 0.05 mass part of stannock (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was added to the reaction kettle. The reaction was then carried out for 6 hours. After allowing to cool, the reaction solution was filtered. The solvent of the filtrate was distilled off and 21 mass parts (yield 60%) of intermediate products were obtained by recrystallization with the hexane / ethyl acetate = 1/1 solution.
다음에, 상기 중간 생성물 20질량부, 아세트산 에틸 200질량부, 탄산수소나트륨 51질량부, 물 200질량부, 및 아세톤 73질량부를 반응 가마에 넣었다. 상기 반응 가마에 OXONE 90질량부를 물 400질량부에 용해시킨 수용액을 1시간 걸쳐서 적하했다. 그 후 7시간 반응시켰다. 상기 반응 가마에 10% 티오황산 나트륨 수용액을 300질량부 가하여 1시간 교반하고, 포화 식염수로 분액하여 유기상을 황산 마그네슘으로 건조했다. 상기 유기상의 용매를 증류 제거하고, 실리카겔 크로마토그래피(전개 용매: 헥산/아세트산 에틸=3/7)로 정제하고, 백색 고체 15질량부(수율 68%)를 얻었다. Next, 20 parts by mass of the intermediate product, 200 parts by mass of ethyl acetate, 51 parts by mass of sodium bicarbonate, 200 parts by mass of water, and 73 parts by mass of acetone were placed in a reaction kiln. The aqueous solution which melt | dissolved 90 mass parts of OXONE in 400 mass parts of water was dripped at the said reaction kiln over 1 hour. The reaction was then carried out for 7 hours. 300 mass parts of 10% sodium thiosulfate aqueous solution was added to the said reaction kiln, it stirred for 1 hour, liquid-separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the said organic phase was distilled off, and it refine | purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 3/7), and 15 mass parts (yield 68%) of white solids were obtained.
또, 생성물은 1H-NMR(300MHz:CDCl3)로 동정했다. 스펙트럼의 각 피크는 7.34-7.19(m, 4H), 5.46(s, 2H), 4.38(d, 4H), 4.30(d, 2H), 4.00(d, 2H), 2.78(d, 2H), 2.66(d, 2H), 1.38(s, 6H)이었다.In addition, the product was identified by 1 H-NMR (300 MHz: CDCl 3 ). Each peak in the spectrum is 7.34-7.19 (m, 4H), 5.46 (s, 2H), 4.38 (d, 4H), 4.30 (d, 2H), 4.00 (d, 2H), 2.78 (d, 2H), 2.66 (d, 2H) and 1.38 (s, 6H).
-구조식(7)로 나타내어지는 화합물의 합성-Synthesis of Compound Represented by Structural Formula (7)
4-히드록시벤질 알콜 30질량부, 탄산칼륨 37질량부, 및 디메틸아세트아미드100질량부를 반응 가마에 넣고, 80℃에서 가열했다. 상기 반응 가마에 3-클로로-2-메틸-1-프로펜 23.6질량부를 0.5시간 걸쳐서 적하했다. 그 후 10시간 반응시켰다. 방냉 후, 상기 반응물을 아세트산 에틸 100질량부로 추출하고, 포화 식염수로 분액하여 유기상을 황산 마그네슘으로 건조했다. 상기 유기상의 용매를 증류 제거하고, 실리카겔 크로마토그래피(전개 용매: 헥산/아세트산 에틸=5/5)로 정제하고, 제 1 중간 생성물 34.5질량부(수율 89%)를 얻었다.30 mass parts of 4-hydroxybenzyl alcohol, 37 mass parts of potassium carbonate, and 100 mass parts of dimethylacetamide were put into the reaction kiln, and it heated at 80 degreeC. 23.6 mass parts of 3-chloro-2-methyl-1-propenes were dripped at the said reaction kiln over 0.5 hour. The reaction was then carried out for 10 hours. After cooling, the reaction mass was extracted with 100 parts by mass of ethyl acetate, separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the said organic phase was distilled off, and it refine | purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 5/5), and 34.5 mass parts (yield 89%) of 1st intermediate products were obtained.
다음에 상기 제 1 중간 생성물 30질량부, 아세트산 에틸 200질량부, 탄산수소나트륨 71질량부, 물 200질량부 및 아세톤 103질량부를 반응 가마에 넣었다. 상기 반응 가마에 OXONE120질량부를 물 500질량부에 용해시킨 수용액을 1시간 걸쳐서 적하했다. 그 후 7시간 반응시켰다. 상기 반응 가마에 10% 티오황산 나트륨 수용액을 300질량부 가하여 1시간 교반하고, 포화 식염수로 분액하여 유기상을 황산 마그네슘으로 건조했다. 상기 유기상의 용매를 증류 제거하고, 실리카겔 크로마토그래피(전개 용매: 헥산/아세트산에틸=5/5)로 정제하여 제 2 중간 생성물 19.5질량부(수율 60%)를 얻었다.Next, 30 mass parts of said 1st intermediate products, 200 mass parts of ethyl acetate, 71 mass parts of sodium hydrogencarbonate, 200 mass parts of water, and 103 mass parts of acetone were put into the reaction kiln. The aqueous solution which melt | dissolved 120 mass parts of OXONE in 500 mass parts of water was dripped at the said reaction kiln over 1 hour. The reaction was then carried out for 7 hours. 300 mass parts of 10% sodium thiosulfate aqueous solution was added to the said reaction kiln, it stirred for 1 hour, liquid-separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the organic phase was distilled off and the residue was purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 5/5) to obtain 19.5 parts by mass (yield 60%) of the second intermediate product.
