KR20230149727A - Photosensitive composition, optical filter, image display device, and solid-state imaging device - Google Patents

Photosensitive composition, optical filter, image display device, and solid-state imaging device Download PDF

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KR20230149727A
KR20230149727A KR1020230043445A KR20230043445A KR20230149727A KR 20230149727 A KR20230149727 A KR 20230149727A KR 1020230043445 A KR1020230043445 A KR 1020230043445A KR 20230043445 A KR20230043445 A KR 20230043445A KR 20230149727 A KR20230149727 A KR 20230149727A
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carbon atoms
parts
photopolymerization initiator
photosensitive composition
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KR1020230043445A
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Korean (ko)
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히로아키 카와우치
히로유키 요시다
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토요잉크Sc홀딩스주식회사
도요 비주얼 솔루션스 주식회사
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Publication of KR20230149727A publication Critical patent/KR20230149727A/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures

Abstract

(요약) 본 발명은, 현상 후의 피막의 물 얼룩을 억제하고, 잔막률이 양호하며, 우수한 패턴을 형성할 수 있는 감광성 조성물의 제공을 목적으로 한다.
(해결 수단) 본 발명은, 알칼리 가용성 수지(A), 중합성 화합물(B), 및 광중합개시제(C)를 포함하고, 상기 광중합개시제(C)는, 하기 일반식(1)으로 표시되는 옥심계 광중합개시제(C1), 및 옥심계 광중합개시제(C1) 이외의 옥심계 광중합개시제(C2)를 포함하는, 감광성 조성물.
[화 1]
일반식(1)

(일반식(1) 중, R1은, 수소 원자, 탄소 원자수 1 ∼ 20의 알킬기, 탄소 원자수 6 ∼ 30의 아릴기, 탄소 원자수 7 ∼ 30의 아릴알킬기, 또는 탄소 원자수 2 ∼ 20의 복소환기를 나타낸다.
R2은, 탄소 원자수 3 ∼ 20의 알킬기, 탄소 원자수 6 ∼ 30의 아릴기, 탄소 원자수 7 ∼ 30의 아릴알킬기, 또는 탄소 원자수 2 ∼ 20의 복소환기를 나타낸다.
R3은, 탄소 원자수 3 ∼ 20의 알킬기, 탄소 원자수 6 ∼ 30의 아릴기, 탄소 원자수 7 ∼ 30의 아릴알킬기, 또는 탄소 원자수 2 ∼ 20의 복소환기를 나타낸다.
R4은, 치환기를 가져도 되는 벤조일기를 나타내고, n은, 1을 나타낸다.)(Summary) The purpose of the present invention is to provide a photosensitive composition that suppresses water stains on the film after development, has a good residual film rate, and can form an excellent pattern.
(Solution) The present invention includes an alkali-soluble resin (A), a polymerizable compound (B), and a photopolymerization initiator (C), wherein the photopolymerization initiator (C) is an oxime represented by the following general formula (1): A photosensitive composition comprising an oxime-based photopolymerization initiator (C1) and an oxime-based photopolymerization initiator (C2) other than the oxime-based photopolymerization initiator (C1).
[Tuesday 1]
General formula (1)

(In General Formula (1), R 1 is a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or 2 to 2 carbon atoms. It represents the heterocycle of 20.
R 2 represents an alkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.
R 3 represents an alkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.
R 4 represents a benzoyl group which may have a substituent, and n represents 1.)

Description

감광성 조성물, 광학 필터, 화상 표시 장치, 및 고체 촬상 소자{PHOTOSENSITIVE COMPOSITION, OPTICAL FILTER, IMAGE DISPLAY DEVICE, AND SOLID-STATE IMAGING DEVICE}Photosensitive composition, optical filter, image display device, and solid-state imaging device {PHOTOSENSITIVE COMPOSITION, OPTICAL FILTER, IMAGE DISPLAY DEVICE, AND SOLID-STATE IMAGING DEVICE}

본 발명은 감광성 조성물, 그것을 이용하는 광학 필터에 관한 것이다.The present invention relates to a photosensitive composition and an optical filter using the same.

화상 표시 장치나 고체 촬상 소자 등에 사용하는 광학 필터의 1종 컬러 필터는, 유리 기판 등의 투명한 기판 상에, 색상이 다른 2종 이상의 미세한 띠상(帶狀)의 필터 세그먼트를 서로 평행하게(스트라이프상으로) 또는 교차하도록 배치한다. 또는, 색상이 다른 2종 이상의 미세한 필터 세그먼트를 종 방향 및 횡 방향의 각각에 있어서 순서대로 배열하도록 배치한다. 이 필터 세그먼트는, 수 미크론 ∼ 수 100미크론의 작은 치수를 갖고 있으며, 색상마다 소정의 배열로 정연하게 배치되어 있다.A color filter, a type of optical filter used in image display devices or solid-state imaging devices, consists of two or more types of fine strip-shaped filter segments of different colors arranged in parallel (in a stripe shape) on a transparent substrate such as a glass substrate. ) or arranged so that they intersect. Alternatively, two or more types of fine filter segments of different colors are arranged in order in each of the longitudinal and transverse directions. These filter segments have small dimensions ranging from a few microns to several 100 microns, and are arranged neatly in a predetermined arrangement for each color.

현재, 컬러 필터의 제조 방법으로서는, 감광성 조성물을, 유리 등의 투명 기판에 도포하고, 건조에 의해 이 도막으로부터 용제를 제거하는 공정, 이 도막을, 원하는 패턴 형상을 갖는 포토마스크를 개재하여 방사선을 조사·경화(이하, 노광이라고 함) 공정, 그 다음에, 이 도막의 미노광부를 세정·제거(이하, 현상이라고 함)하는 공정, 그 후, 필요에 따라 경화막을 충분히 경화시키기 위해 가열 처리(이하, 포스트 베이크라고 함) 공정에 의해 1색째의 필터 세그먼트 패턴을 얻는다. 그리고, 이것과 마찬가지의 조작을 행함으로써 다른 색의 필터 세그먼트 패턴을 형성하고, 컬러 필터를 완성한다.Currently, the manufacturing method of a color filter includes the process of applying a photosensitive composition to a transparent substrate such as glass, removing the solvent from the coating film by drying, and exposing the coating film to radiation through a photomask having a desired pattern shape. An irradiation/curing (hereinafter referred to as exposure) process, followed by a process of cleaning and removing the unexposed portion of the coating film (hereinafter referred to as development), and then, if necessary, heat treatment (hereinafter referred to as development) to sufficiently cure the cured film. The first color filter segment pattern is obtained through a process (hereinafter referred to as post-bake). Then, by performing an operation similar to this, filter segment patterns of different colors are formed, and the color filter is completed.

상기 현상 공정은, 현상액으로서 알칼리성의 현상액을 이용하여, 미노광 부분을 세정·제거한다. 그때, 노광된 부분이 빠지거나, 벗겨져 패턴 형상에 결함이 발생한다는 문제가 있었다. 또한, 알칼리성의 현상액에 도막이 노출되었을 경우, 도막이 변색되는 현상(이하, 물 얼룩이라고 함)이 발생하는 문제도 있었다. 그 때문에, 현상 공정에서 패턴 형상의 불량과 물 얼룩이 발생하지 않는 감광성 조성물이 요구되고 있다. 또한, 현상 공정이나 포스트 베이크 공정 시에, 미반응물 등이 용출(溶出)이나 기화(氣化)됨으로써 도막의 막두께가 변화하는(이하, 잔막률이라고 함) 문제도 있었다.In the development process, an alkaline developer is used as a developer to clean and remove the unexposed portion. At that time, there was a problem that the exposed portion was missing or peeled off, causing defects in the pattern shape. Additionally, when the coating film is exposed to an alkaline developer, there is a problem of discoloration of the coating film (hereinafter referred to as water staining). Therefore, there is a demand for a photosensitive composition that does not cause pattern shape defects and water stains during the development process. In addition, there was a problem that the film thickness of the coating film changed (hereinafter referred to as residual film rate) due to the elution or vaporization of unreacted substances during the development process or post-bake process.

물 얼룩을 개선하기 위한 노력으로서, 특허문헌 1에는, 특정 구조의 불소계 계면활성제를 포함하는 레지스트 조성물이 개시되어 있다. 또한, 현상 시의 패턴 결함을 개선하기 위한 노력으로서, 특허문헌 2에는, 알킬렌옥사이드 구조를 갖는 중합성 화합물을 포함하는 착색 조성물이 개시되어 있다. 또한, 고농도의 착색제를 포함하는 경우의 패턴 형성성을 개선하기 위한 노력으로서, 특허문헌 3에는, 다관능 티올 화합물 및 아세토페논 화합물을 포함하는 착색 감광성 수지 조성물이 개시되어 있다.As an effort to improve water stains, Patent Document 1 discloses a resist composition containing a fluorine-based surfactant with a specific structure. Additionally, as an effort to improve pattern defects during development, Patent Document 2 discloses a coloring composition containing a polymerizable compound having an alkylene oxide structure. Additionally, as an effort to improve pattern formation when a high concentration of colorant is included, Patent Document 3 discloses a colored photosensitive resin composition containing a polyfunctional thiol compound and an acetophenone compound.

일본 특허공개 2016-102212호 공보Japanese Patent Publication No. 2016-102212 일본 특허공개 2014-142582호 공보Japanese Patent Publication No. 2014-142582 일본 특허공개 2004-83857호 공보Japanese Patent Publication No. 2004-83857

그러나, 특허문헌 1 ∼ 3 중 어느 조성물도 물 얼룩, 패턴 형상을 만족할 수 있는 것은 아니었다. 또한, 잔막률에 관해서는 고려되고 있지 않아, 만족스럽지 못했다.However, none of the compositions in Patent Documents 1 to 3 could satisfy water stains and pattern shapes. Additionally, the residual film rate was not taken into consideration and was not satisfactory.

본 발명은, 현상 후의 피막의 물 얼룩을 억제하고, 잔막률이 양호하며, 우수한 패턴을 형성할 수 있는 감광성 조성물의 제공을 목적으로 한다.The purpose of the present invention is to provide a photosensitive composition that suppresses water stains on a film after development, has a good residual film rate, and can form an excellent pattern.

[1] 본 발명은, 알칼리 가용성 수지(A), 중합성 화합물(B), 및 광중합개시제(C)를 포함하는 감광성 조성물로서,[1] The present invention is a photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), and a photopolymerization initiator (C),

상기 광중합개시제(C)는, 하기 일반식(1)으로 표시되는 옥심계 광중합개시제(C1), 및 옥심계 광중합개시제(C1) 이외의 옥심계 광중합개시제(C2)를 포함하는, 감광성 조성물이다.The photopolymerization initiator (C) is a photosensitive composition containing an oxime-based photopolymerization initiator (C1) represented by the following general formula (1), and an oxime-based photopolymerization initiator (C2) other than the oxime-based photopolymerization initiator (C1).

[화 1][Tuesday 1]

일반식(1)General formula (1)

(일반식(1) 중, R1은, 수소 원자, 탄소 원자수 1 ∼ 20의 알킬기, 탄소 원자수 6 ∼ 30의 아릴기, 탄소 원자수 7 ∼ 30의 아릴알킬기, 또는 탄소 원자수 2 ∼ 20의 복소환기를 나타낸다.(In General Formula (1), R 1 is a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or 2 to 2 carbon atoms. It represents the heterocycle of 20.

R2은, 탄소 원자수 3 ∼ 20의 알킬기, 탄소 원자수 6 ∼ 30의 아릴기, 탄소 원자수 7 ∼ 30의 아릴알킬기, 또는 탄소 원자수 2 ∼ 20의 복소환기를 나타낸다.R 2 represents an alkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.

R3은, 탄소 원자수 3 ∼ 20의 알킬기, 탄소 원자수 6 ∼ 30의 아릴기, 탄소 원자수 7 ∼ 30의 아릴알킬기, 또는 탄소 원자수 2 ∼ 20의 복소환기를 나타낸다.R 3 represents an alkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.

R4은, 치환기를 가져도 되는 벤조일기를 나타내고, n은, 1을 나타낸다.)R 4 represents a benzoyl group which may have a substituent, and n represents 1.)

[2] 상기 옥심계 광중합개시제(C1)와 상기 옥심계 광중합개시제(C1) 이외의 옥심계 광중합개시제(C2)의 질량비는, 90:10 ∼ 10:90인, [1]에 기재된 감광성 조성물.[2] The photosensitive composition according to [1], wherein the mass ratio of the oxime-based photopolymerization initiator (C1) and the oxime-based photopolymerization initiator (C2) other than the oxime-based photopolymerization initiator (C1) is 90:10 to 10:90.

[3] 상기 옥심계 광중합개시제(C1)와 상기 옥심계 광중합개시제(C1) 이외의 옥심계 광중합개시제(C2)의 합계 함유량은, 상기 광중합개시제(C) 100질량％ 중, 50질량％ 이상인, [1] 또는 [2]에 기재된 감광성 조성물.[3] The total content of the oxime-based photopolymerization initiator (C1) and the oxime-based photopolymerization initiator (C2) other than the oxime-based photopolymerization initiator (C1) is 50% by mass or more, based on 100% by mass of the photopolymerization initiator (C). The photosensitive composition according to [1] or [2].

[4] 상기 알칼리 가용성 수지(A)는, 지환식 탄화수소 함유 단량체 단위(a1), 및 카르복시기 함유 단량체 단위(a2)를 함유하는 알칼리 가용성 수지(A1)를 포함하는, [1] 내지 [3] 중 어느 것에 기재된 감광성 조성물.[4] The alkali-soluble resin (A) includes an alicyclic hydrocarbon-containing monomer unit (a1) and an alkali-soluble resin (A1) containing a carboxyl group-containing monomer unit (a2), [1] to [3] The photosensitive composition according to any one of the above.

[5] 상기 알칼리 가용성 수지(A1)는, 상기 지환식 탄화수소 함유 단량체 단위(a1)를, 상기 알칼리 가용성 수지(A1)의 전체 구성 단위 중, 5 ∼ 60몰％ 포함하는, [1] 내지 [4] 중 어느 것에 기재된 감광성 조성물.[5] The alkali-soluble resin (A1) contains 5 to 60 mol% of the alicyclic hydrocarbon-containing monomer unit (a1) based on the total constituent units of the alkali-soluble resin (A1), [1] to [ 4] The photosensitive composition according to any one of the above.

[6] 티올계 연쇄 이동제(D)를 더 포함하는, [1] 내지 [5] 중 어느 것에 기재된 감광성 조성물.[6] The photosensitive composition according to any one of [1] to [5], further comprising a thiol-based chain transfer agent (D).

[7] 기판, 및 [1] 내지 [6] 중 어느 것에 기재된 감광성 조성물로 형성되어 이루어지는 필터 세그먼트를 갖는, 광학 필터.[7] An optical filter having a substrate and a filter segment formed of the photosensitive composition according to any one of [1] to [6].

[8] [7]에 기재된 광학 필터를 갖는, 화상 표시 장치.[8] An image display device having the optical filter described in [7].

[9] [7]에 기재된 광학 필터를 갖는, 고체 촬상 소자.[9] A solid-state imaging device having the optical filter described in [7].

상기의 본 발명에 의하면, 현상 후의 피막의 물 얼룩을 억제하고, 잔막률이 양호하며, 우수한 패턴을 형성할 수 있는 감광성 조성물을 제공할 수 있다. 또한, 본 발명은, 광학 필터, 화상 표시 장치, 및 고체 촬상 소자를 제공할 수 있다.According to the above-described present invention, it is possible to provide a photosensitive composition that suppresses water stains on the film after development, has a good residual film rate, and can form an excellent pattern. Additionally, the present invention can provide an optical filter, an image display device, and a solid-state imaging device.

이하에, 본 발명의 감광성 조성물을 실시하기 위한 형태에 대해서 상세하게 설명한다. 또, 본 발명은, 이하의 실시형태에 제한되는 것이 아니고, 과제를 해결 가능한 범위 내에서 변형하여 실시할 수 있다.Below, modes for implementing the photosensitive composition of the present invention will be described in detail. In addition, the present invention is not limited to the following embodiments, and can be implemented with modifications within the range capable of solving the problem.