최후에, m-크실릴렌디이소시아네이트 5질량부와 상기 제 2 중간생성물 10.6질량부와 아세트산 에틸 50질량부를 반응 가마에 넣고, 55℃에서 가열했다. 상기 반응 가마에, 스타녹트(요시토미제약사 제작)를 0.05질량부 가했다. 그 후 6시간 반응시켰다. 방냉 후, 상기 반응 용액을 여과하고, 여액의 용매를 증류 제거하고, 아세트산 에틸로 재결정함으로써 백색 고체 7질량부(수율 44%)를 얻었다. 상기 백 색 고체의 융점은 113-115℃이었다.Finally, 5 parts by mass of m-xylylene diisocyanate, 10.6 parts by mass of the second intermediate product, and 50 parts by mass of ethyl acetate were placed in a reaction kiln and heated at 55 ° C. To the reaction kiln, 0.05 parts by mass of stannock (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was added. The reaction was then carried out for 6 hours. After cooling, the reaction solution was filtered, the solvent of the filtrate was distilled off, and recrystallized with ethyl acetate to obtain 7 parts by mass of a white solid (yield 44%). The melting point of the white solid was 113-115 ° C.
또한, 생성물은 1H-NMR(300MHz:CDCl3)로 동정했다. 스펙트럼의 각 피크는 7.32-7.11(m, 8H), 6.84(d, 4H), 4.97(br, 2H), 4.35-4.25(m, 8H), 3.99(q, 4H), 2.87(m, 6H), 2.72(d, 2H), 1.48(s, 6H)이었다.In addition, the product was identified by 1 H-NMR (300 MHz: CDCl 3 ). Each peak in the spectrum is 7.32-7.11 (m, 8H), 6.84 (d, 4H), 4.97 (br, 2H), 4.35-4.25 (m, 8H), 3.99 (q, 4H), 2.87 (m, 6H) , 2.72 (d, 2H), 1.48 (s, 6H).
-구조식(8)로 나타내어지는 에폭시 수지 화합물의 합성--Synthesis of epoxy resin compound represented by Structural Formula (8)-
4-히드록시벤질알콜 30질량부, 탄산칼륨 37질량부, 및 디메틸아세트아미드 100질량부를 반응 가마에 넣고, 80℃에서 가열했다. 상기 반응 가마에 3-클로로-2-메틸-1-프로펜 23.6질량부를 0.5시간 걸쳐서 적하했다. 그 후 10시간 반응시켰다. 방냉 후, 상기 반응물을 아세트산 에틸 100질량부로 추출하고, 포화 식염수로 분액하여 유기상을 황산 마그네슘으로 건조했다. 상기 유기상의 용매를 증류 제거하고, 실리카겔 크로마토그래피(전개 용매: 헥산/아세트산 에틸=5/5)로 정제하고, 제 1 중간 생성물 34.5질량부(수율 89%)를 얻었다.30 mass parts of 4-hydroxybenzyl alcohol, 37 mass parts of potassium carbonate, and 100 mass parts of dimethylacetamide were put into the reaction kiln, and it heated at 80 degreeC. 23.6 mass parts of 3-chloro-2-methyl-1-propenes were dripped at the said reaction kiln over 0.5 hour. The reaction was then carried out for 10 hours. After cooling, the reaction mass was extracted with 100 parts by mass of ethyl acetate, separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the said organic phase was distilled off, and it refine | purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 5/5), and 34.5 mass parts (yield 89%) of 1st intermediate products were obtained.
다음에, 상기 제 1 중간 생성물 30질량부, 아세트산 에틸 200질량부, 탄산수소나트륨 71질량부, 물 200질량부, 및 아세톤 103질량부를 반응 가마에 넣었다. 상기 반응 가마에 OXONE 120질량부를 물 500질량부에 용해시킨 수용액을 1시간 걸쳐서 적하했다. 그 후 7시간 반응시켰다. 상기 반응 가마에, 10% 티오황산 나트륨 수용액을 300질량부 가하여 1시간 교반하고, 포화 식염수로 분액하여 유기상을 황산마그네슘으로 건조했다. 상기 유기상의 용매를 증류 제거하고, 실리카겔 크로마토그래피(전개 용매: 헥산/아세트산 에틸=5/5)로 정제하고, 제 2 중간 생성물 19.5질 량부(수율 60%)를 얻었다.Next, 30 mass parts of said 1st intermediate products, 200 mass parts of ethyl acetate, 71 mass parts of sodium hydrogencarbonate, 200 mass parts of water, and 103 mass parts of acetone were put into the reaction kiln. The aqueous solution which melt | dissolved 120 mass parts of OXONE in 500 mass parts of water was dripped at the said reaction kiln over 1 hour. The reaction was then carried out for 7 hours. 300 mass parts of 10% sodium thiosulfate aqueous solution was added to the said reaction kiln, it stirred for 1 hour, liquid-separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the said organic phase was distilled off, and it refine | purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 5/5), and 19.5 mass parts (yield 60%) of 2nd intermediate products were obtained.