본 발명에 있어서, 「(메타)아크릴로일」, 「(메타)아크릴」, 「(메타)아크릴산」, 「(메타)아크릴레이트」, 또는 「(메타)아크릴아미드」란, 특별히 설명이 없는 한, 각각, 「아크릴로일 및／또는 메타아크릴로일」, 「아크릴 및／또는 메타아크릴」, 「아크릴산 및／또는 메타아크릴산」, 「아크릴레이트 및／또는 메타크릴레이트」, 또는 「아크릴아미드 및／또는 메타아크릴아미드」를 의미한다. 또한, 「C.I.」는, 컬러 인덱스(C.I.; The Society of Dyers and Colourists 발행)를 의미한다. 중합성 불포화기는, 에틸렌성 불포화 이중 결합이다.In the present invention, “(meth)acryloyl”, “(meth)acrylic”, “(meth)acrylic acid”, “(meth)acrylate”, or “(meth)acrylamide” refers to substances without particular explanation. As long as, respectively, “acryloyl and/or methacryloyl”, “acrylic and/or methacrylic”, “acrylic acid and/or methacrylic acid”, “acrylate and/or methacrylate”, or “acrylamide” and/or methacrylamide.” Additionally, “C.I.” means Color Index (C.I.; published by The Society of Dyers and Colourists). The polymerizable unsaturated group is an ethylenically unsaturated double bond.

또한, 본 발명에 있어서의 화합물의 분자량에 관해서는, 분자량을 특정할 수 있는 저분자 화합물에 대해서는, 계산에 의해 산출한 값(식량), 또는 ESi-MS(일렉트로 스프레이 이온화 질량 분석법)에 의해 측정한 분자량이며, 분자량의 분포를 가지는 화합물에 대해서는, 테트라히드로퓨란을 용제로 했을 경우의 겔퍼미에이션 크로마토그래피로 측정되는 폴리스티렌 환산의 중량 평균 분자량이다. 중합성 화합물(B)은, 경화에 의해 피막을 형성하는 화합물이다. 단량체는, 중합에 의해 수지를 형성하는 화합물이다. 단량체는, 미반응 상태이며, 단량체 단위는, 단량체를 중합 후에 수지를 형성하고 있는 상태이다.In addition, regarding the molecular weight of the compound in the present invention, for low molecular compounds whose molecular weight can be specified, the value calculated by calculation (food weight) or measured by ESi-MS (electro spray ionization mass spectrometry) It is the molecular weight, and for compounds with molecular weight distribution, it is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as the solvent. The polymerizable compound (B) is a compound that forms a film by curing. A monomer is a compound that forms a resin by polymerization. The monomer is in an unreacted state, and the monomer unit is in a state of forming a resin after polymerizing the monomer.

<감광성 조성물><Photosensitive composition>

본 발명의 일 실시형태는, 감광성 조성물에 관한 것이다. 본 발명의 감광성 조성물은, 알칼리 가용성 수지(A), 중합성 화합물(B), 및 광중합개시제(C)를 포함하는 감광성 조성물로서,One embodiment of the present invention relates to a photosensitive composition. The photosensitive composition of the present invention is a photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), and a photopolymerization initiator (C),

상기 광중합개시제(C)는, 하기 일반식(1)으로 표시되는 옥심계 광중합개시제(C1), 및 옥심계 광중합개시제(C1) 이외의 옥심계 광중합개시제(C2)를 포함한다. 본 발명의 감광성 조성물은, 패턴 형성 가능하며, 피막을 형성하고 광경화하여 사용하는 것이 바람직하다. 상기 피막은, 예를 들면, 화상 표시 장치, 고체 촬상 소자의 광학 디바이스에 편성하는 용도가 바람직하다.The photopolymerization initiator (C) includes an oxime-based photopolymerization initiator (C1) represented by the following general formula (1), and an oxime-based photopolymerization initiator (C2) other than the oxime-based photopolymerization initiator (C1). The photosensitive composition of the present invention can be patterned, and is preferably used by forming a film and photocuring it. The film is preferably used in optical devices such as image display devices and solid-state imaging devices.

일반식(1)General formula (1)

[화 2][Tuesday 2]

일반식(1) 중, R1은, 수소 원자, 탄소 원자수 1 ∼ 20의 알킬기, 탄소 원자수 6 ∼ 30의 아릴기, 탄소 원자수 7 ∼ 30의 아릴알킬기, 또는 탄소 원자수 2 ∼ 20의 복소환기를 나타낸다.In general formula (1), R 1 is a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or 2 to 20 carbon atoms. It represents the heterocyclic group of .

R2은, 탄소 원자수 3 ∼ 20의 알킬기, 탄소 원자수 6 ∼ 30의 아릴기, 탄소 원자수 7 ∼ 30의 아릴알킬기, 또는 탄소 원자수 2 ∼ 20의 복소환기를 나타낸다.R 2 represents an alkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.

R3은, 탄소 원자수 3 ∼ 20의 알킬기, 탄소 원자수 6 ∼ 30의 아릴기, 탄소 원자수 7 ∼ 30의 아릴알킬기, 또는 탄소 원자수 2 ∼ 20의 복소환기를 나타낸다.R 3 represents an alkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.

R4은, 치환기를 가져도 되는 벤조일기를 나타내고, n은, 1을 나타낸다.R 4 represents a benzoyl group which may have a substituent, and n represents 1.

이하, 일 실시형태의 감광성 조성물에 포함되거나, 또는 포함될 수 있는 성분을 상세하게 설명한다.Hereinafter, components that are included or may be included in the photosensitive composition of one embodiment will be described in detail.

[광중합개시제(C)][Light polymerization initiator (C)]

본 발명의 감광성 조성물은, 광중합개시제(C)로서, 일반식(1)으로 표시되는 옥심계 광중합개시제(C1), 및 옥심계 광중합개시제(C1) 이외의 옥심계 광중합개시제(C2)를 포함한다.The photosensitive composition of the present invention contains, as a photopolymerization initiator (C), an oxime-based photopolymerization initiator (C1) represented by general formula (1), and an oxime-based photopolymerization initiator (C2) other than the oxime-based photopolymerization initiator (C1). .

(C1)과 다른 구조인 (C2)를 병용함으로써, 유효하게 이용할 수 있는 광의 파장 영역이 퍼져 감도가 향상됨으로써, 피막이 강인(强靭)해져 물 얼룩, 잔막률이 양호해지는 것으로 생각된다.It is believed that by using (C2), which has a structure different from (C1), in combination, the wavelength range of light that can be effectively used is spread and sensitivity is improved, thereby making the film stronger and improving water staining and residual film rate.

(옥심계 광중합개시제(C1))(Oxime-based photopolymerization initiator (C1))

옥심계 광중합개시제(C1)는, 하기 일반식(1)으로 표시되는 화합물이다.The oxime-based photopolymerization initiator (C1) is a compound represented by the following general formula (1).

일반식(1)General formula (1)

[화 3][Tuesday 3]

일반식(1) 중, R1은, 수소 원자, 탄소 원자수 1 ∼ 20의 알킬기, 탄소 원자수 6 ∼ 30의 아릴기, 탄소 원자수 7 ∼ 30의 아릴알킬기, 또는 탄소 원자수 2 ∼ 20의 복소환기를 나타낸다.In general formula (1), R 1 is a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or 2 to 20 carbon atoms. It represents the heterocyclic group of .

R2은, 탄소 원자수 3 ∼ 20의 알킬기, 탄소 원자수 6 ∼ 30의 아릴기, 탄소 원자수 7 ∼ 30의 아릴알킬기, 또는 탄소 원자수 2 ∼ 20의 복소환기를 나타낸다.R 2 represents an alkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.

R3은, 탄소 원자수 3 ∼ 20의 알킬기, 탄소 원자수 6 ∼ 30의 아릴기, 탄소 원자수 7 ∼ 30의 아릴알킬기, 또는 탄소 원자수 2 ∼ 20의 복소환기를 나타낸다.R 3 represents an alkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.

R4은, 임의의 1가의 치환기를 나타낸다. n은, 0 ∼ 3의 정수를 나타낸다.R 4 represents an arbitrary monovalent substituent. n represents an integer of 0 to 3.

일반식(1) 중, R1은, 수소 원자, 탄소 원자수 1 ∼ 20의 알킬기, 탄소 원자수 6 ∼ 30의 아릴기, 탄소 원자수 7 ∼ 30의 아릴알킬기, 또는 탄소 원자수 2 ∼ 20의 복소환기를 나타낸다.In general formula (1), R 1 is a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or 2 to 20 carbon atoms. It represents the heterocyclic group of .

탄소 원자수 1 ∼ 20의 알킬기는, 직쇄상 알킬기, 분기상 알킬기, 환상(環狀) 알킬기, 그들의 결합한 기를 들 수 있다. 예를 들면, 메틸기, 에틸기, 프로필기, 이소프로필기, 부틸기, 이소부틸기, t-부틸기, 펜틸기, 이소펜틸기, 헥실기, 헵틸기, 옥틸기, 이소옥틸기, 2-에틸헥실기, 노닐기, 이소노닐기, 데실기, 이소데실기, 운데실기, 도데실기, 헥사데실기, 시클로펜틸기, 시클로펜틸메틸기, 시클로헥실기, 시클로헥실메틸기 등을 들 수 있다.The alkyl group having 1 to 20 carbon atoms includes a linear alkyl group, a branched alkyl group, a cyclic alkyl group, and a combination thereof. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group. Examples include syl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, hexadecyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, and cyclohexylmethyl group.

탄소 원자수 6 ∼ 30의 아릴기는, 예를 들면, 페닐기, 톨릴기, 자일릴기, 에틸페닐기, 나프틸기, 안트릴기 등을 들 수 있다.Examples of the aryl group having 6 to 30 carbon atoms include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group, and anthryl group.

탄소 원자수 7 ∼ 30의 아릴알킬기는, 예를 들면, 벤질기, α-메틸벤질기, α,α-디메틸벤질기, 페닐에틸기 등을 들 수 있다.Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, and phenylethyl group.

탄소 원자수 2 ∼ 20의 복소환기는, 예를 들면, 피리딜기, 피리미딜기, 퓨릴기, 테트라히드로퓨릴기, 디옥솔라닐기, 이미다졸리딜기, 옥사졸리딜기, 피페리딜기, 모르폴리닐기 등을 들 수 있다.Heterocyclic groups having 2 to 20 carbon atoms include, for example, pyridyl group, pyrimidyl group, furyl group, tetrahydrofuryl group, dioxolanyl group, imidazolidyl group, oxazolidyl group, piperidyl group, and morpholinyl group. etc. can be mentioned.

상기 중에서도, 반응성의 관점에서, 메틸기, 에틸기, 또는 페닐기가 바람직하고, 메틸기, 또는 에틸기가 보다 바람직하다.Among the above, from the viewpoint of reactivity, a methyl group, an ethyl group, or a phenyl group is preferable, and a methyl group or an ethyl group is more preferable.

일반식(1) 중, R2은, 탄소 원자수 3 ∼ 20의 알킬기, 탄소 원자수 6 ∼ 30의 아릴기, 탄소 원자수 7 ∼ 30의 아릴알킬기, 또는 탄소 원자수 2 ∼ 20의 복소환기를 나타낸다.In general formula (1), R 2 is an alkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms. represents.

탄소 원자수 3 ∼ 20의 알킬기는, 직쇄상 알킬기, 분기상 알킬기, 환상 알킬기, 그들의 결합한 기를 들 수 있다. 예를 들면, 프로필기, 이소프로필기, 부틸기, 이소부틸기, t-부틸기, 펜틸기, 이소펜틸기, 헥실기, 헵틸기, 옥틸기, 이소옥틸기, 2-에틸헥실기, 노닐기, 이소노닐기, 데실기, 이소데실기, 운데실기, 도데실기, 헥사데실기, 시클로펜틸기, 시클로펜틸메틸기, 시클로헥실기, 시클로헥실메틸기 등을 들 수 있다.The alkyl group having 3 to 20 carbon atoms includes a straight-chain alkyl group, a branched alkyl group, a cyclic alkyl group, and a combination thereof. For example, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group. , isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, hexadecyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, etc.

탄소 원자수 6 ∼ 30의 아릴기는, 예를 들면, 페닐기, 톨릴기, 자일릴기, 에틸페닐기, 나프틸기, 안트릴기 등을 들 수 있다.Examples of the aryl group having 6 to 30 carbon atoms include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group, and anthryl group.

탄소 원자수 7 ∼ 30의 아릴알킬기는, 예를 들면, 벤질기, α-메틸벤질기, α,α-디메틸벤질기, 페닐에틸기 등을 들 수 있다.Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, and phenylethyl group.

탄소 원자수 2 ∼ 20의 복소환기는, 예를 들면, 피리딜기, 피리미딜기, 퓨릴기, 테트라히드로퓨릴기, 디옥솔라닐기, 이미다졸리딜기, 옥사졸리딜기, 피페리딜기, 모르폴리닐기 등을 들 수 있다.Heterocyclic groups having 2 to 20 carbon atoms include, for example, pyridyl group, pyrimidyl group, furyl group, tetrahydrofuryl group, dioxolanyl group, imidazolidyl group, oxazolidyl group, piperidyl group, and morpholinyl group. etc. can be mentioned.

상기 중에서도, 패턴 형상의 관점에서, 탄소 원자수 3 ∼ 20의 알킬기가 바람직하고, 탄소 원자수 3 ∼ 8의 알킬기가 보다 바람직하고, 펜틸기가 더 바람직하다.Among the above, from the viewpoint of the pattern shape, an alkyl group with 3 to 20 carbon atoms is preferable, an alkyl group with 3 to 8 carbon atoms is more preferable, and a pentyl group is still more preferable.

일반식(1) 중, R3은, 탄소 원자수 3 ∼ 20의 알킬기, 탄소 원자수 6 ∼ 30의 아릴기, 탄소 원자수 7 ∼ 30의 아릴알킬기, 또는 탄소 원자수 2 ∼ 20의 복소환기를 나타낸다.In general formula (1), R 3 is an alkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms. represents.

탄소 원자수 3 ∼ 20의 알킬기는, 직쇄상 알킬기, 분기상 알킬기, 환상 알킬기, 그들의 결합한 기를 들 수 있다. 예를 들면, 프로필기, 이소프로필기, 부틸기, 이소부틸기, t-부틸기, 펜틸기, 이소펜틸기, 헥실기, 헵틸기, 옥틸기, 이소옥틸기, 2-에틸헥실기, 노닐기, 이소노닐기, 데실기, 이소데실기, 운데실기, 도데실기, 헥사데실기, 시클로펜틸기, 시클로펜틸메틸기, 시클로헥실기, 시클로헥실메틸기 등을 들 수 있다.The alkyl group having 3 to 20 carbon atoms includes a straight-chain alkyl group, a branched alkyl group, a cyclic alkyl group, and a combination thereof. For example, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group. , isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, hexadecyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, etc.

탄소 원자수 6 ∼ 30의 아릴기는, 예를 들면, 페닐기, 톨릴기, 자일릴기, 에틸페닐기, 나프틸기, 안트릴기 등을 들 수 있다.Examples of the aryl group having 6 to 30 carbon atoms include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group, and anthryl group.

탄소 원자수 7 ∼ 30의 아릴알킬기는, 예를 들면, 벤질기, α-메틸벤질기, α,α-디메틸벤질기, 페닐에틸기 등을 들 수 있다.Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, and phenylethyl group.

탄소 원자수 2 ∼ 20의 복소환기는, 예를 들면, 피리딜기, 피리미딜기, 퓨릴기, 테트라히드로퓨릴기, 디옥솔라닐기, 이미다졸리딜기, 옥사졸리딜기, 피페리딜기, 모르폴리닐기 등을 들 수 있다.Heterocyclic groups having 2 to 20 carbon atoms include, for example, pyridyl group, pyrimidyl group, furyl group, tetrahydrofuryl group, dioxolanyl group, imidazolidyl group, oxazolidyl group, piperidyl group, and morpholinyl group. etc. can be mentioned.