최후에, 톨릴렌디이소시아네이트 3.4질량부, 상기 제 2 중간 생성물 7.7질량부, 및 아세트산 에틸 40질량부를 반응 가마에 넣고, 55℃에서 가열했다. 상기 반응 가마에 스타녹트(요시토미제약사 제작)를 0.05질량부 가했다. 그 후, 6시간 반응시켰다. 방냉 후, 상기 유기상의 용매를 증류 제거하고, 실리카겔 크로마토그래피(전개 용매: 헥산/아세트산에틸=5/5)로 정제함으로써 유상 물질 9.5질량부(수율 83%)를 얻었다.Finally, 3.4 mass parts of tolylene diisocyanate, 7.7 mass parts of said 2nd intermediate products, and 40 mass parts of ethyl acetate were put into the reaction kiln, and it heated at 55 degreeC. 0.05 mass part of stannock (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was added to the reaction kettle. Then, it was reacted for 6 hours. After cooling, the solvent of the said organic phase was distilled off and it refine | purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 5/5), and 9.5 mass parts (yield 83%) of oily substances were obtained.
또, 생성물은 1H-NMR(300MHz:CDCl3)로 동정했다. 스펙트럼의 각 피크는 7.73(s, 1H), 7.22(d, 1H), 7.15(d, 4H), 7.08(d, 1H), 6.87(d, 4H), 6.59(s, 1H), 6.39(s, 1H), 4.33(t, 2H), 3.98(q, 4H), 3.83(t, 2H), 2.95-2.72(m, 8H), 2.19(s, 3H), 1.49(s, 6H)이었다.In addition, the product was identified by 1 H-NMR (300 MHz: CDCl 3 ). Each peak in the spectrum is 7.73 (s, 1H), 7.22 (d, 1H), 7.15 (d, 4H), 7.08 (d, 1H), 6.87 (d, 4H), 6.59 (s, 1H), 6.39 (s , 1H), 4.33 (t, 2H), 3.98 (q, 4H), 3.83 (t, 2H), 2.95-2.72 (m, 8H), 2.19 (s, 3H), 1.49 (s, 6H).
-구조식(9)로 나타내어지는 화합물의 합성-Synthesis of Compound Represented by Structural Formula (9)
디페닐메탄디이소시아네이트 20질량부, 2-메틸-2-프로펜-1-올 11.8질량부, 아세트산 에틸 60질량부를 반응 가마에 넣고, 55℃에서 가열했다. 상기 반응 가마에 스타녹트(요시토미제약사 제작)를 0.05질량부 가했다. 그 후, 6시간 반응시켰다. 방냉 후, 반응 용액을 여과했다. 상기 여액의 용매를 증류 제거하고, 헥산/아세트산 에틸=1/1 용액으로 재결정함으로써 중간 생성물 19.5질량부(수율 62%)를 얻었다.20 mass parts of diphenylmethane diisocyanate, 11.8 mass parts of 2-methyl-2- propene-1-ols, and 60 mass parts of ethyl acetate were put into the reaction kettle, and it heated at 55 degreeC. 0.05 mass part of stannock (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was added to the reaction kettle. Then, it was reacted for 6 hours. After allowing to cool, the reaction solution was filtered. The solvent of the filtrate was distilled off and recrystallized from a hexane / ethyl acetate = 1/1 solution to obtain 19.5 parts by mass (yield 62%) of an intermediate product.
다음에, 상기 중간 생성물 18질량부, 아세트산 에틸 200질량부, 탄산수소나 트륨 40질량부, 물 200질량부, 및 아세톤 65질량부를 반응 가마에 넣었다. 상기 반응 가마에 OXONE 80질량부를 물 350질량부에 용해시킨 수용액을 1시간 걸쳐서 적하했다. 그 후 7시간 반응시켰다. 상기 반응 가마에, 10% 티오황산 나트륨 수용액을 300질량부 가하여 1시간 교반하고, 포화 식염수로 분액하여 유기상을 황산 마그네슘으로 건조했다. 상기 유기상의 용매를 증류 제거하고, 실리카겔 크로마토그래피(전개 용매: 헥산/아세트산 에틸=3/7)로 정제하고, 백색고체 15.4질량부(수율 73%)을 얻었다.Next, 18 parts by mass of the intermediate product, 200 parts by mass of ethyl acetate, 40 parts by mass of hydrogen or sodium carbonate, 200 parts by mass of water, and 65 parts by mass of acetone were placed in a reaction kiln. The aqueous solution which melt | dissolved 80 mass parts of OXONE in 350 mass parts of water was dripped at the said reaction kiln over 1 hour. The reaction was then carried out for 7 hours. 300 mass parts of 10% sodium thiosulfate aqueous solution was added to the said reaction kiln, it stirred for 1 hour, liquid-separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the said organic phase was distilled off, and it refine | purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 3/7), and 15.4 mass parts (yield 73%) of white solids were obtained.