상기 중에서도, 물 얼룩의 억제의 관점에서, 탄소 원자수 3 ∼ 15의 분기상의 알킬기가 바람직하고, 탄소 원자수 5 ∼ 12의 분기상의 알킬기가 보다 바람직하고, 3-메틸부틸기, 2-에틸헥실기가 더 바람직하다.Among the above, from the viewpoint of suppressing water stains, a branched alkyl group having 3 to 15 carbon atoms is preferable, a branched alkyl group having 5 to 12 carbon atoms is more preferable, and 3-methylbutyl group and 2-ethylhexyl group are preferable. Practical skills are more desirable.

일반식(1) 중, R4은, 임의의 1가의 치환기를 나타낸다.In General Formula (1), R 4 represents an arbitrary monovalent substituent.

1가의 치환기로서는, 메틸기, 에틸기 등의 탄소 원자수 1 ∼ 20의 알킬기; 메톡시기, 에톡시기 등의 탄소 원자수 1 ∼ 20의 알콕시기; F, Cl, Br, I 등의 할로겐 원자; 탄소 원자수 1 ∼ 20의 아실기; 탄소 원자수 1 ∼ 20의 알킬에스테르기; 탄소 원자수 1 ∼ 20의 알콕시카르보닐기; 탄소 원자수 1 ∼ 20의 할로겐화알킬기, 탄소 원자수 4 ∼ 20의 방향족환기; 아미노기; 탄소 원자수 1 ∼ 20의 아미노알킬기; 수산기; 니트로기; 시아노기; 치환기를 가져도 되는 벤조일기; 치환기를 가져도 되는 테노일기 등을 들 수 있다. 벤조일기, 또는 테노일기가 가져도 되는 치환기로서는, 탄소 원자수 1 ∼ 10의 알킬기, 탄소 원자수 1 ∼ 10의 알콕시기, 탄소 원자수 1 ∼ 10의 알콕시카르보닐기 등을 들 수 있고, 1 ∼ 3개의 범위에서 가져도 된다.Examples of the monovalent substituent include alkyl groups having 1 to 20 carbon atoms, such as methyl and ethyl groups; Alkoxy groups having 1 to 20 carbon atoms, such as methoxy group and ethoxy group; Halogen atoms such as F, Cl, Br, and I; Acyl group having 1 to 20 carbon atoms; Alkyl ester group having 1 to 20 carbon atoms; Alkoxycarbonyl group having 1 to 20 carbon atoms; Halogenated alkyl group having 1 to 20 carbon atoms, aromatic ring group having 4 to 20 carbon atoms; amino group; Aminoalkyl group having 1 to 20 carbon atoms; hydroxyl group; nitro group; Cyano group; Benzoyl group which may have a substituent; Examples include tenoyl group which may have a substituent. Substituents that the benzoyl group or thenoyl group may have include an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an alkoxycarbonyl group with 1 to 10 carbon atoms, and the like. You can have it within the range of dogs.

상기 중에서도, 반응성의 관점에서, 치환기를 가져도 되는 벤조일기가 바람직하고, 치환기가 알콕시카르보닐기인 벤조일기가 보다 바람직하다.Among the above, from the viewpoint of reactivity, a benzoyl group which may have a substituent is preferable, and a benzoyl group whose substituent is an alkoxycarbonyl group is more preferable.

일반식(1) 중, n은, 0 ∼ 3의 정수를 나타낸다. 이들 중에서도, 라디칼 생성 효율의 관점에서, 0 또는 1이 바람직하고, 1이 보다 바람직하다.In General Formula (1), n represents an integer of 0 to 3. Among these, from the viewpoint of radical production efficiency, 0 or 1 is preferable, and 1 is more preferable.

옥심계 광중합개시제(C1)의 제조 방법은, 공지된 방법을 이용할 수 있다. 예를 들면, 국제공개 제2008／078678호, 국제공개 제2014／050738호, 일본 특허공표 2016-519675호 공보 등에 기재된 방법을 들 수 있다.The method for producing the oxime-based photopolymerization initiator (C1) can be a known method. For example, the method described in International Publication No. 2008/078678, International Publication No. 2014/050738, Japanese Patent Publication No. 2016-519675, etc. can be mentioned.

이하, 일반식(1)으로 표시되는 화합물의 구체예를 나타낸다. 또, 본 발명은 이들에 한정되지 않는다.Hereinafter, specific examples of the compound represented by general formula (1) are shown. Additionally, the present invention is not limited to these.

[화 4][Tuesday 4]

[화 5][Tuesday 5]

화학식 (2) ∼ (7)의 화합물 중에서도, 물 얼룩의 억제, 패턴 형상, 및 잔막률의 관점에서, 화학식(7)의 화합물이 바람직하다.Among the compounds of formulas (2) to (7), the compound of formula (7) is preferable from the viewpoints of water stain suppression, pattern shape, and residual film rate.

옥심계 광중합개시제(C1)는, 단독 또는 2종류 이상을 병용하여 사용할 수 있다.The oxime-based photopolymerization initiator (C1) can be used individually or in combination of two or more types.

(옥심계 광중합개시제(C2))(Oxime-based photopolymerization initiator (C2))

옥심계 광중합개시제(C2)는, 일반식(1)으로 표시되는 옥심계 광중합개시제(C1) 이외의 광중합개시제이다. 옥심계 광중합개시제(C2)의 시판품은, 예를 들면, BASF Japan Ltd. 제조의 IRGACURE OXE-01, 02, 03, 04, ADEKA CORPORATION 제조의 ADEKA ARKLS N-1919, NCi-730, 831, 930, Changzhou Tronly New Electronic Materials Co., Ltd. 제조의 TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 346, 358, 380, 365, 610, 3054, 3057, IGM Resins Inc. 제조의 OMNIRAD1312, 1314, 1316, Samyang Corporation 제조의 SPI-02, 03, 04, 05, 06, 07, Daito Chemix Corporation 제조의 DFI-020, 306, EOX-01 등을 들 수 있다.The oxime-based photopolymerization initiator (C2) is a photopolymerization initiator other than the oxime-based photopolymerization initiator (C1) represented by General Formula (1). Commercially available oxime-based photopolymerization initiator (C2) is available from BASF Japan Ltd., for example. Manufactured by IRGACURE OXE-01, 02, 03, 04, ADEKA CORPORATION Manufactured by ADEKA ARKLS N-1919, NCi-730, 831, 930, Changzhou Tronly New Electronic Materials Co., Ltd. Manufactured by TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 346, 358, 380, 365, 610, 3054, 3057, IGM Resins Inc. OMNIRAD1312, 1314, and 1316 manufactured by Samyang Corporation, SPI-02, 03, 04, 05, 06, 07 manufactured by Daito Chemix Corporation, and DFI-020, 306, and EOX-01 manufactured by Daito Chemix Corporation.

옥심계 광중합개시제(C2)는, 예를 들면, 이하의 화합물을 들 수 있다. 단, 본 발명은 이들에 한정되지 않는다.Examples of the oxime-based photopolymerization initiator (C2) include the following compounds. However, the present invention is not limited to these.

[화 6][Tuesday 6]

[화 7][Tuesday 7]

화학식 (8) ∼ (16)의 화합물의 제조 방법은, 예를 들면, 일본 특허공표 2004-534797호 공보, 일본 특허공개 2008-80068호 공보, 일본 특허공표 2012-526185호 공보, 국제공개 제2015／036910호, 국제공개 제2015／152153호, 일본 특허공표 2016-504270호 공보, 일본 특허공표 2017-512886호 공보 등에 기재된 방법을 들 수 있다.Methods for producing compounds of formulas (8) to (16) include, for example, Japanese Patent Application Publication No. 2004-534797, Japanese Patent Application Publication No. 2008-80068, Japanese Patent Application Publication No. 2012-526185, and International Publication No. 2015. /036910, International Publication No. 2015/152153, Japanese Patent Publication No. 2016-504270, Japanese Patent Publication No. 2017-512886, etc.

옥심계 광중합개시제(C2)는, 화학식 (8) ∼ (16)의 화합물 중에서도, 물 얼룩의 억제, 패턴 형상, 및 잔막률의 관점에서, 화학식 (11) ∼ (16)의 화합물로 이루어지는 군에서 선택되는 1종 이상이 바람직하다.The oxime-based photopolymerization initiator (C2) is, among the compounds of formulas (8) to (16), from the group consisting of compounds of formulas (11) to (16) from the viewpoint of suppression of water stains, pattern shape, and residual film rate. It is preferable to select one or more types.

옥심계 광중합개시제(C2)는, 단독 또는 2종류 이상을 병용하여 사용할 수 있다.The oxime-based photopolymerization initiator (C2) can be used individually or in combination of two or more types.

옥심계 광중합개시제(C1)와 옥심계 광중합개시제(C2)의 질량비는, 물 얼룩의 억제, 패턴 형상, 및 잔막률의 관점에서, 90:10 ∼ 10:90이 바람직하고, 80:20 ∼ 20:80이 보다 바람직하고, 70:30 ∼ 30:70이 더 바람직하다.The mass ratio of the oxime-based photopolymerization initiator (C1) and the oxime-based photopolymerization initiator (C2) is preferably 90:10 to 10:90, and 80:20 to 20, from the viewpoint of suppression of water stains, pattern shape, and residual film rate. :80 is more preferable, and 70:30 to 30:70 is more preferable.

옥심계 광중합개시제(C1)와 옥심계 광중합개시제(C2)의 합계 함유량은, 물 얼룩의 억제, 패턴 형상, 및 잔막률의 관점에서, 광중합개시제(C) 100질량％ 중, 50질량％ 이상이 바람직하고, 80질량％ 이상인 것이 보다 바람직하다.The total content of the oxime-based photopolymerization initiator (C1) and the oxime-based photopolymerization initiator (C2) is 50% by mass or more out of 100% by mass of the photopolymerization initiator (C) from the viewpoint of suppression of water stains, pattern shape, and residual film rate. It is preferable, and it is more preferable that it is 80 mass % or more.

((C1) 및 (C2) 이외의 광중합개시제(C3))(Photopolymerization initiator (C3) other than (C1) and (C2))

본 발명의 감광성 조성물은, 옥심계 광중합개시제(C1) 및 옥심계 광중합개시제(C2) 이외의 광중합개시제(C3)(이하, 그 외 광중합개시제(C3)라고도 함)를 포함할 수 있다.The photosensitive composition of the present invention may contain a photopolymerization initiator (C3) (hereinafter also referred to as other photopolymerization initiators (C3)) other than the oxime-based photopolymerization initiator (C1) and the oxime-based photopolymerization initiator (C2).

그 외 광중합개시제(C3)는, 광에 의해 중합성 화합물(B)의 중합을 개시 가능한 화합물이면, 특별히 제한은 없고, 공지된 광중합개시제를 이용할 수 있다. 예를 들면, 4-페녹시디클로로아세토페논, 4-t-부틸-디클로로아세토페논, 디에톡시아세토페논, 1-(4-이소프로필페닐)-2-히드록시-2-메틸프로판-1-온, 1-히드록시시클로헥실페닐케톤, 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노프로판-1-온, 2-(디메틸아미노)-1-[4-(4-모르폴리노)페닐]-2-(페닐메틸)-1-부타논, 또는 2-(디메틸아미노)-2-[(4-메틸페닐)메틸]-1-[4-(4-모르폴리닐)페닐]-1-부타논 등의 아세토페논계 화합물;The photopolymerization initiator (C3) is not particularly limited as long as it is a compound capable of initiating polymerization of the polymerizable compound (B) with light, and any known photopolymerization initiator can be used. For example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one , 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-( 4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholy) acetophenone-based compounds such as nyl)phenyl]-1-butanone;

2,4,6-트리클로로-s-트리아진, 2-페닐-4,6-비스(트리클로로메틸)-s-트리아진, 2-(p-메톡시페닐)-4,6-비스(트리클로로메틸)-s-트리아진, 2-(p-톨릴)-4,6-비스(트리클로로메틸)-s-트리아진, 2-피페로닐-4,6-비스(트리클로로메틸)-s-트리아진, 2,4-비스(트리클로로메틸)-6-스티릴-s-트리아진, 2-(나프토-1-일)-4,6-비스(트리클로로메틸)-s-트리아진, 2-(4-메톡시-나프토-1-일)-4,6-비스(트리클로로메틸)-s-트리아진, 2,4-트리클로로메틸-(피페로닐)-6-트리아진, 또는 2,4-트리클로로메틸-(4'-메톡시스티릴)-6-트리아진 등의 트리아진계 화합물;2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis( Trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl) -s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s -Triazine, 2-(4-methoxy-naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)- Triazine-based compounds such as 6-triazine or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;

비스(2,4,6-트리메틸벤조일)페닐포스핀옥사이드, 또는 디페닐-2,4,6-트리메틸벤조일포스핀옥사이드 등의 아실포스핀계 화합물; Acylphosphine-based compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide;

9,10-페난트렌퀴논, 캄퍼퀴논, 에틸안트라퀴논 등의 퀴논계 화합물; 보레이트계 화합물; 카르바졸계 화합물; 이미다졸계 화합물; 혹은, 티타노센계 화합물 등을 들 수 있다.Quinone-based compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate-based compounds; carbazole-based compounds; Imidazole-based compounds; Alternatively, titanocene-based compounds, etc. can be mentioned.

그 외 광중합개시제(C3)는, 단독 또는 2종류 이상을 병용하여 사용할 수 있다.Other photopolymerization initiators (C3) can be used individually or in combination of two or more types.

광중합개시제(C)의 함유량은, 중합성 화합물(B) 100질량부에 대하여, 광경화성의 관점에서, 1 ∼ 100질량부가 바람직하고, 3 ∼ 50질량부가 보다 바람직하고, 5 ∼ 25질량부가 더 바람직하다.The content of the photopolymerization initiator (C) is preferably 1 to 100 parts by mass, more preferably 3 to 50 parts by mass, and more preferably 5 to 25 parts by mass from the viewpoint of photocurability, relative to 100 parts by mass of the polymerizable compound (B). desirable.

[알칼리 가용성 수지(A)][Alkali-soluble resin (A)]

본 발명의 감광성 조성물은, 알칼리 가용성 수지(A)를 포함한다.The photosensitive composition of the present invention contains an alkali-soluble resin (A).

알칼리 가용성 수지(A)는, 알칼리 현상액에 용해되는 수지이면 되고, 공지된 수지를 이용할 수 있다. 알칼리 가용성 수지(B)는, 비감광성 알칼리 가용성 수지, 감광성 알칼리 가용성 수지로 분류할 수 있다. 알칼리 가용성 수지(A)는, 예를 들면, 카르복시기, 인산기, 설폰산기, 히드록시기, 페놀성 히드록시기 등의 알칼리 가용성기를 갖는다. 이들 중에서도, 카르복시기가 바람직하다.The alkali-soluble resin (A) may be any resin that dissolves in an alkaline developer, and any known resin can be used. Alkali-soluble resin (B) can be classified into non-photosensitive alkali-soluble resin and photosensitive alkali-soluble resin. The alkali-soluble resin (A) has, for example, alkali-soluble groups such as a carboxyl group, a phosphoric acid group, a sulfonic acid group, a hydroxy group, and a phenolic hydroxy group. Among these, a carboxyl group is preferable.

비감광성 알칼리 가용성 수지는, 예를 들면, 산성기를 갖는 아크릴 수지, α-올레핀／(무수)말레산 공중합체, 스티렌／스티렌설폰산 공중합체, 에틸렌／(메타)아크릴산 공중합체, 또는 이소부틸렌／(무수)말레산 공중합체 등을 들 수 있다. 감광성 알칼리 가용성 수지는, 중합성 불포화기를 갖는 알칼리 가용성 수지이다. 또한, 알칼리 가용성 수지(A)는, 에폭시기나 옥세타닐기 등의 열경화성기를 함유할 수 있다.Non-photosensitive alkali-soluble resins include, for example, an acrylic resin having an acidic group, α-olefin/(anhydride) maleic acid copolymer, styrene/styrene sulfonic acid copolymer, ethylene/(meth)acrylic acid copolymer, or isobutylene. ／(Anhydrous) maleic acid copolymer, etc. are mentioned. Photosensitive alkali-soluble resin is an alkali-soluble resin having a polymerizable unsaturated group. Additionally, the alkali-soluble resin (A) may contain a thermosetting group such as an epoxy group or oxetanyl group.