또, 생성물은 1H-NMR(300MHz: CDCl3)로 동정했다. 스펙트럼의 각 피크는 7.30(d, 4H), 7.12(d, 4H), 6.76(s, 2H), 4.37(d, 2H), 4.07(d, 2H), 3.91(s, 2H), 2.83(d, 2H), 2.71(d, 2H), 1.43(s, 6H)이었다.In addition, the product was identified by 1 H-NMR (300 MHz: CDCl 3 ). Each peak in the spectrum is 7.30 (d, 4H), 7.12 (d, 4H), 6.76 (s, 2H), 4.37 (d, 2H), 4.07 (d, 2H), 3.91 (s, 2H), 2.83 (d , 2H), 2.71 (d, 2H) and 1.43 (s, 6H).
-구조식(31)로 나타내어지는 에폭시 수지 화합물의 합성-Synthesis of Epoxy Resin Compound Represented by Structural Formula (31)
톨릴렌디이소시아네이트 20질량부, 2-메틸-2-프로펜-1-올 17질량부, 및 아세트산 에틸 50질량부를 반응 가마에 넣고 55℃에서 가열했다. 상기 반응 가마에 스타녹트(요시토미제약사 제작)를 0.05질량부 가했다. 그 후 6시간 반응시켰다. 방냉 후 반응 용액을 여과했다. 상기 여액의 용매를 증류 제거하고, 헥산/아세트산에틸=1/1 용액으로 재결정함으로써 중간 생성물 20.5질량부(수율 56%)를 얻었다.20 mass parts of tolylene diisocyanate, 17 mass parts of 2-methyl-2-propene-1-ols, and 50 mass parts of ethyl acetate were put into the reaction kiln, and it heated at 55 degreeC. 0.05 mass part of stannock (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was added to the reaction kettle. The reaction was then carried out for 6 hours. After allowing to cool, the reaction solution was filtered. The solvent of the filtrate was distilled off and recrystallized with a hexane / ethyl acetate = 1/1 solution to obtain 20.5 parts by mass of an intermediate product (yield 56%).
다음에, 상기 중간 생성물 20질량부, 아세트산 에틸 150질량부, 탄산수소나트륨 53질량부, 물 150질량부, 및 아세톤 77질량부를 반응 가마에 넣었다. 상기 반응 가마에 OXONE 95질량부를 물 400질량부에 용해시킨 수용액을 1시간 걸쳐서 적하 했다. 그 후 7시간 반응시켰다. 상기 반응 가마에 10% 티오황산 나트륨 수용액을 300질량부 가하여 1시간 교반하고, 포화 식염수로 분액하여 유기상을 황산 마그네슘으로 건조했다. 상기 유기상의 용매를 증류 제거하고, 실리카겔 크로마토그래피(전개 용매: 헥산/아세트산 에틸=5/5)로 정제하고, 유상 물질 11질량부(수율 50%)를 얻었다.Next, 20 parts by mass of the intermediate product, 150 parts by mass of ethyl acetate, 53 parts by mass of sodium bicarbonate, 150 parts by mass of water, and 77 parts by mass of acetone were placed in a reaction kiln. An aqueous solution in which 95 parts by mass of OXONE was dissolved in 400 parts by mass of water was added dropwise to the reaction kettle over 1 hour. The reaction was then carried out for 7 hours. 300 mass parts of 10% sodium thiosulfate aqueous solution was added to the said reaction kiln, it stirred for 1 hour, liquid-separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the said organic phase was distilled off, and it refine | purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 5/5), and 11 mass parts (yield 50%) of oily substances were obtained.
또한, 생성물은 1H-NMR(300MHz:CDCl3)로 동정했다. 스펙트럼의 각 피크는 7.82(s, 1H), 7.21(d, 1H), 7.10(d, 1H), 6.74(s, 1H), 6.51(s, 1H), 4.36(t, 2H), 4.05(d, 2H), 2.82(m, 2H), 2.76(m, 2H), 2.21(s, 3H), 1.43(s, 6H)이다.In addition, the product was identified by 1 H-NMR (300 MHz: CDCl 3 ). Each peak in the spectrum is 7.82 (s, 1H), 7.21 (d, 1H), 7.10 (d, 1H), 6.74 (s, 1H), 6.51 (s, 1H), 4.36 (t, 2H), 4.05 (d , 2H), 2.82 (m, 2H), 2.76 (m, 2H), 2.21 (s, 3H), 1.43 (s, 6H).