알칼리 가용성 수지(A)의 중량 평균 분자량(Mw)은, 현상성의 관점에서, 2,000 ∼ 40,000이 바람직하고, 3,000 ∼ 30,000이 보다 바람직하고, 4,000 ∼ 20,000이 더 바람직하다. 또한, Mw／Mn의 값은 10 이하가 바람직하다. 적당한 중량 평균 분자량(Mw)에 의해 기판에 대한 밀착성, 및 현상 용해성이 향상된다.From the viewpoint of developability, the weight average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and still more preferably 4,000 to 20,000. Additionally, the value of Mw/Mn is preferably 10 or less. An appropriate weight average molecular weight (Mw) improves adhesion to the substrate and solubility in development.

알칼리 가용성 수지(A)의 산가는, 50 ∼ 200㎎KOH／g이 바람직하고, 70 ∼ 180㎎KOH／g이 보다 바람직하고, 90 ∼ 170㎎KOH／g이 더 바람직하다. 적당한 산가에 의해 기판에 대한 밀착성, 및 현상 용해성이 향상된다.The acid value of the alkali-soluble resin (A) is preferably 50 to 200 mgKOH/g, more preferably 70 to 180 mgKOH/g, and still more preferably 90 to 170 mgKOH/g. Adhesion to the substrate and solubility in development are improved by an appropriate acid value.

알칼리 가용성 수지(A)의 함유량은, 감광성 조성물의 불휘발분 100질량％ 중, 1 ∼ 80질량％가 바람직하고, 5 ∼ 60질량％가 보다 바람직하고, 10 ∼ 50질량％가 더 바람직하다.The content of the alkali-soluble resin (A) is preferably 1 to 80% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 50% by mass, based on 100% by mass of non-volatile matter of the photosensitive composition.

알칼리 가용성 수지(A)는, 단독 또는 2종류 이상을 병용하여 사용할 수 있다.The alkali-soluble resin (A) can be used individually or in combination of two or more types.

알칼리 가용성 수지(A)는, 패턴 형성의 관점에서, 감광성 알칼리 가용성 수지를 포함하는 것이 바람직하다.The alkali-soluble resin (A) preferably contains a photosensitive alkali-soluble resin from the viewpoint of pattern formation.

(알칼리 가용성 수지(A1))(Alkali soluble resin (A1))

본 발명의 감광성 조성물은, 알칼리 가용성 수지(A)로서, 물 얼룩의 억제, 잔막률, 패턴 형성의 관점에서, 지환식 탄화수소 함유 단량체 단위(a1), 및 카르복시기 함유 단량체 단위(a2)를 함유하는 알칼리 가용성 수지(A1)를 포함하는 것이 바람직하다.The photosensitive composition of the present invention is an alkali-soluble resin (A), which contains an alicyclic hydrocarbon-containing monomer unit (a1) and a carboxyl group-containing monomer unit (a2) from the viewpoint of suppressing water stains, remaining film rate, and pattern formation. It is preferred that it contains an alkali-soluble resin (A1).

소수성(疎水性)이 높고, 유연성과 강직성을 겸비한 지환식 탄화수소 구조는, 현상액과의 친화성이 낮고 강인한 피막을 형성할 수 있다고 추측되어, 물 얼룩의 억제, 잔막률, 및 패턴 형성성이 향상된다. 그리고, 또한, 고감도인 옥심계 광중합개시제(C1)와 옥심계 광중합개시제(C2)를 조합함으로써, 보다 강인한 피막을 형성할 수 있었다고 추측한다.It is assumed that the alicyclic hydrocarbon structure, which has high hydrophobicity and combines flexibility and rigidity, has low affinity with the developer and can form a strong film, suppressing water stains, improving the remaining film rate and pattern formation. do. Furthermore, it is assumed that a stronger film could be formed by combining the highly sensitive oxime-based photopolymerization initiator (C1) and the oxime-based photopolymerization initiator (C2).

〔지환식 탄화수소 함유 단량체 단위(a1)〕[Alicyclic hydrocarbon-containing monomer unit (a1)]

지환식 탄화수소 함유 단량체는, 예를 들면, 이소보르닐(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, 디시클로펜타닐(메타)아크릴레이트, 디시클로펜테닐(메타)아크릴레이트, 디시클로펜타닐옥시에틸(메타)아크릴레이트, 디시클로펜테닐옥시에틸(메타)아크릴레이트, 아다만틸(메타)아크릴레이트 등을 들 수 있다. 이들 중에서도, 패턴 형성의 관점에서, 디시클로펜타닐(메타)아크릴레이트, 디시클로펜테닐(메타)아크릴레이트, 디시클로펜타닐옥시에틸(메타)아크릴레이트가 바람직하다.Alicyclic hydrocarbon-containing monomers include, for example, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclofentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclofentanyl. Examples include oxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and adamantyl (meth)acrylate. Among these, from the viewpoint of pattern formation, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferable.

〔카르복시기 함유 단량체 단위(a2)〕[Carboxyl group-containing monomer unit (a2)]

카르복시기 함유 단량체는, 예를 들면, 아크릴산, 메타크릴산, 크로톤산, 이타콘산, 말레산, 푸말산 등을 들 수 있다. 또한, α-(히드록시메틸)아크릴산과 같은, 동일 분자 중에 히드록시기 및 카르복시기를 함유하는 단량체도 들 수 있다. 이들 중에서도, 아크릴산, 메타크릴산이 바람직하다.Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid. Additionally, monomers containing a hydroxy group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid, can also be mentioned. Among these, acrylic acid and methacrylic acid are preferable.

〔그 외 단량체 단위(a3)〕[Other monomer units (a3)]

알칼리 가용성 수지(A1)는, 지환식 탄화수소 함유 단량체(a1), 및 카르복시기 함유 단량체 단위(a2) 이외에 그 외 단량체 단위(a3)를 함유할 수 있다.The alkali-soluble resin (A1) may contain other monomer units (a3) in addition to the alicyclic hydrocarbon-containing monomer (a1) and the carboxyl group-containing monomer unit (a2).

그 외 단량체는, 예를 들면, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, n-프로필(메타)아크릴레이트, 이소프로필(메타)아크릴레이트, n-부틸(메타)아크릴레이트, 이소부틸(메타)아크릴레이트, t-부틸(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, 스테아릴(메타)아크릴레이트, 라우릴(메타)아크릴레이트, 페닐(메타)아크릴레이트, 벤질(메타)아크릴레이트, 페녹시에틸(메타)아크릴레이트, 페녹시디에틸렌글리콜(메타)아크릴레이트, 메톡시폴리프로필렌글리콜(메타)아크릴레이트, 에톡시폴리에틸렌글리콜(메타)아크릴레이트 등의 (메타)아크릴레이트류;Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and isopropyl (meth)acrylate. Butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, etc. Acrylates;

2-히드록시에틸(메타)아크릴레이트, 2- 또는 3-히드록시프로필(메타)아크릴레이트, 2- 또는 3- 또는 4-히드록시부틸(메타)아크릴레이트, 글리세롤모노(메타)아크릴레이트, 또는 시클로헥산디메탄올모노(메타)아크릴레이트 등의 수산기 함유 (메타)아크릴레이트류;2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono (meth)acrylate, or hydroxyl group-containing (meth)acrylates such as cyclohexanedimethanol mono(meth)acrylate;

히드록시알킬(메타)아크릴레이트에, 에틸렌옥사이드, 프로필렌옥사이드, 및／또는 부틸렌옥사이드 등을 부가 중합시킨 폴리에테르모노(메타)아크릴레이트나, 폴리γ-발레로락톤, 폴리ε-카프로락톤, 및／또는 폴리12-히드록시스테아르산 등을 부가한 폴리에스테르모노(메타)아크릴레이트류;Polyether mono(meth)acrylate obtained by addition polymerizing ethylene oxide, propylene oxide, and/or butylene oxide to hydroxyalkyl (meth)acrylate, polyγ-valerolactone, polyε-caprolactone, and/or polyester mono(meth)acrylates added with poly12-hydroxystearic acid, etc.;

글리시딜(메타)아크릴레이트, 메틸글리시딜(메타)아크릴레이트, 2-글리시독시에틸(메타)아크릴레이트, 3,4-에폭시부틸(메타)아크릴레이트, 및 3,4-에폭시시클로헥실(메타)아크릴레이트 등의 에폭시기 함유 (메타)아크릴레이트류;Glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclo Epoxy group-containing (meth)acrylates such as hexyl (meth)acrylate;

(메타)아크릴아미드, N,N-디메틸(메타)아크릴아미드, N,N-디에틸(메타)아크릴아미드, N-이소프로필(메타)아크릴아미드, 다이아세톤(메타)아크릴아미드, 또는 아크릴로일모르폴린 등의 (메타)아크릴아미드류;(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acrylamide (meth)acrylamides such as morpholine;

스티렌, 또는 α-메틸스티렌 등의 스티렌류;Styrenes such as styrene or α-methylstyrene;

에틸비닐에테르, n-프로필비닐에테르, 이소프로필비닐에테르, n-부틸비닐에테르, 또는 이소부틸비닐에테르 등의 비닐에테르류;Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether;

아세트산비닐, 또는 프로피온산비닐 등의 지방산 비닐류;Fatty acid vinyls such as vinyl acetate or vinyl propionate;

페닐말레이미드, 메틸말레이미드, 에틸말레이미드, 1,2-비스말레이미드에탄, 1,6-비스말레이미드헥산, 3-말레이미드프로피온산, 6,7-메틸렌디옥시-4-메틸-3-말레이미드쿠마린, 4,4'-비스말레이미드디페닐메탄, 비스(3-에틸-5-메틸-4-말레이미드페닐)메탄, N,N'-1,3-페닐렌디말레이미드, N,N'-1,4-페닐렌디말레이미드, N-(1-피레닐)말레이미드, N-(2,4,6-트리클로로페닐)말레이미드, N-(4-아미노페닐)말레이미드, N-(4-니트로페닐)말레이미드, N-벤질말레이미드, N-브로모메틸-2,3-디클로로말레이미드, N-숙신이미딜-3-말레이미드벤조에이트, N-숙신이미딜-3-말레이미드프로피오네이트, N-숙신이미딜-4-말레이미드부티레이트, N-숙신이미딜-6-말레이미드헥사노에이트, N-[4-(2-벤조이미다졸릴)페닐]말레이미드, 9-말레이미드아크리딘 등의 N-치환 말레이미드류;Phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimide ethane, 1,6-bismaleimide hexane, 3-maleimide propionic acid, 6,7-methylenedioxy-4-methyl-3- Maleimide coumarin, 4,4'-bismaleimide diphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, N,N'-1,3-phenylenedimaleimide, N, N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl- 3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzoimidazolyl)phenyl]malei N-substituted maleimides such as mead and 9-maleimide acridine;

2-(메타)아크릴로일옥시에틸애시드포스페이트, 상술한 수산기 함유 (메타)아크릴레이트의 수산기에, 예를 들면 5산화인이나 폴리인산 등의 인산에스테르화제를 반응시킨 화합물 등의 인산에스테르기 함유 (메타)아크릴레이트류 등을 들 수 있다.2-(meth)acryloyloxyethyl acid phosphate, containing a phosphoric acid ester group, such as a compound obtained by reacting the hydroxyl group of the above-mentioned hydroxyl group-containing (meth)acrylate with a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid. (meth)acrylates, etc. can be mentioned.

알칼리 가용성 수지(A1)는, 지환식 탄화수소 함유 단량체 단위(a1), 및 카르복시기 함유 단량체 단위(a2)를 함유하면 좋고, 그 합성 방법은 한정되지 않는다. 이하, 바람직한 합성법인 방법(i), 방법(ii)을 설명한다.The alkali-soluble resin (A1) may contain an alicyclic hydrocarbon-containing monomer unit (a1) and a carboxyl group-containing monomer unit (a2), and its synthesis method is not limited. Hereinafter, preferred synthesis methods, method (i) and method (ii), will be described.

<방법(i)><Method (i)>

방법(i)은, 예를 들면, 지환식 탄화수소 함유 단량체, 및 카르복시기 함유 단량체의 공중합체를 합성함으로써, 알칼리 가용성 수지(A1)를 합성할 수 있다.Method (i) can synthesize alkali-soluble resin (A1), for example, by synthesizing a copolymer of an alicyclic hydrocarbon-containing monomer and a carboxyl group-containing monomer.

<방법(ii)><Method (ii)>

방법(ii)은, 예를 들면, 지환식 탄화수소 함유 단량체, 및 에폭시기 함유 단량체의 공중합체를 합성한다. 그 다음에, 상기 공중합체의 에폭시기에, 카르복시기 함유 단량체를 부가하고, 생성된 수산기와 산무수물을 에스테르화 반응시킴으로써, 알칼리 가용성 수지(A1)를 합성할 수 있다.Method (ii) synthesizes, for example, a copolymer of an alicyclic hydrocarbon-containing monomer and an epoxy group-containing monomer. Next, alkali-soluble resin (A1) can be synthesized by adding a carboxyl group-containing monomer to the epoxy group of the copolymer and subjecting the resulting hydroxyl group and acid anhydride to an esterification reaction.

에폭시기 함유 단량체는, 예를 들면, 글리시딜(메타)아크릴레이트, 메틸글리시딜(메타)아크릴레이트, 2-글리시독시에틸(메타)아크릴레이트, 3,4-에폭시부틸(메타)아크릴레이트, 및 3,4-에폭시시클로헥실(메타)아크릴레이트를 들 수 있다. 이들 중에서도, 반응성의 관점에서, 글리시딜(메타)아크릴레이트가 바람직하다.Epoxy group-containing monomers include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, and 3,4-epoxybutyl (meth)acrylate. ate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferable from the viewpoint of reactivity.

산무수물은, 예를 들면, 테트라히드로무수프탈산, 무수프탈산, 헥사히드로무수프탈산, 무수숙신산, 무수말레산 등을 들 수 있다. 이들은, 단독 또는 2종 이상 병용하여 사용할 수 있다.Examples of acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These can be used individually or in combination of two or more types.

지환식 탄화수소 함유 단량체 단위(a1)의 함유량은, 물 얼룩의 억제, 패턴 형성의 관점에서, 알칼리 가용성 수지(A1)의 전체 구성 단위 100질량％ 중, 5 ∼ 60질량％가 바람직하고, 10 ∼ 50질량％가 보다 바람직하다.The content of the alicyclic hydrocarbon-containing monomer unit (a1) is preferably 5 to 60% by mass, based on 100% by mass of the total structural units of the alkali-soluble resin (A1), from the viewpoint of suppressing water stains and forming patterns, and is 10 to 10% by mass. 50 mass% is more preferable.

알칼리 가용성 수지(A1)의 함유량은, 물 얼룩의 억제, 잔막률, 및 패턴 형성의 관점에서, 알칼리 가용성 수지(A) 100질량％ 중, 50질량％ 이상이 바람직하고, 70질량％ 이상이 보다 바람직하다.The content of the alkali-soluble resin (A1) is preferably 50% by mass or more, and more preferably 70% by mass or more, based on 100% by mass of the alkali-soluble resin (A), from the viewpoint of suppression of water stains, residual film rate, and pattern formation. desirable.

(알칼리 가용성 수지(A2))(Alkali soluble resin (A2))

본 발명의 감광성 조성물은, 알칼리 가용성 수지(A)로서, 알칼리 가용성 수지(A1) 이외의 알칼리 가용성 수지(A2)를 함유할 수 있다.The photosensitive composition of the present invention may contain an alkali-soluble resin (A2) other than the alkali-soluble resin (A1) as the alkali-soluble resin (A).

[중합성 화합물(B)][Polymerizable compound (B)]

본 발명의 감광성 조성물은, 중합성 화합물(B)을 포함한다.The photosensitive composition of the present invention contains a polymerizable compound (B).

중합성 화합물(B)은, 모노머, 올리고머를 들 수 있다. 중합성 불포화기는, 예를 들면, 비닐기, (메타)알릴기, (메타)아크릴로일기, (메타)아크릴로일옥시기 등을 들 수 있다. 중합성 화합물(B)은, 예를 들면, 락톤 변성된 중합성 화합물(B1), 산기(酸基)를 갖는 중합성 화합물(B2), 우레탄 결합을 갖는 중합성 화합물(B3), 그 외 중합성 화합물(B4) 등을 들 수 있다.Polymerizable compounds (B) include monomers and oligomers. Examples of the polymerizable unsaturated group include vinyl group, (meth)allyl group, (meth)acryloyl group, and (meth)acryloyloxy group. The polymerizable compound (B) includes, for example, lactone-modified polymerizable compound (B1), polymerizable compound (B2) having an acid group, polymerizable compound (B3) having a urethane bond, and other polymerizable compounds. compounds (B4), etc.

(락톤 변성된 중합성 화합물(B1))(Lactone-modified polymerizable compound (B1))

본 발명의 감광성 조성물은, 물 얼룩의 억제의 관점에서, 락톤 변성된 중합성 화합물(B1)을 포함하는 것이 바람직하다.The photosensitive composition of the present invention preferably contains a lactone-modified polymerizable compound (B1) from the viewpoint of suppressing water stains.

락톤 변성된 중합성 화합물(B1)은, 분자 내에 락톤에 의해 변성된 구조를 갖는 화합물이다. 락톤 변성된 중합성 화합물(B1)은, 트리메틸올에탄, 디트리메틸올에탄, 트리메틸올프로판, 디트리메틸올프로판, 펜타에리트리톨, 트리펜타에리트리톨, 글리세린, 디글리세롤, 트리메틸올멜라민 등의 다가 알코올과, (메타)아크릴산 및 ε-카프로락톤 혹은 그 외의 락톤 화합물을 에스테르화함으로써 얻어진다. 락톤 변성된 중합성 화합물(B1)은, 하기 일반식(17)으로 표시되는 화합물이 바람직하다.The lactone-modified polymerizable compound (B1) is a compound that has a structure modified by lactone in its molecule. The lactone-modified polymerizable compound (B1) is a polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, tripentaerythritol, glycerin, diglycerol, and trimethylolmelamine. It is obtained by esterifying (meth)acrylic acid and ε-caprolactone or other lactone compounds. The lactone-modified polymerizable compound (B1) is preferably a compound represented by the following general formula (17).

일반식(17)General formula (17)

[화 8][Tuesday 8]

일반식(17) 중, 6개의 R은 모두 하기 일반식(18)으로 표시되는 기, 또는 6개의 R 중 1 ∼ 5개는 하기 일반식(18)으로 표시되는 기이며, 나머지는 하기 일반식(19)으로 표시되는 기이다.In general formula (17), all six R are groups represented by the following general formula (18), or 1 to 5 of the six R are groups represented by the following general formula (18), and the remainder are represented by the following general formula It is a group represented by (19).

일반식(18)General formula (18)

[화 9][Tuesday 9]

일반식(18) 중, R1은 수소 원자, 또는 메틸기를 나타내고, m은 1 또는 2의 정수이며, *는 일반식(17)의 산소 원자와 결합하는 결합수(結合手)이다.In General Formula (18), R 1 represents a hydrogen atom or a methyl group, m is an integer of 1 or 2, and * is the bond number that bonds to the oxygen atom in General Formula (17).

일반식(19)General formula (19)

[화 10][Tuesday 10]

일반식(19) 중, R1은 수소 원자, 또는 메틸기를 나타내고, *는 일반식(17)의 산소 원자와 결합하는 결합수이다.In General Formula (19), R 1 represents a hydrogen atom or a methyl group, and * is the bond number bonded to the oxygen atom in General Formula (17).

락톤 변성된 중합성 화합물(B1)은, 예를 들면, Nippon Kayaku Co., Ltd. 제조의 KAYARAD DPCA 시리즈로서 시판되고 있으며, DPCA-20(상기 일반식 (17) ∼ (19)에서, m ＝ 1, 일반식(18)에 표시되는 기의 수 ＝ 2, R1은 모두 수소 원자인 화합물), DPCA-30(상기 일반식 (17) ∼ (19)에서, m ＝ 1, 일반식(18)에 표시되는 기의 수 ＝ 3, R1은 모두 수소 원자인 화합물), DPCA-60(상기 일반식 (17) ∼ (19)에서, m ＝ 1, 일반식(18)에 표시되는 기의 수 ＝ 6, R1은 모두 수소 원자인 화합물), DPCA-120(상기 일반식 (17) ∼ (19)에서, m ＝ 2, 일반식(18)에 표시되는 기의 수 ＝ 6, R1은 모두 수소 원자인 화합물) 등을 들 수 있다.The lactone-modified polymerizable compound (B1) is manufactured by Nippon Kayaku Co., Ltd., for example. It is commercially available as the KAYARAD DPCA series manufactured by DPCA-20 (in the general formulas (17) to (19) above, m = 1, the number of groups represented in the general formula (18) = 2, and R 1 is all hydrogen atoms. phosphorus compound), DPCA-30 (a compound in which, in the above general formulas (17) to (19), m = 1, the number of groups represented in general formula (18) = 3, and R 1 is all a hydrogen atom), DPCA- 60 (in the general formulas (17) to (19), m = 1, the number of groups represented in the general formula (18) = 6, R 1 is a compound where all are hydrogen atoms), DPCA-120 (the general formula ( In 17) to (19), compounds in which m = 2, the number of groups represented in general formula (18) = 6, and R 1 is all hydrogen atoms) can be mentioned.

락톤 변성된 중합성 화합물(B1)은, 물 얼룩의 억제의 관점에서, 상기 일반식 (17) ∼ (19)에서, m ＝ 1, 일반식(18)에 표시되는 기의 수 ＝ 2 ∼ 6, R1은 모두 수소 원자인 화합물이 바람직하고, 상기 일반식 (17) ∼ (19)에서, m ＝ 1, 일반식(18)에 표시되는 기의 수 ＝ 2 또는 3, R1은 모두 수소 원자인 화합물이 보다 바람직하다.From the viewpoint of suppressing water stains, the lactone-modified polymerizable compound (B1) has m = 1 in the general formulas (17) to (19), and the number of groups represented in the general formula (18) = 2 to 6. , R 1 is preferably a compound in which all are hydrogen atoms, and in the general formulas (17) to (19), m = 1, the number of groups represented in general formula (18) = 2 or 3, and R 1 is all hydrogen. Compounds that are atoms are more preferred.

락톤 변성된 중합성 화합물(B1)의 함유량은, 물 얼룩의 억제의 관점에서, 중합성 화합물(B) 100질량％ 중, 5 ∼ 80질량％가 바람직하고, 10 ∼ 70질량％가 보다 바람직하고, 20 ∼ 60질량％가 더 바람직하다.The content of the lactone-modified polymeric compound (B1) is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, based on 100% by mass of the polymeric compound (B) from the viewpoint of suppressing water stains. , 20 to 60 mass% is more preferable.

(산기를 갖는 중합성 화합물(B2))(Polymerizable compound having an acid group (B2))

본 발명의 감광성 조성물은, 알칼리 현상성, 패턴 형성의 관점에서, 산기를 갖는 중합성 화합물(B2)을 포함하는 것이 바람직하다. 산기를 갖는 중합성 화합물(B2)의 산기는, 예를 들면, 설폰산기, 카르복시기, 인산기 등을 들 수 있다. 이들 중에서도, 카르복시기가 바람직하다.The photosensitive composition of the present invention preferably contains a polymerizable compound (B2) having an acid group from the viewpoint of alkali developability and pattern formation. Examples of the acid group of the polymerizable compound (B2) having an acid group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group. Among these, a carboxyl group is preferable.

산기를 갖는 중합성 화합물(B2)은, 예를 들면, 다가 알코올과 (메타)아크릴산과의 유리(遊離) 수산기 함유 폴리(메타)아크릴레이트류와, 디카르복시산류와의 에스테르화물; 다가 카르복시산과, 모노히드록시알킬(메타)아크릴레이트류와의 에스테르화물 등을 들 수 있다.Examples of the polymerizable compound (B2) having an acid group include esters of poly(meth)acrylates containing free hydroxyl groups of polyhydric alcohols and (meth)acrylic acid, and dicarboxylic acids; Esterified products of polyhydric carboxylic acids and monohydroxyalkyl (meth)acrylates, etc. can be mentioned.

다가 알코올은, 예를 들면, 에틸렌글리콜, 프로필렌글리콜, 폴리에틸렌글리콜, 폴리프로필렌글리콜, 글리세린, 트리메틸올프로판, 디트리메틸올프로판, 펜타에리트리톨, 디펜타에리트리톨 등을 들 수 있다.Examples of polyhydric alcohols include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

디카르복시산류는, 예를 들면, 말론산, 숙신산, 말레산, 글루타르산, 프탈산, 이타콘산 등을 들 수 있다.Examples of dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, and itaconic acid.

다가 카르복시산은, 예를 들면, 트리멜리트산, 피로멜리트산 등을 들 수 있다.Examples of polyhydric carboxylic acids include trimellitic acid and pyromellitic acid.

모노히드록시알킬(메타)아크릴레이트류는, 예를 들면, 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 2-히드록시부틸(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 펜타에리트리톨트리아크릴레이트, 2-히드록시-3-아크릴로일옥시프로필메타크릴레이트 등을 들 수 있다.Monohydroxyalkyl (meth)acrylates include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4 -Hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, etc. are mentioned.

산기를 갖는 중합성 화합물(B2)의 시판품은, OSAKA ORGANIC CHEMICAL INDUSTRY LTD. 제조의 Viscoat＃2500P, TOAGOSEI CO., LTD. 제조의 Aronix M-5300, M-5400, M-5700, M-510, M-520, M-521 등을 들 수 있다.The commercially available polymerizable compound (B2) having an acid group is manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD. Manufactured by Viscoat #2500P, TOAGOSEI CO., LTD. Examples include Aronix M-5300, M-5400, M-5700, M-510, M-520, and M-521.

산기를 갖는 중합성 화합물(B2)의 함유량은, 알칼리 현상성, 패턴 형성의 관점에서, 중합성 화합물(B) 100질량％ 중, 5 ∼ 80질량％가 바람직하고, 10 ∼ 70질량％인 것이 보다 바람직하고, 20 ∼ 60질량％인 것이 더 바람직하다.The content of the polymerizable compound (B2) having an acid group is preferably 5 to 80 mass%, and is preferably 10 to 70 mass%, based on 100 mass% of the polymerizable compound (B), from the viewpoint of alkali developability and pattern formation. It is more preferable, and it is still more preferable that it is 20-60 mass %.

(우레탄 결합을 갖는 중합성 화합물(B3))(Polymerizable compound having a urethane bond (B3))

본 발명의 감광성 조성물은, 패턴 형성의 관점에서, 우레탄 결합을 갖는 중합성 화합물(B3)을 포함하는 것이 바람직하다.The photosensitive composition of the present invention preferably contains a polymerizable compound (B3) having a urethane bond from the viewpoint of pattern formation.

우레탄 결합을 갖는 중합성 화합물(B3)은, 예를 들면, 수산기를 갖는 (메타)아크릴레이트에 다관능 이소시아네이트를 반응시켜 얻어지는 우레탄(메타)아크릴레이트나, 다가 알코올에 다관능 이소시아네이트를 반응시키고, 또한 수산기를 갖는 (메타)아크릴레이트를 반응시켜 얻어지는 우레탄(메타)아크릴레이트 등을 들 수 있다.The polymerizable compound (B3) having a urethane bond is, for example, urethane (meth)acrylate obtained by reacting polyfunctional isocyanate with (meth)acrylate having a hydroxyl group, or reacting polyfunctional isocyanate with polyhydric alcohol, Additionally, urethane (meth)acrylate obtained by reacting (meth)acrylate having a hydroxyl group can be mentioned.

상기 수산기를 갖는 (메타)아크릴레이트는, 예를 들면, 2-히드록시에틸(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 트리메틸올프로판디(메타)아크릴레이트, 펜타에리트리톨트리(메타)아크릴레이트, 디트리메틸올프로판트리(메타)아크릴레이트, 디펜타에리트리톨펜타(메타)아크릴레이트, 디펜타에리트리톨에틸렌옥사이드 변성 펜타(메타)아크릴레이트, 디펜타에리트리톨프로필렌옥사이드 변성 펜타(메타)아크릴레이트, 디펜타에리트리톨카프로락톤 변성 펜타(메타)아크릴레이트, 글리세롤아크릴레이트메타크릴레이트, 글리세롤디메타크릴레이트, 2-히드록시-3-아크릴로일프로필메타크릴레이트, 에폭시기 함유 화합물과 카르복시(메타)아크릴레이트의 반응물, 수산기 함유 폴리올폴리아크릴레이트 등을 들 수 있다.(meth)acrylates having the hydroxyl group include, for example, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropanedi(meth)acrylate, and pentaerythritol. Tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide modified penta(meth)acrylate, dipentaerythritol propylene oxide modified Penta(meth)acrylate, dipentaerythritol caprolactone modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, epoxy group Examples include reactants of containing compounds and carboxy (meth)acrylates, and hydroxyl group-containing polyol polyacrylates.

상기 다관능 이소시아네이트는, 예를 들면, 방향족 디이소시아네이트인 톨릴렌디이소시아네이트, 디페닐메틸렌디이소시아네이트, 자일렌디이소시아네이트, 지방족 디이소시아네이트인 트리메틸렌디이소시아네이트, 테트라메틸렌디이소시아네이트, 헥사메틸렌디이소시아네이트, 지환식 디이소시아네이트인 이소포론디이소시아네이트나, 이들 뷰렛체, 이소시아네이트누레이트체, 트리메틸올프로판 어덕트체 등을 들 수 있다.The polyfunctional isocyanate is, for example, aromatic diisocyanate such as tolylene diisocyanate, diphenylmethylene diisocyanate, xylene diisocyanate, and aliphatic diisocyanate such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and alicyclic diisocyanate. Examples include isophorone diisocyanate, which is isocyanate, and these biuret products, isocyanate nurate products, and trimethylolpropane adduct products.

우레탄 결합을 갖는 중합성 화합물(B3)은, 현상성의 관점에서, 또한, 산기를 갖는 것도 바람직하다. 산기는, 예를 들면, 설폰산기, 카르복시기, 인산기 등을 들 수 있다. 그 중에서도, 카르복시기가 바람직하다.The polymerizable compound (B3) having a urethane bond also preferably has an acid group from the viewpoint of developability. Examples of acid groups include sulfonic acid groups, carboxyl groups, and phosphoric acid groups. Among them, a carboxyl group is preferable.

우레탄 결합을 갖는 중합성 화합물(B3)에 산기를 도입하는 방법은, 예를 들면, 우선, 상기 수산기를 갖는 (메타)아크릴레이트와 상기 다관능 이소시아네이트를 반응시킨다. 그 다음에, 생성물에 카르복시기를 갖는 메르캅토 화합물을 부가시키는 방법으로 합성할 수 있다.To introduce an acid group into the polymerizable compound (B3) having a urethane bond, for example, first, the (meth)acrylate having the hydroxyl group is reacted with the polyfunctional isocyanate. Next, it can be synthesized by adding a mercapto compound having a carboxyl group to the product.

상기 카르복시기를 갖는 메르캅토 화합물은, 예를 들면, 메르캅토아세트산, 2-메르캅토프로피온산, 3-메르캅토프로피온산, o-메르캅토벤조산, 2-메르캅토니코틴산, 메르캅토숙신산 등을 들 수 있다.Examples of the mercapto compound having the carboxyl group include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

우레탄 결합을 갖는 중합성 화합물(B3)의 함유량은, 패턴 형성의 관점에서, 중합성 화합물(B) 100질량％ 중, 5 ∼ 80질량％가 바람직하고, 10 ∼ 70질량％가 보다 바람직하고, 20 ∼ 60질량％가 더 바람직하다.From the viewpoint of pattern formation, the content of the polymerizable compound (B3) having a urethane bond is preferably 5 to 80 mass%, more preferably 10 to 70 mass%, based on 100 mass% of the polymerizable compound (B). 20 to 60 mass% is more preferable.