(실시예 14)(Example 14)
실시예 1에 있어서, 감광성 조성물 중의 상기 구조식(46)으로 나타내어지는 바인더 40.0질량부를 상기 구조식(46)으로 나타내어지는 바인더 20.0질량부와 이하에 나타내는 합성예 a로 얻어진 불포화기를 갖는 아크릴 수지(B1) 20질량부로 변경하는 것 이외는 실시예 1과 동일한 방법으로 감광성 조성물을 조제하고, 실시예 1과 동일한 방법으로 감광성 필름 및 적층체를 조제하고, 영구 패턴을 형성했다.In Example 1, the acrylic resin (B1) which has 40.0 mass parts of binders represented by the said structural formula (46) in the photosensitive composition, and 20.0 mass parts of binders represented by the said structural formula (46), and the unsaturated group obtained by the synthesis example a shown below. Except having changed into 20 mass parts, the photosensitive composition was prepared by the method similar to Example 1, the photosensitive film and the laminated body were prepared by the method similar to Example 1, and the permanent pattern was formed.
또한, 실시예 1과 동일하게 하여 상기 제조한 감광성 필름에 대해서, 택성, 노광 감도, 해상도, 노광 속도, 및 보존 안정성의 평가를 행하고, 상기 형성한 영구 패턴에 대해서 연필 경도 및 유전 특성의 평가를 행했다. 그 결과, 노광 감도는 30mJ/cm2, 해상도는 70㎛, 노광 속도는 13mJ/cm2이었다. 그 밖의 결과를 표 3에 나타낸다.In addition, evaluation of tackiness, exposure sensitivity, resolution, exposure speed, and storage stability was performed on the photosensitive film prepared in the same manner as in Example 1, and evaluation of pencil hardness and dielectric properties was performed on the formed permanent pattern. Done. As a result, the exposure sensitivity was 30 mJ / cm 2 , the resolution was 70 μm, and the exposure speed was 13 mJ / cm 2 . Other results are shown in Table 3.
-합성예 a(아크릴 수지(B1)의 합성)-Synthesis Example a (Synthesis of Acrylic Resin (B1))-
메틸메타크릴레이트 45.1질량부, 메타크릴산 47.3질량부, 아조이소발레로니트릴 1질량부, 프로필렌글리콜모노메틸에테르 215질량부로 이루어지는 혼합 용액을 질소 가스 분위기 하, 90℃의 반응 용기 중에 3시간 걸쳐서 적하했다. 적하 후, 4시간 반응하고, 아크릴 수지(A1)를 얻었다.A mixed solution consisting of 45.1 parts by mass of methyl methacrylate, 47.3 parts by mass of methacrylic acid, 1 part by mass of azoisovaleronitrile, and 215 parts by mass of propylene glycol monomethyl ether is placed in a reaction vessel at 90 ° C. under a nitrogen gas atmosphere for 3 hours. Dropped. After dripping, it reacted for 4 hours and obtained acrylic resin (A1).
다음에 얻어진 아크릴 수지(A1)용액에 사이크로머 A200(다이셀화학공업(주) 제작) 54.7질량부 및 하이드로퀴논모노메틸에테르 0.2질량부, 트리페닐포스핀 1질량부를 첨가하고, 공기를 블로잉하면서 80℃에서 8시간 반응시켜, 불포화기를 갖는 아크릴 수지(B1) 용액(고형분 산가; 111, Mw; 18,000, 2중 결합 당량 2.3mmol/g, 프로필렌글리콜모노메틸에테르 41질량% 용액)을 얻었다.Next, 54.7 parts by mass of cyclomer A200 (manufactured by Daicel Chemical Industries, Ltd.), 0.2 parts by mass of hydroquinone monomethyl ether, and 1 part by mass of triphenylphosphine were added to the obtained acrylic resin (A1) solution while blowing air. It reacted at 80 degreeC for 8 hours, and obtained the acrylic resin (B1) solution (solid acid value; 111, Mw; 18,000, double bond equivalent 2.3mmol / g, propylene glycol monomethyl ether solution) which has an unsaturated group.
(실시예 15)(Example 15)
실시예 1에 있어서, 감광성 조성물 중의 상기 구조식(46)으로 나타내지는 바인더 40.0질량부를 상기 구조식(46)으로 나타내어지는 바인더 20.0질량부와 이하에 나타내는 합성예 b에서 얻어진 불포화기를 갖는 아크릴 수지(B2) 20질량부로 변경하는 것 이외는, 실시예 1과 동일하게 하여 감광성 조성물을 조제하고, 실시예 1과 동일하게 하여 감광성 필름 및 적층체를 조제하고, 영구 패턴을 형성했다.In Example 1, acrylic resin (B2) which has 40.0 mass parts of binders represented by the said structural formula (46) in the photosensitive composition, and 20.0 mass parts of binders represented by the said structural formula (46), and the unsaturated group obtained by the synthesis example b shown below. Except having changed into 20 mass parts, the photosensitive composition was prepared like Example 1, the photosensitive film and the laminated body were prepared like Example 1, and the permanent pattern was formed.