(그 외 중합성 화합물(B4))(Other polymerizable compounds (B4))

그 외 중합성 화합물(B4)은, 예를 들면, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, β-카르복시에틸(메타)아크릴레이트, 폴리에틸렌글리콜디(메타)아크릴레이트, 1,6-헥산디올디(메타)아크릴레이트, 트리에틸렌글리콜디(메타)아크릴레이트, 폴리프로필렌글리콜디(메타)아크릴레이트, 트리메틸올프로판트리(메타)아크릴레이트, 페녹시테트라에틸렌글리콜(메타)아크릴레이트, 페녹시헥사에틸렌글리콜(메타)아크릴레이트, 트리메틸올프로판 PO 변성 트리(메타)아크릴레이트, 트리메틸올프로판 EO 변성 트리(메타)아크릴레이트, 이소시아누르산 EO 변성 디(메타)아크릴레이트, 이소시아누르산 EO 변성 트리(메타)아크릴레이트, 디트리메틸올프로판테트라(메타)아크릴레이트, 펜타에리트리톨트리(메타)아크릴레이트, 펜타에리트리톨테트라(메타)아크릴레이트, 1,6-헥산디올디글리시딜에테르디(메타)아크릴레이트, 비스페놀A디글리시딜에테르디(메타)아크릴레이트, 네오펜틸글리콜디글리시딜에테르디(메타)아크릴레이트, 디펜타에리트리톨헥사(메타)아크릴레이트, 디펜타에리트리톨펜타(메타)아크릴레이트, 트리시클로데카닐(메타)아크릴레이트, 메틸올화 멜라민의 (메타)아크릴산에스테르, 에폭시(메타)아크릴레이트 등의 각종 아크릴산에스테르 및 메타크릴산에스테르, 스티렌, 아세트산비닐, 히드록시에틸비닐에테르, 에틸렌글리콜디비닐에테르, 펜타에리트리톨트리비닐에테르, (메타)아크릴아미드, N-히드록시메틸(메타)아크릴아미드, N-비닐포름아미드, 아크릴로니트릴 등을 들 수 있다. 또, EO는 에틸렌옥시, PO는 프로필렌옥시이다.Other polymerizable compounds (B4) include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, Cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, Polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol(meth)acrylate, phenoxyhexaethylene glycol(meth)acrylate, trimethylolpropane PO modified tri(meth)acrylate ) Acrylate, trimethylolpropane EO modified tri(meth)acrylate, isocyanuric acid EO modified di(meth)acrylate, isocyanuric acid EO modified tri(meth)acrylate, ditrimethylolpropane tetra(meth) Acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di( Meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate Various acrylic acid esters and methacrylic acid esters such as methylolated melamine (meth)acrylic acid ester and epoxy (meth)acrylate, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trimethylene. Vinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile, etc. are mentioned. Additionally, EO is ethyleneoxy and PO is propyleneoxy.

그 외 중합성 화합물(B4)의 시판품은, 예를 들면, Nippon Kayaku Co., Ltd. 제조의 KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, 및 TOAGOSEI CO., LTD. 제조의 Aronix M-303, M-305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, OSAKA ORGANIC CHEMICAL INDUSTRY LTD. 제조의 Viscoat＃310HP, ＃335HP, ＃700, ＃295, ＃330, ＃360, ＃GPT, ＃400, ＃405, kyoeisha chemical co., ltd. 제조의 AH-600, AT-600, SHIN-NAKAMURA CHEMICAL CO., LTD. 제조의 NK 에스테르 A-9300, ABE-300, A-DOG, A-DCP, A-BPE-4, DAICEL-ALLNEX LTD. 제조의 EBECRYL40, 130, 140, 145, Osaka Gas Chemicals Co., Ltd. 제조의 OGSOL EA-0200, 0300 등을 들 수 있다.Other commercial products of polymerizable compound (B4) include, for example, Nippon Kayaku Co., Ltd. Manufactured by KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA -2C, D-310, D-330, and TOAGOSEI CO., LTD. Manufacturing Aronix M-303, M-305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400 , M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, OSAKA ORGANIC CHEMICAL INDUSTRY LTD. Manufactured by Viscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, #405, kyoeisha chemical co., ltd. Manufacturing AH-600, AT-600, SHIN-NAKAMURA CHEMICAL CO., LTD. Manufactured by NK Ester A-9300, ABE-300, A-DOG, A-DCP, A-BPE-4, DAICEL-ALLNEX LTD. Manufactured by EBECRYL40, 130, 140, 145, Osaka Gas Chemicals Co., Ltd. Examples include OGSOL EA-0200 and 0300 manufactured by OGSOL.

중합성 화합물(B)은, 단독 또는 2종류 이상을 병용하여 사용할 수 있다.The polymerizable compound (B) can be used individually or in combination of two or more types.

중합성 화합물(B)은, 물 얼룩의 억제, 잔막률, 및 패턴 형성의 관점에서, 락톤 변성된 중합성 화합물(B1), 산기를 갖는 중합성 화합물(B2), 및 우레탄 결합 및 산기를 갖는 중합성 화합물(B3)로 이루어지는 군에서 선택되는 1종 이상이 바람직하고, 2종 이상이 보다 바람직하다.The polymerizable compound (B) is a lactone-modified polymerizable compound (B1), a polymerizable compound (B2) having an acid group, and a polymerizable compound (B2) having a urethane bond and an acid group from the viewpoint of suppressing water stains, remaining film rate, and pattern formation. One or more types selected from the group consisting of polymerizable compounds (B3) is preferable, and two or more types are more preferable.

중합성 화합물(B)의 함유량은, 감광성 조성물의 불휘발분 100질량％ 중, 1 ∼ 60질량％가 바람직하고, 2 ∼ 50질량％가 보다 바람직하다.The content of the polymerizable compound (B) is preferably 1 to 60% by mass, and more preferably 2 to 50% by mass, based on 100% by mass of non-volatile matter of the photosensitive composition.

[티올계 연쇄 이동제(D)][Thiol-based chain transfer agent (D)]

본 발명의 감광성 조성물은, 물 얼룩의 억제, 패턴 형성의 관점에서, 티올계 연쇄 이동제(D)를 포함하는 것이 바람직하다.The photosensitive composition of the present invention preferably contains a thiol-based chain transfer agent (D) from the viewpoint of suppressing water stains and forming patterns.

티올계 연쇄 이동제(D)는, 티올기(SH기)를 2 이상 갖는 다관능 티올이 바람직하다. 또, 티올계 연쇄 이동제는, SH기를 4 이상 갖는 것이 보다 바람직하다. 관능기 수가 증가하면 피막의 표면에서 최심부까지 광경화되기 쉬워진다.The thiol-based chain transfer agent (D) is preferably a polyfunctional thiol having two or more thiol groups (SH groups). Moreover, it is more preferable that the thiol-based chain transfer agent has 4 or more SH groups. As the number of functional groups increases, photocuring from the surface to the deepest part of the film becomes easier.

다관능 티올은, 예를 들면, 헥산디티올, 데칸디티올, 1,4-부탄디올비스티오프로피오네이트, 1,4-부탄디올비스티오글리콜레이트, 에틸렌글리콜비스티오글리콜레이트, 에틸렌글리콜비스티오프로피오네이트, 트리메틸올프로판트리스티오글리콜레이트, 트리메틸올프로판트리스티오프로피오네이트, 트리메틸올프로판트리스(3-메르캅토부틸레이트), 펜타에리트리톨테트라키스티오글리콜레이트, 펜타에리트리톨테트라키스티오프로피오네이트, 트리메르캅토프로피온산트리스(2-히드록시에틸)이소시아누레이트, 1,4-디메틸메르캅토벤젠, 2,4,6-트리메르캅토-s-트리아진, 2-(N,N-디부틸아미노)-4,6-디메르캅토-s-트리아진 등을 들 수 있고, 바람직하게는, 에틸렌글리콜비스티오프로피오네이트, 트리메틸올프로판트리스티오프로피오네이트, 펜타에리트리톨테트라키스티오프로피오네이트 등을 들 수 있다.Polyfunctional thiols include, for example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropionate. Cypionate, Trimethylolpropane Tristioglycolate, Trimethylolpropane Tristiopropionate, Trimethylolpropane Tris(3-Mercaptobutyrate), Pentaerythritol Tetrachistioglycolate, Pentaerythritol Tetrachisthiopropio Nate, trimercaptopropionic acid, tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N- dibutylamino)-4,6-dimercapto-s-triazine, etc., preferably ethylene glycol bisthiopropionate, trimethylolpropane trithiopropionate, and pentaerythritol tetrakistio. Propionate, etc. can be mentioned.

티올계 연쇄 이동제(D)는, 단독 또는 2종류 이상을 병용하여 사용할 수 있다.The thiol-based chain transfer agent (D) can be used alone or in combination of two or more types.

티올계 연쇄 이동제(D)의 함유량은, 감광성 조성물의 불휘발분 100질량부 중, 1 ∼ 10질량부가 바람직하고, 2 ∼ 8질량부가 보다 바람직하다.The content of the thiol-based chain transfer agent (D) is preferably 1 to 10 parts by mass, more preferably 2 to 8 parts by mass, based on 100 parts by mass of non-volatile matter of the photosensitive composition.

[착색제(E)][Colorant (E)]

본 발명의 감광성 조성물은, 착색제(E)를 함유할 수 있다.The photosensitive composition of the present invention may contain a colorant (E).

착색제(E)는, 안료, 및 염료 중 어느 것이어도 좋고, 병용할 수 있다.The colorant (E) may be either a pigment or a dye, and can be used in combination.

(안료)(pigment)

안료는, 컬러 인덱스에 있어서 피그먼트로 분류되고 있는 화합물이다.Pigments are compounds classified as pigments in the color index.

적색 안료는, 예를 들면, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, 일본 특허공개 2014-134712호 공보에 기재된 안료, 일본 특허 제6368844호 공보에 기재된 안료 등을 들 수 있다. 이들 중에서도, 내열성, 내광성, 및 투과율의 관점에서, C.I. Pigment Red 48:1, 122, 177, 224, 242, 269, 254, 291, 295, 296, 일본 특허공개 2014-134712호 공보에 기재된 안료, 일본 특허 제6368844호 공보에 기재된 안료가 바람직하고, C.I. Pigment Red 177, 254, 291, 295, 296, 일본 특허공개 2014-134712호 공보에 기재된 안료, 일본 특허 제6368844호 공보에 기재된 안료가 더 바람직하다.Red pigments are, for example, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 2 08, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 2 54, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 2 80, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, the pigment described in Japanese Patent Application Laid-Open No. 2014-134712, the pigment described in Japanese Patent No. 6368844, etc. Among these, from the viewpoint of heat resistance, light resistance, and transmittance, C.I. Pigment Red 48:1, 122, 177, 224, 242, 269, 254, 291, 295, 296, the pigment described in Japanese Patent Application Laid-Open No. 2014-134712, the pigment described in Japanese Patent No. 6368844 are preferred, and C.I. Pigment Red 177, 254, 291, 295, 296, the pigment described in Japanese Patent Application Laid-Open No. 2014-134712, and the pigment described in Japanese Patent No. 6368844 are more preferable.

등색(橙色) 안료는, 예를 들면, C.I. Pigment Orange 36, 38, 43, 64, 71, 73 등을 들 수 있다.Orange pigments include, for example, C.I. Pigment Orange 36, 38, 43, 64, 71, 73, etc. are included.

황색 안료는, 예를 들면, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, 일본 특허공개 2012-226110호 공보에 기재된 안료 등을 들 수 있다. 이들 중에서도, C.I. Pigment Yellow 138, 139, 150, 185, 231, 233, 일본 특허공개 2012-226110호 공보에 기재된 안료가 바람직하다.Yellow pigments are, for example, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 1 53, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 1 88, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, and pigments described in Japanese Patent Application Laid-Open No. 2012-226110. Among these, C.I. Pigment Yellow 138, 139, 150, 185, 231, 233, and the pigments described in Japanese Patent Application Laid-Open No. 2012-226110 are preferred.

녹색 안료는, 예를 들면, C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63 등을 들 수 있다. 이들 중에서도, C.I. Pigment Green 36, 58, 59, 62, 63이 바람직하다.Green pigments are, for example, C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, etc. Among these, C.I. Pigment Green 36, 58, 59, 62, 63 are preferred.

청색 안료는, 예를 들면, C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 등을 들 수 있다. 이들 중에서도, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6이 바람직하다.Blue pigments are, for example, C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, Examples include 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Among these, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are preferred.

자색 안료는, 예를 들면, C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 등을 들 수 있다. 이들 중에서도, C.I. Pigment Violet 19, 23이 바람직하다.Purple pigments are, for example, C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, Examples include 37, 39, 42, 44, 47, 49, 50, etc. Among these, C.I. Pigment Violet 19, 23 is preferred.

흑색 안료는, 구체적으로는, C.I. Pigment Black 1, 6, 7, 12, 20, 31 등을 들 수 있다. 또한, 적색 안료, 황색 안료, 청색 안료, 녹색 안료, 및 자색 안료에서 선택되는 적어도 2종 이상의 안료를 이용하여 흑색 착색제로 해도 된다.The black pigment is, specifically, C.I. Pigment Black 1, 6, 7, 12, 20, 31, etc. Additionally, at least two pigments selected from red pigments, yellow pigments, blue pigments, green pigments, and purple pigments may be used to form a black colorant.

안료 중에서 무기 안료는, 예를 들면, 산화티탄, 황산바륨, 아연화, 황산납, 황색 납, 아연 황, 벵갈라(적색 산화철(iii)), 카드뮴 적, 군청, 감청, 산화크롬 녹, 코발트 녹, 앰버, 합성철 흑 등을 들 수 있다.Among the pigments, inorganic pigments include, for example, titanium oxide, barium sulfate, zinc oxide, lead sulfate, lead yellow, zinc sulphate, Bengala (red iron(iii) oxide), cadmium red, ultramarine blue, royal blue, chromium oxide rust, cobalt rust, Examples include amber and synthetic iron black.

(염료)(dyes)

염료는, 예를 들면, 산성 염료, 직접 염료, 염기성 염료, 조염(造鹽) 염료, 유용성(油溶性) 염료, 분산 염료, 반응 염료, 매염 염료, 건염 염료, 황화 염료 등을 들 수 있다. 또한, 이들 유도체나, 염료를 레이크화한 레이크 안료도 들 수 있다.Examples of dyes include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. Additionally, lake pigments obtained by laking these derivatives and dyes can also be used.

산성 염료는, 설폰산이나 카르복시산 등의 산성기를 갖는 것이 바람직하다. 또한, 산성 염료와, 4급 암모늄염 화합물, 3급 아민 화합물, 2급 아민 화합물, 또는 1급 아민 화합물 등의 함(含)질소 화합물과의 염인 조염 화합물이 바람직하다. 또한, 이들 관능기를 갖는 수지 성분과 산성 염료와의 염인 조염 화합물도 바람직하다. 또한, 조염 화합물은, 설폰아미드화하여 설폰산아미드 화합물로 변성함으로써 내성(내광성, 내용제성)이 우수한 감광성 조성물을 얻기 쉽다.The acid dye preferably has an acidic group such as sulfonic acid or carboxylic acid. Additionally, a salt-forming compound that is a salt of an acid dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound is preferable. Additionally, a salt-forming compound that is a salt of a resin component having these functional groups and an acidic dye is also preferred. Additionally, the salt-forming compound is easily converted into a sulfonic acid amide compound through sulfonamidation to obtain a photosensitive composition with excellent resistance (light resistance, solvent resistance).

또한, 산성 염료와 오늄염기를 갖는 화합물과의 조염 화합물도, 내성(내광성, 내용제성)이 우수하기 때문에 바람직하다. 또, 오늄염기를 갖는 화합물은, 양이온성기를 갖는 수지가 바람직하다.Additionally, a salt-formation compound of an acid dye and a compound having an onium base is also preferable because it is excellent in resistance (light resistance, solvent resistance). Moreover, the compound having an onium base is preferably a resin having a cationic group.