또한, 실시예 1과 동일하게 하여 상기 제조한 감광성 필름에 대해서, 택성, 노광 감도, 해상도, 노광 속도, 및 보존 안정성의 평가를 행하고, 상기 형성한 영구 패턴에 대해서 연필 경도 및 유전 특성의 평가를 행했다. 그 결과, 노광 감도는 30mJ/cm2, 해상도는 70㎛, 노광 속도는 13mJ/cm2이었다. 그 밖의 결과를 표 3에 나타낸다.In addition, evaluation of tackiness, exposure sensitivity, resolution, exposure speed, and storage stability was performed on the photosensitive film prepared in the same manner as in Example 1, and evaluation of pencil hardness and dielectric properties was performed on the formed permanent pattern. Done. As a result, the exposure sensitivity was 30 mJ / cm 2 , the resolution was 70 μm, and the exposure speed was 13 mJ / cm 2 . Other results are shown in Table 3.
-합성예 b(아크릴 수지(B2)의 합성)-Synthesis Example b (synthesis of acrylic resin (B2))
메틸메타크릴레이트 45.1질량부, 메타크릴산 47.3질량부, 아조이소발레로니트릴 1질량부, 프로필렌글리콜모노메틸에테르 215질량부로 이루어지는 혼합 용액을 질소 가스 분위기 하, 90℃의 반응 용기 중에 3시간 걸쳐서 적하했다. 적하 후 4시간 반응하고, 아크릴 수지(A2)를 얻었다.A mixed solution consisting of 45.1 parts by mass of methyl methacrylate, 47.3 parts by mass of methacrylic acid, 1 part by mass of azoisovaleronitrile, and 215 parts by mass of propylene glycol monomethyl ether is placed in a reaction vessel at 90 ° C. under a nitrogen gas atmosphere for 3 hours. Dropped. It reacted for 4 hours after dripping, and obtained acrylic resin (A2).
다음에, 얻어진 아크릴 수지(A2) 용액에 글리시딜메타크릴레이트 35.9질량부 및 하이드로퀴논모노메틸에테르 0.2질량부, 트리페닐포스핀 1질량부를 가하고, 공기를 블로잉하면서 80℃에서 8시간 반응시켜서, 불포화기를 갖는 아크릴 수지(B2) 용액(고형분 산가; 104, Mw; 20,000, 2중 결합 당량 2.0mmol/g, 프로필렌글리콜모노메틸에테르 37질량%용액)을 얻었다.Next, 35.9 mass parts of glycidyl methacrylate, 0.2 mass part of hydroquinone monomethyl ether, and 1 mass part of triphenylphosphines are added to the obtained acrylic resin (A2) solution, and it is made to react at 80 degreeC for 8 hours, blowing air, And acrylic resin (B2) solution (solid acid value; 104, Mw; 20,000, double bond equivalent 2.0mmol / g, 37 mass% solution of propylene glycol monomethyl ether) which have an unsaturated group were obtained.
(실시예 16∼19)(Examples 16 to 19)
상기 실시예 1, 5, 7 및 10에 있어서, 노광 장치를 일본특허공개 2005-258431호 공보의 단락번호[0383]∼ [0393]에 기재되어 있는 패턴 형성 장치로 대신한 것 이외는, 실시예 1과 동일하게 하여 상기 제조한 감광성 조성물 및 감광성 필름에 대해서, 택성, 노광 감도, 해상도, 노광 속도의 평가를 행하고, 상기 형성한 영구 패턴에 대해서 연필 경도, 및 유전 특성의 평가를 행했다. 실시예 16∼19에 있어서의 노광 감도는 30mJ/cm2, 해상도는 70㎛, 노광 속도는 7mJ/cm2이다. 연필 경 도, 유전 특성, 보존 안정성에 관한 결과를 표 3에 나타낸다.Examples 1, 5, 7, and 10, except that the exposure apparatus was replaced with the pattern forming apparatus described in paragraphs [0383] to [0393] of JP-A-2005-258431. In the same manner as in 1, the prepared photosensitive composition and the photosensitive film were evaluated for tackiness, exposure sensitivity, resolution, and exposure speed, and pencil hardness and dielectric properties were evaluated for the formed permanent pattern. The exposure sensitivity in Examples 16-19 is 30 mJ / cm <2> , the resolution is 70 micrometers, and an exposure speed is 7 mJ / cm <2> . Table 3 shows the results of pencil hardness, dielectric properties, and storage stability.
(비교예 1)(Comparative Example 1)
실시예 1에 있어서, 감광성 조성물 중의 상기 구조식(1)로 나타내어지는 화합물을 2,2'-비스(4-글리시딜페닐)프로판으로 변경한 것 이외는, 실시예 1과 동일하게 하여 감광성 조성물을 조제하고, 실시예 1과 동일하게 하여 감광성 필름 및 적층체를 조제하고, 영구 패턴을 형성했다.In Example 1, except having changed the compound represented by the said Structural formula (1) in the photosensitive composition into 2,2'-bis (4-glycidyl phenyl) propane, it carried out similarly to Example 1, and the photosensitive composition Was prepared, the photosensitive film and the laminated body were prepared like Example 1, and the permanent pattern was formed.
또한 실시예 1과 동일하게 하여 상기 제조한 감광성 필름에 대해서, 택성, 노광 감도, 해상도, 노광 속도, 및 보존 안정성의 평가를 행하고, 상기 형성한 영구 패턴에 대해서 연필 경도 및 유전 특성의 평가를 행했다. 또, 비교예 1 및 이후의 비교예 2, 3에 있어서, 노광 감도는 30mJ/cm2, 해상도는 70㎛, 노광 속도는 13mJ/cm2이었다. 그 밖의 결과를 표 3에 나타낸다.In addition, the tackiness, the exposure sensitivity, the resolution, the exposure speed, and the storage stability were evaluated for the photosensitive film prepared in the same manner as in Example 1, and the pencil hardness and dielectric properties were evaluated for the formed permanent pattern. . In Comparative Example 1 and Comparative Examples 2 and 3 thereafter, the exposure sensitivity was 30 mJ / cm 2 , the resolution was 70 μm, and the exposure speed was 13 mJ / cm 2 . Other results are shown in Table 3.
(비교예 2)(Comparative Example 2)
실시예 1에 있어서, 감광성 조성물 중의 상기 구조식(1)로 나타내어지는 화합물을 에피 코트 YX4000(재팬에폭시레진사 제작, 에폭시 수지)로 변경한 것 이외는 실시예 1과 동일한 방법으로 감광성 조성물을 제조하고, 실시예 1과 동일하게 하여 감광성 필름 및 적층체를 제조하고, 영구 패턴을 형성했다.In Example 1, the photosensitive composition was manufactured by the method similar to Example 1 except having changed the compound represented by the said Structural formula (1) in the photosensitive composition to Epicoat YX4000 (made by Japan Epoxy Resin Co., Ltd., epoxy resin). In the same manner as in Example 1, a photosensitive film and a laminate were manufactured, and a permanent pattern was formed.
또한, 실시예 1과 동일한 방법으로 상기 제조한 감광성 필름에 대해서, 택성, 노광 감도, 해상도, 노광 속도, 및 보존 안정성의 평가를 행하고, 상기 형성한 영구 패턴에 대해서 연필 경도 및 유전 특성의 평가를 행했다. 결과를 표 3에 나타 낸다.Moreover, about the photosensitive film manufactured above by the method similar to Example 1, evaluation of tackiness, exposure sensitivity, resolution, exposure speed, and storage stability is performed, and evaluation of pencil hardness and dielectric property is performed about the formed permanent pattern. Done. The results are shown in Table 3.
(비교예 3)(Comparative Example 3)
실시예 1에 있어서, 감광성 조성물 중의 상기 구조식(1)로 나타내어지는 화합물을 TEPIC(닛산화학공업사 제작, 에폭시 수지)로 변경하는 것 이외는, 실시예 1과 동일하게 하여 감광성 조성물을 제조하고, 실시예 1과 동일한 방법으로 감광성 필름 및 적층체를 조제하고, 영구 패턴을 형성했다.In Example 1, the photosensitive composition was manufactured and performed similarly to Example 1 except having changed the compound represented by the said Structural formula (1) in the photosensitive composition into TEPIC (made by Nissan Chemical Corporation, epoxy resin). In the same manner as in Example 1, a photosensitive film and a laminate were prepared to form a permanent pattern.
또한, 실시예 1과 동일하게 하여 상기 제조한 감광성 필름에 대해서, 택성, 노광 감도, 해상도, 노광 속도, 및 보존 안정성의 평가를 행하고, 상기 형성한 영구 패턴에 대해서 연필 경도 및 유전 특성의 평가를 행했다. 결과를 표 3에 나타낸다.In addition, evaluation of tackiness, exposure sensitivity, resolution, exposure speed, and storage stability was performed on the photosensitive film prepared in the same manner as in Example 1, and evaluation of pencil hardness and dielectric properties was performed on the formed permanent pattern. Done. The results are shown in Table 3.