염기성 염료는, 그대로도 사용할 수 있지만, 유기산이나 과염소산 또는 그 금속염과 염을 형성하는 조염 화합물이 바람직하다. 염기성 염료의 조염 화합물은, 내성(내광성, 내용제성)이나, 안료와의 친화성이 우수하기 때문에 바람직하다. 또한, 염기성 염료의 조염 화합물에서, 카운터 이온으로서 기능하는 음이온 성분은, 유기 설폰산, 유기 황산, 불소기 함유 인 음이온 화합물, 불소기 함유 붕소 음이온 화합물, 시아노기 함유 질소 음이온 화합물, 할로겐화 탄화수소기를 갖는 유기산의 공역염기를 갖는 음이온 화합물, 산성 염료를 조염한 조염 화합물이 바람직하다. 또, 조염 화합물은, 분자 중에 중합성 불포화기를 함유하면 내성이 보다 향상된다.The basic dye can be used as is, but a salt-forming compound that forms a salt with an organic acid, perchloric acid, or a metal salt thereof is preferred. Salt-forming compounds of basic dyes are preferred because they are excellent in resistance (light resistance, solvent resistance) and affinity with pigments. In addition, in the salt formation compound of a basic dye, the anionic component that functions as a counter ion includes organic sulfonic acid, organic sulfuric acid, a phosphorus anionic compound containing a fluorine group, a boron anionic compound containing a fluorine group, a nitrogen anionic compound containing a cyano group, and a halogenated hydrocarbon group-containing compound. Anionic compounds having a conjugated base of an organic acid and salt-forming compounds prepared by salt-forming an acidic dye are preferable. In addition, the resistance of the salt-forming compound is further improved when it contains a polymerizable unsaturated group in the molecule.

염료의 화학 구조는, 예를 들면, 아조계 염료, 디스아조계 염료, 아조메틴계 염료(인도아닐린계 염료, 인도페놀계 염료 등), 디피로메텐계 염료, 퀴논계 염료(벤조퀴논계 염료, 나프토퀴논계 염료, 안트라퀴논계 염료, 안트라피리돈계 염료 등), 카르보늄계 염료(디페닐메탄계 염료, 트리페닐메탄계 염료, 크산텐계 염료, 아크리딘계 염료 등), 퀴논이민계 염료(옥사진계 염료, 티아진계 염료 등), 아진계 염료, 폴리메틴계 염료(옥소놀계 염료, 멜로시아닌계 염료, 아릴리덴계 염료, 스티릴계 염료, 시아닌계 염료, 스쿠알륨계 염료, 클로코늄계 염료 등), 퀴나프탈론계 염료, 프탈로시아닌계 염료, 서브프탈로시아닌계 염료, 페리논계 염료, 인디고계 염료, 티오인디고계 염료, 퀴놀린계 염료, 니트로계 염료, 니트로소계 염료, 로다민계 염료, 및 그들 금속 착체계 염료 등에서 선택되는 염료에서 유래된 색소 구조를 들 수 있다.The chemical structures of dyes include, for example, azo-based dyes, disazo-based dyes, azomethine-based dyes (indaniline-based dyes, indophenol-based dyes, etc.), dipyromethene-based dyes, and quinone-based dyes (benzoquinone-based dyes, Naphthoquinone-based dyes, anthraquinone-based dyes, anthrapyridone-based dyes, etc.), carbonium-based dyes (diphenylmethane-based dyes, triphenylmethane-based dyes, xanthene-based dyes, acridine-based dyes, etc.), quinone imine-based dyes ( Oxazine-based dyes, thiazine-based dyes, etc.), azine-based dyes, polymethine-based dyes (oxonol-based dyes, melocyanine-based dyes, arylidene-based dyes, styryl-based dyes, cyanine-based dyes, squalium-based dyes, chlorconium-based dyes dyes, etc.), quinaphthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perrinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and them. Examples include dye structures derived from dyes selected from metal complex dyes and the like.

이들 중에서도, 색상, 색 분리성, 색 얼룩 등의 색 특성의 관점에서, 아조계 염료, 크산텐계 염료, 시아닌계 염료, 트리페닐메탄계 염료, 안트라퀴논계 염료, 디피로메텐계 염료, 스쿠알륨계 염료, 퀴나프탈론계 염료, 프탈로시아닌계 염료, 서브프탈로시아닌계 염료에서 선택되는 색소에서 유래된 색소 구조가 바람직하고, 크산텐계 염료, 시아닌계 염료, 트리페닐메탄계 염료, 안트라퀴논계 염료, 디피로메텐계 염료, 프탈로시아닌계 염료에서 선택되는 색소에서 유래된 색소 구조가 보다 바람직하다.Among these, from the viewpoint of color characteristics such as color, color separation, and color staining, azo-based dyes, xanthene-based dyes, cyanine-based dyes, triphenylmethane-based dyes, anthraquinone-based dyes, dipyromethene-based dyes, and squalium-based dyes. A dye structure derived from a dye selected from dyes, quinaphthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes is preferable, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, and dipyromethane dyes are preferred. A pigment structure derived from a pigment selected from ten-based dyes and phthalocyanine-based dyes is more preferable.

착색제(E)는, 단독, 또는 2종류 이상을 병용하여 사용할 수 있다.The colorant (E) can be used individually or in combination of two or more types.

착색제(E)의 함유량은, 감광성 조성물의 불휘발분 100질량％ 중, 5 ∼ 70질량％가 바람직하고, 10 ∼ 60질량％가 보다 바람직하다.The content of the colorant (E) is preferably 5 to 70% by mass, and more preferably 10 to 60% by mass, based on 100% by mass of non-volatile matter of the photosensitive composition.

(안료의 미세화)(Pigment refinement)

안료는, 미세화하여 이용하는 것이 바람직하다. 미세화 방법은, 특별히 한정되는 것이 아니고, 예를 들면, 습식 마쇄, 건식 마쇄, 용해 석출법 모두 사용할 수 있다. 이들 중에서도, 습식 마쇄의 1종인 니더법에 의한 솔트 밀링 처리가 바람직하다. 미세화 안료의 TEM(투과형 전자 현미경)에 의해 구해지는 평균 일차 입자경은, 5 ∼ 90㎚가 바람직하다. 또, 분산성, 콘트라스트비의 관점에서, 평균 일차 입자경은 10 ∼ 70㎚가 보다 바람직하다.It is preferable to use the pigment after micronizing it. The micronization method is not particularly limited, and for example, wet friction grinding, dry friction grinding, and melting and precipitation methods can all be used. Among these, salt milling treatment by the kneader method, which is a type of wet friction grinding, is preferable. The average primary particle diameter of the micronized pigment determined by TEM (transmission electron microscope) is preferably 5 to 90 nm. Moreover, from the viewpoint of dispersibility and contrast ratio, the average primary particle diameter is more preferably 10 to 70 nm.

솔트 밀링 처리란, 안료와 수용성 무기염과 수용성 유기 용제와의 혼합물을, 니더, 2개 롤 밀, 3개 롤 밀, 볼 밀, 어트리터(attritor), 샌드 밀 등의 혼련기를 이용하여, 가열하면서 기계적으로 혼련한 후, 수세(水洗)에 의해 수용성 무기염과 수용성 유기 용제를 제거하는 처리이다. 수용성 무기염은, 파쇄 조제로서 기능하는 것이며, 솔트 밀링 시에 무기염의 경도(硬度)의 높이를 이용하여 안료가 파쇄된다. 안료를 솔트 밀링 처리할 때의 조건을 최적화함으로써, 일차 입자경이 매우 미세하며, 또한, 분포의 폭이 좁고, 샤프한 입도 분포를 가지는 안료를 얻을 수 있다.Salt milling treatment refers to heating a mixture of pigment, water-soluble inorganic salt, and water-soluble organic solvent using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. This is a treatment to remove water-soluble inorganic salts and water-soluble organic solvents by mechanically kneading and then washing with water. The water-soluble inorganic salt functions as a crushing aid, and the pigment is crushed using the hardness level of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment with a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

수용성 무기염은, 염화나트륨, 염화칼륨, 황산나트륨 등을 들 수 있다. 수용성 무기염은, 가격의 점에서 염화나트륨(식염)이 바람직하다. 수용성 무기염의 사용량은, 처리 효율과 생산 효율의 양면에서, 안료 100질량부에 대하여, 50 ∼ 2,000질량부가 바람직하고, 300 ∼ 1,000질량부가 보다 바람직하다.Water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate. The water-soluble inorganic salt is preferably sodium chloride (table salt) from the viewpoint of cost. The amount of water-soluble inorganic salt used is preferably 50 to 2,000 parts by mass, more preferably 300 to 1,000 parts by mass, per 100 parts by mass of the pigment, from the viewpoint of both processing efficiency and production efficiency.

수용성 유기 용제는, 안료 및 수용성 무기염을 습윤하는 기능을 하는 것이며, 물에 용해(혼화)하며, 또한 이용하는 무기염을 실질적으로 용해하지 않는 용제이다. 단, 솔트 밀링 시에 온도가 상승하여, 용제가 증발하기 쉬운 상태가 되기 때문에, 안전성의 점에서, 비점 120℃ 이상의 고(高)비점 용제가 바람직하다. 예를 들면, 2-메톡시에탄올, 2-부톡시에탄올, 2-(이소펜틸옥시)에탄올, 2-(헥실옥시)에탄올, 디에틸렌글리콜, 디에틸렌글리콜모노에틸에테르, 디에틸렌글리콜모노부틸에테르, 트리에틸렌글리콜, 트리에틸렌글리콜모노메틸에테르, 액상의 폴리에틸렌글리콜, 1-메톡시-2-프로판올, 1-에톡시-2-프로판올, 디프로필렌글리콜, 디프로필렌글리콜모노메틸에테르, 디프로필렌글리콜모노에틸에테르, 액상의 폴리프로필렌글리콜 등이 이용된다. 수용성 유기 용제의 사용량은, 안료 100질량부에 대하여, 5 ∼ 1,000질량부가 바람직하고, 50 ∼ 500질량부가 보다 바람직하다.The water-soluble organic solvent is a solvent that functions to wet the pigment and the water-soluble inorganic salt, dissolves (miscible) in water, and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent becomes prone to evaporation, a high boiling point solvent with a boiling point of 120°C or higher is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl. Ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol Monoethyl ether, liquid polypropylene glycol, etc. are used. The amount of the water-soluble organic solvent used is preferably 5 to 1,000 parts by mass, and more preferably 50 to 500 parts by mass, per 100 parts by mass of the pigment.

솔트 밀링 처리에는, 필요에 따라 수지를 첨가해도 된다. 상기 수지의 종류는 특별히 한정되지 않고, 천연 수지, 변성 천연 수지, 합성 수지, 천연 수지에 의해 변성된 합성 수지 등을 들 수 있다. 이들 중에서도, 실온에서 고체이며, 수불용성이 바람직하며, 또한 상기 유기 용제에 일부 가용이 바람직하다. 수지의 첨가량은, 안료 100질량부에 대하여, 2 ∼ 200질량부가 바람직하다.Resin may be added to the salt milling treatment as needed. The type of the resin is not particularly limited and includes natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, it is preferable that it is solid at room temperature, insoluble in water, and partially soluble in the above organic solvent. The amount of resin added is preferably 2 to 200 parts by mass per 100 parts by mass of the pigment.

[색소 유도체(F)][Pigment derivative (F)]

본 발명의 감광성 조성물은, 색소 유도체(F)를 함유할 수 있다.The photosensitive composition of the present invention may contain a dye derivative (F).

색소 유도체(F)는, 유기 색소 잔기에 산성기, 염기성기, 중성기 등을 갖는 화합물이다. 색소 유도체(F)는, 예를 들면, 술포기, 카르복시기, 인산기 등의 산성 치환기를 갖는 화합물, 및 이들 아민염이나, 설폰아미드기나 말단에 3급 아미노기 등의 염기성 치환기를 갖는 화합물, 페닐기나 프탈이미드알킬기 등의 중성 치환기를 갖는 화합물을 들 수 있다.The dye derivative (F) is a compound having an acidic group, a basic group, a neutral group, etc. in the organic dye residue. The dye derivative (F) is, for example, a compound having an acidic substituent such as a sulfo group, a carboxyl group, or a phosphoric acid group, and an amine salt thereof, a sulfonamide group, or a compound having a basic substituent such as a tertiary amino group at the terminal, a phenyl group, or a phthal group. Compounds having a neutral substituent such as an imidealkyl group can be mentioned.

유기 색소는, 예를 들면 디케토피롤로피롤계 안료, 안트라퀴논계 안료, 퀴나크리돈계 안료, 디옥사진계 안료, 페리논계 안료, 페릴렌계 안료, 티아진인디고계 안료, 트리아진계 안료, 벤즈이미다졸론계 안료, 벤조이소인돌 등의 인돌계 안료, 이소인돌린계 안료, 이소인돌리논계 안료, 퀴나프탈론계 안료, 나프톨계 안료, 스렌계 안료, 금속 착체계 안료, 아조, 디스아조, 폴리아조 등의 아조계 안료 등을 들 수 있다.Organic pigments include, for example, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, and benzimidazolone. pigments, indole-based pigments such as benzoisoindole, isoindoline-based pigments, isoindolinone-based pigments, quinaphthalone-based pigments, naphthol-based pigments, srene-based pigments, metal complex-based pigments, azo, disazo, and polyazo. and azo pigments such as these.