표 3의 결과로부터, 일반식(1)∼(3)으로 나타내어지는 화합물로부터 선택되는 적어도 1종의 화합물을 함유하는 실시예 1∼19의 감광성 조성물을 사용하여 제조한 감광성 필름에 있어서의 감광층은 택성, 노광 감도 및 해상도가 우수하고, 상기 감광성 필름을 이용하여 형성한 영구 패턴에 있어서의 경화층의 표면 경도, 유전 특성이 양호하고, 종래 공지의 에폭시 수지 화합물을 열가교제로서 사용한 비교예 1∼3의 감광성 필름에 비하여, 보존 안정성이 매우 우수하다는 것이 확인되었다. 특히, 상기 화합물의 감광성 조성물 중에서의 함유량이 0.01∼15질량%인 실시예 1∼2, 5∼19의 감광성 필름은 보존 안정성 및 유전 특성의 쌍방이 매우 우수하다는 것이 판명되었다.From the result of Table 3, the photosensitive layer in the photosensitive film manufactured using the photosensitive composition of Examples 1-19 containing at least 1 sort (s) of compound chosen from the compound represented by General formula (1)-(3). Comparative example 1 which was excellent in silver tackiness, exposure sensitivity, and resolution, the surface hardness of the hardened layer and the dielectric property in the permanent pattern formed using the said photosensitive film was favorable, and used the conventionally well-known epoxy resin compound as a thermal crosslinking agent. It was confirmed that storage stability is very excellent compared with the photosensitive film of -3. In particular, it turned out that the photosensitive films of Examples 1-2 and 5-19 whose content in the photosensitive composition of the said compound are 0.01-15 mass% are excellent both in storage stability and dielectric properties.
또한, 실시예 1, 5, 7 및 10과 동일한 감광성 필름을 사용한 실시예 16∼19에서는, 고휘도 광원으로 고속 변조 가능하고, 또한, 토릭 렌즈에 의한 광학계 변형 보정이 가능한 패턴 형성 장치를 사용했기 때문에, 해상도 및 노광 속도가 우수하다는 것이 확인되고, 고정밀한 영구 패턴이 형성되는 것이 확인되었다.In addition, in Examples 16 to 19 using the same photosensitive film as in Examples 1, 5, 7 and 10, since a pattern forming apparatus capable of high-speed modulation with a high brightness light source and optical system distortion correction by a toric lens was used, It was confirmed that the resolution and the exposure speed were excellent, and that a high-precision permanent pattern was formed.
본 발명의 감광성 조성물 및 상기 감광성 조성물을 사용한 감광성 필름은 보존시의 상온 하에서는 반응을 일으키지 않고, 가열에 의해 가교 반응을 개시하고, 경화막의 양호한 막경도가 얻어지는 화합물을 함유하고, UV노광에 의해 화상 형성가능하고, 표면의 택성이 작고, 라미네이트성 및 취급성이 양호하고, 보존 안정성이 우수하고, 고감도이고, 현상성이 우수하고, 현상 후에 우수한 내약품성, 표면 경도, 내열성, 유전 특성 등을 발현시키기 때문에 프린트 배선판(다층 배선 기판, 빌드업 배선 기판 등)의 보호막, 층간 절연막, 및 솔더 레지스트 패턴, 및 컬러 필터나 골재, 리브재, 스페이서, 격벽 등의 디스플레이용 부재, 홀로그램, 마이크로머신, 프루프 등의 영구 패턴 형성용으로서 널리 사용할 수 있다.The photosensitive composition of this invention and the photosensitive film using the said photosensitive composition contain the compound which does not produce reaction under normal temperature at the time of storage, starts a crosslinking reaction by heating, and obtains the favorable film hardness of a cured film, and is imaged by UV exposure. Formable, small surface tack, good lamination and handleability, excellent storage stability, high sensitivity, developability, excellent chemical resistance, surface hardness, heat resistance, dielectric properties after development Protective films of printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), interlayer insulating films, and solder resist patterns, and display members such as color filters, aggregates, ribs, spacers, partition walls, holograms, micromachines, and proofs. It can be used widely for permanent pattern formation, such as these.
또한, 본 발명의 영구 패턴은 내약품성, 표면경도, 내열성, 유전 특성, 전기절연성이 우수하다. 이 때문에, 프린트 배선판(다층 배선 기판, 빌드업 배선 기판등)의 보호막, 층간 절연막, 솔더 레지스트 패턴 및 컬러 필터나 골재, 리브재, 스페이서, 격벽 등의 디스플레이용 부재, 홀로그램, 마이크로머신, 프루프 등의 영구 패턴 형성용으로서 널리 사용할 수 있다고 하는 점에서 바람직하게 사용할 수 있다.In addition, the permanent pattern of the present invention is excellent in chemical resistance, surface hardness, heat resistance, dielectric properties, electrical insulation. For this reason, protective films of printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), interlayer insulating films, solder resist patterns, display members such as color filters, aggregates, ribs, spacers, partition walls, holograms, micromachines, proofs, and the like. It can be used preferably from the point which can be used widely for permanent pattern formation of the resin.
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WO2014103516A1 (en) * | 2012-12-27 | 2014-07-03 | 日立化成株式会社 | Photosensitive resin composition, photosensitive film, and method for forming resist pattern |
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EP1431325A1 (en) * | 2002-12-17 | 2004-06-23 | Sika Technology AG | Heat-curable epoxy resin composition with improved low-temperatur impact strength |
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