구체적으로는, 디케토피롤로피롤계 색소 유도체로서는, 일본 특허공개 2001-220520호 공보, 국제공개 제2009／081930호, 국제공개 제2011／052617호, 국제공개 제2012／102399호, 일본 특허공개 2017-156397호 공보, 프탈로시아닌계 색소 유도체로서는, 일본 특허공개 2007-226161호 공보, 국제공개 제2016／163351호, 일본 특허공개 2017-165820호 공보, 일본 특허 제5753266호 공보, 안트라퀴논계 색소 유도체로서는, 일본 특허공개 소 63-264674호 공보, 일본 특허공개 평 09-272812호 공보, 일본 특허공개 평 10-245501호 공보, 일본 특허공개 평 10-265697호 공보, 일본 특허공개 2007-079094호 공보, 국제공개 제2009／025325호, 퀴나크리돈계 색소 유도체로서는, 일본 특허공개 소 48-54128호 공보, 일본 특허공개 평 03-9961호 공보, 일본 특허공개 2000-273383호 공보, 디옥사진계 색소 유도체로서는, 일본 특허공개 2011-162662호 공보, 티아진인디고계 색소 유도체로서는, 일본 특허공개 2007-314785호 공보, 트리아진계 색소 유도체로서는, 일본 특허공개 소 61-246261호 공보, 일본 특허공개 평 11-199796호 공보, 일본 특허공개 2003-165922호 공보, 일본 특허공개 2003-168208호 공보, 일본 특허공개 2004-217842호 공보, 일본 특허공개 2007-314681호 공보, 벤조이소인돌계 색소 유도체로서는, 일본 특허공개 2009-57478호 공보, 퀴나프탈론계 색소 유도체로서는, 일본 특허공개 2003-167112호 공보, 일본 특허공개 2006-291194호 공보, 일본 특허공개 2008-31281호 공보, 일본 특허공개 2012-226110호 공보, 나프톨계 색소 유도체로서는, 일본 특허공개 2012-208329호 공보, 일본 특허공개 2014-5439호 공보, 아조계 색소 유도체로서는, 일본 특허공개 2001-172520호 공보, 일본 특허공개 2012-172092호 공보, 산성 치환기로서는, 일본 특허공개 2004-307854호 공보, 염기성 치환기로서는, 일본 특허공개 2002-201377호 공보, 일본 특허공개 2003-171594호 공보, 일본 특허공개 2005-181383호 공보, 일본 특허공개 2005-213404호 공보 등에 기재된 공지된 색소 유도체를 들 수 있다. 또, 이들 문헌에는, 색소 유도체를 유도체, 안료 유도체, 분산제, 안료 분산제 또는 단순히 화합물 등이라고 기재하고 있는 경우가 있지만, 상기한 유기 색소 잔기에 산성기, 염기성기, 중성기 등의 치환기를 갖는 화합물은, 색소 유도체와 동의(同義)이다.Specifically, as diketopyrrolopyrrole dye derivatives, Japanese Patent Application Laid-Open No. 2001-220520, International Publication No. 2009/081930, International Publication No. 2011/052617, International Publication No. 2012/102399, Japanese Patent Publication No. 2017 -156397, as phthalocyanine pigment derivatives, Japanese Patent Application Laid-Open No. 2007-226161, International Publication No. 2016/163351, Japanese Patent Application Laid-Open No. 2017-165820, Japanese Patent No. 5753266, as an anthraquinone pigment derivative , Japanese Patent Application Laid-Open No. 63-264674, Japanese Patent Application Laid-Open No. 09-272812, Japanese Patent Application Laid-Open No. 10-245501, Japanese Patent Application Laid-Open No. 10-265697, Japanese Patent Application Laid-Open No. 2007-079094, International Publication No. 2009/025325, as quinacridone-based dye derivatives, Japanese Patent Application Laid-Open No. 48-54128, Japanese Patent Application Laid-Open No. 03-9961, and Japanese Patent Application Laid-Open No. 2000-273383, as dioxazine-based pigment derivatives, Japanese Patent Application Laid-Open No. 2011-162662, as a thiazine indigo pigment derivative, Japanese Patent Application Publication No. 2007-314785, and as a triazine pigment derivative, Japanese Patent Application Laid-Open No. 61-246261 and Japanese Patent Application Laid-Open No. 11-199796 Publication, Japanese Patent Laid-Open No. 2003-165922, Japanese Patent Laid-Open No. 2003-168208, Japanese Patent Laid-Open No. 2004-217842, Japanese Patent Laid-Open No. 2007-314681, benzoisoindole pigment derivatives include Japanese Patent Laid-Open 2009 -57478, quinaphthalone-based dye derivatives include Japanese Patent Application Laid-Open No. 2003-167112, Japanese Patent Application Laid-Open No. 2006-291194, Japanese Patent Application Laid-Open No. 2008-31281, Japanese Patent Application Laid-Open No. 2012-226110, and naphthol. Examples of the azo-based dye derivatives include Japanese Patent Application Laid-Open No. 2012-208329 and Japanese Patent Application Laid-Open No. 2014-5439; examples of azo-based pigment derivatives include Japanese Patent Application Laid-Open No. 2001-172520 and Japanese Patent Application Laid-Open No. 2012-172092; examples of acidic substituents include , Japanese Patent Application Laid-Open No. 2004-307854, basic substituents include Japanese Patent Application Laid-Open No. 2002-201377, Japanese Patent Application Laid-Open No. 2003-171594, Japanese Patent Application Laid-Open No. 2005-181383, Japanese Patent Application Laid-Open No. 2005-213404, etc. The known pigment derivatives described can be mentioned. In addition, in these documents, the dye derivative may be described as a derivative, pigment derivative, dispersant, pigment dispersant, or simply a compound, but it is a compound having a substituent such as an acidic group, a basic group, or a neutral group on the organic dye residue. is synonymous with pigment derivative.

색소 유도체(F)는, 단독 또는 2종류 이상을 병용하여 사용할 수 있다.The dye derivative (F) can be used individually or in combination of two or more types.

색소 유도체(F)의 함유량은, 착색제(E) 100질량부에 대하여, 1 ∼ 20질량부가 바람직하고, 2 ∼ 10질량부가 보다 바람직하다.The content of the dye derivative (F) is preferably 1 to 20 parts by mass, and more preferably 2 to 10 parts by mass, relative to 100 parts by mass of the colorant (E).

[분산 수지(G)][Dispersion Resin (G)]

본 발명의 감광성 조성물은, 분산 수지(G)를 함유할 수 있다.The photosensitive composition of the present invention may contain a dispersion resin (G).

분산 수지(G)는, 착색제(E)에 친화성이 높은 흡착기를 갖고 있는 수지가 바람직하다. 흡착기는, 염기성기, 및 산성기 중 1종 이상 갖고 있는 것이 바람직하고, 현상성의 관점에서, 산성기를 갖는 것이 바람직하다.The dispersion resin (G) is preferably a resin having an adsorbent group with high affinity for the colorant (E). The adsorbent group preferably has at least one of a basic group and an acidic group, and from the viewpoint of developability, it preferably has an acidic group.

염기성기는, 예를 들면, 1급 아미노기, 2급 아미노기, 3급 아미노기, 4급 암모니아염기, 및 함질소 복소환 등 질소 원자를 함유하는 기 등을 들 수 있다.Examples of the basic group include groups containing a nitrogen atom, such as primary amino group, secondary amino group, tertiary amino group, quaternary ammonia base, and nitrogen-containing heterocycle.

산성기는, 예를 들면, 카르복시기, 인산기, 설폰산기 등을 들 수 있다. 이들 중에서도, 안료에의 흡착성, 현상성의 관점에서 카르복시기, 인산기가 바람직하다.Examples of acidic groups include carboxyl groups, phosphoric acid groups, and sulfonic acid groups. Among these, a carboxyl group and a phosphoric acid group are preferable from the viewpoint of adsorption to the pigment and developability.

분산 수지(G)의 수지종은, 예를 들면, 우레탄 수지, 폴리아크릴레이트 등의 폴리카르복시산에스테르, 불포화 폴리아미드, 폴리카르복시산, 폴리카르복시산 (부분) 아민염, 폴리카르복시산암모늄염, 폴리카르복시산알킬아민염, 폴리실록산, 장쇄 폴리아미노아마이드인산염, 수산기 함유 폴리카르복시산에스테르나, 이들 변성물, 폴리(저급 알킬렌이민)와 유리의 카르복시기를 갖는 폴리에스테르와의 반응에 의해 형성된 아미드나 그 염 등, (메타)아크릴산-스티렌 공중합체, (메타)아크릴산-(메타)아크릴산에스테르 공중합체, 스티렌-말레산 공중합체, 폴리비닐알코올, 폴리비닐피롤리돈 등의 수용성 수지나 수용성 고분자 화합물, 폴리에스테르계, 변성 폴리아크릴레이트계, 에틸렌옥사이드／프로필렌옥사이드 부가 화합물, 인산에스테르계 등을 들 수 있다.Resin species of the dispersion resin (G) include, for example, urethane resin, polycarboxylic acid ester such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, Polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters and their modified products, amides and salts thereof formed by the reaction of poly(lower alkyleneimine) with polyesters having free carboxyl groups, (meth)acrylic acid, etc. -Water-soluble resins or water-soluble polymer compounds such as styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, polyester-based, modified polyacrylic Rate type, ethylene oxide/propylene oxide addition compound, phosphoric acid ester type, etc. are mentioned.

분산 수지(G)의 구조는, 예를 들면, 랜덤 구조, 블록 구조, 그래프트 구조, 빗형 구조, 및 성형(星型) 구조 등을 들 수 있다. 이들 중에서도, 분산 안정성의 관점에서, 블록 구조, 또는 빗형 구조가 바람직하다.The structure of the dispersion resin (G) includes, for example, random structure, block structure, graft structure, comb structure, and star structure. Among these, a block structure or a comb-shaped structure is preferable from the viewpoint of dispersion stability.

분산 수지(G)의 시판품은, 예를 들면, BYK JAPAN K.K. 제조의 Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164, 또는 Anti-Terra-U203, 204, 또는 BYK-P104, P104S, 220S, 또는 Lactimon, Lactimon-WS, 또는 Bykumen 등, The Lubrizol Corporation 제조의 SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500 등, BASF Japan Ltd. 제조의 EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503 등, Ajinomoto Fine-Techno Co., Inc. 제조의 AJISPER PA111, PB711, PB821, PB822, PB824 등, 일본 특허공개 2008-029901호 공보, 일본 특허공개 2009-155406호 공보, 일본 특허공개 2010-185934호 공보, 일본 특허공개 2011-157416호 공보, 국제공개 2008／007776호, 일본 특허공개 2008-029901호 공보, 일본 특허공개 2009-155406호 공보, 일본 특허공개 2010-185934호 공보, 일본 특허공개 2011-157416호 공보, 일본 특허공개 2009-251481호 공보, 일본 특허공개 2007-23195호 공보, 일본 특허공개 1996-143651호 공보 등에 기재된 수지를 들 수 있다.Commercially available products of dispersion resin (G) include, for example, BYK JAPAN K.K. Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, of manufacture 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164, or Anti-Terra-U203, 204, or BY K-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen et al., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000 from The Lubrizol Corporation , 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., BASF Japan Ltd. Manufactured EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 430 0, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajinomoto Fine-Techno Co., Inc. Manufactured by AJISPER PA111, PB711, PB821, PB822, PB824, etc., Japanese Patent Laid-open No. 2008-029901, Japanese Patent Laid-Open No. 2009-155406, Japanese Patent Laid-Open No. 2010-185934, Japanese Patent Laid-Open No. 2011-157416, International Publication No. 2008/007776, Japanese Patent Application Publication No. 2008-029901, Japanese Patent Application Publication No. 2009-155406, Japanese Patent Application Publication No. 2010-185934, Japanese Patent Application Publication No. 2011-157416, Japanese Patent Application Publication No. 2009-251481 Resins described in Japanese Patent Application Publication No. 2007-23195, Japanese Patent Application Publication No. 1996-143651, etc. may be mentioned.

분산 수지(G)는, 단독 또는 2종류 이상을 병용하여 사용할 수 있다.The dispersion resin (G) can be used individually or in combination of two or more types.

분산 수지(G)의 함유량은, 분산 안정성의 관점에서, 착색제(E) 100질량부에 대하여, 3 ∼ 200질량부가 바람직하고, 5 ∼ 100질량부가 보다 바람직하다.From the viewpoint of dispersion stability, the content of the dispersion resin (G) is preferably 3 to 200 parts by mass, and more preferably 5 to 100 parts by mass, relative to 100 parts by mass of the colorant (E).

[증감제(H)][Sensitizer (H)]

본 발명의 감광성 조성물은, 증감제(H)를 함유할 수 있다.The photosensitive composition of the present invention may contain a sensitizer (H).

증감제(H)는, 예를 들면, 칼콘 유도체, 디벤잘아세톤 등으로 대표되는 불포화 케톤류, 벤질이나 캄퍼퀴논 등으로 대표되는 1,2-디케톤 유도체, 벤조인 유도체, 플루오렌 유도체, 나프토퀴논 유도체, 안트라퀴논 유도체, 크산텐 유도체, 티오크산텐 유도체, 크산톤 유도체, 티오크산톤 유도체, 쿠마린 유도체, 케토쿠마린 유도체, 시아닌 유도체, 멜로시아닌 유도체, 옥소놀 유도체 등의 폴리메틴 색소, 아크리딘 유도체, 아진 유도체, 티아진 유도체, 옥사진 유도체, 인돌린 유도체, 아줄렌 유도체, 아줄레늄 유도체, 스쿠알륨 유도체, 포르피린 유도체, 테트라페닐포르피린 유도체, 트리아릴메탄 유도체, 테트라벤조포르피린 유도체, 테트라피라지노포르피라진 유도체, 프탈로시아닌 유도체, 테트라아자포르피라진 유도체, 테트라퀴녹살릴로포르피라진 유도체, 나프탈로시아닌 유도체, 서브프탈로시아닌 유도체, 피릴륨 유도체, 티오피릴륨 유도체, 테트라피린 유도체, 아눌렌 유도체, 스피로피란 유도체, 스피로옥사진 유도체, 티오스피로피란 유도체, 금속 아렌 착체, 유기 루테늄 착체, 또는 미힐러케톤 유도체, α-아실옥시에스테르, 아실옥사이드, 메틸페닐글리옥실레이트, 벤질, 9,10-페난트렌퀴논, 캄퍼퀴논, 에틸안트라퀴논, 4,4'-디에틸이소프탈로페논, 3,3' 또는 4,4'-테트라(t-부틸퍼옥시카르보닐)벤조페논, 4,4'-비스(디에틸아미노)벤조페논 등을 들 수 있다.The sensitizer (H) is, for example, unsaturated ketones such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and naphtho. Polymethine pigments such as quinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, melocyanin derivatives, and oxonol derivatives, Acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squalium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, trialrylmethane derivatives, tetrabenzoporphyrin derivatives, Tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalylloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetrapyrine derivatives, annulene derivatives, spiro Pyran derivatives, spiroxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxyesters, acyloxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone , camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis( Diethylamino) benzophenone, etc. are mentioned.

증감제(H) 중에서, 티오크산톤 유도체, 미힐러케톤 유도체, 카르바졸 유도체가 바람직하다. 구체적인 화합물은, 2,4-디에틸티오크산톤, 2-클로로티오크산톤, 2,4-디클로로티오크산톤, 2-이소프로필티오크산톤, 4-이소프로필티오크산톤, 1-클로로-4-프로폭시티오크산톤, 4,4'-비스(디메틸아미노)벤조페논, 4,4'-비스(디에틸아미노)벤조페논, 4,4'-비스(에틸메틸아미노)벤조페논, N-에틸카르바졸, 3-벤조일-N-에틸카르바졸, 3,6-디벤조일-N-에틸카르바졸 등이 바람직하다.Among the sensitizers (H), thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferable. Specific compounds include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro- 4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N -Ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N-ethylcarbazole, etc. are preferred.

증감제(H)는, 단독 또는 2종류 이상을 병용하여 사용할 수 있다.The sensitizer (H) can be used individually or in combination of two or more types.

증감제(H)의 함유량은, 광중합개시제(C) 100질량부에 대하여, 3 ∼ 60질량부가 바람직하고, 5 ∼ 50질량부가 보다 바람직하다. 적량 함유하면 광경화성, 현상성이 향상된다.The content of the sensitizer (H) is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass, per 100 parts by mass of the photopolymerization initiator (C). Containing an appropriate amount improves photocurability and developability.

[열경화성 화합물(I)][Thermosetting compound (I)]

본 발명의 감광성 조성물은, 열경화성 화합물(I)을 함유할 수 있다. 이에 따라, 가열 공정에서 열경화성 화합물(I)이 반응하여, 가교 밀도가 높아지기 때문에 내열성이 향상된다.The photosensitive composition of the present invention may contain a thermosetting compound (I). Accordingly, the thermosetting compound (I) reacts in the heating process and the crosslinking density increases, thereby improving heat resistance.

열경화성 화합물(I)은, 저분자 화합물이나, 수지와 같은 고분자량 화합물이어도 된다. 열경화성 화합물(I)은, 예를 들면, 에폭시 화합물, 옥세탄 화합물, 벤조구아나민 화합물, 로진 변성 말레산 화합물, 로진 변성 푸말산 화합물, 멜라민 화합물, 요소(尿素) 화합물, 및 페놀 화합물을 들 수 있다. 이들 중에서도 에폭시 화합물 및 옥세탄 화합물이 바람직하다.The thermosetting compound (I) may be a low molecular weight compound or a high molecular weight compound such as a resin. Thermosetting compounds (I) include, for example, epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. there is. Among these, epoxy compounds and oxetane compounds are preferable.

(에폭시 화합물(I1))(Epoxy compound (I1))

에폭시 화합물(I1)은, 예를 들면, 비스페놀류(비스페놀A, 비스페놀F, 비스페놀S, 비페놀, 비스페놀AD 등), 페놀류(페놀, 알킬 치환 페놀, 방향족 치환 페놀, 나프톨, 알킬 치환 나프톨, 디히드록시벤젠, 알킬 치환 디히드록시벤젠, 디히드록시나프탈렌 등)와 각종 알데히드(포름알데히드, 아세토알데히드, 알킬알데히드, 벤즈알데히드, 알킬 치환 벤즈알데히드, 히드록시벤즈알데히드, 나프토알데히드, 글루타르알데히드, 프탈알데히드, 크로톤알데히드, 신남알데히드 등)와의 중축합물, 페놀류와 각종 디엔 화합물(디시클로펜타디엔, 테르펜류, 비닐시클로헥센, 노르보르나디엔, 비닐노르보르넨, 테트라히드로인덴, 디비닐벤젠, 디비닐비페닐, 디이소프로페닐비페닐, 부타디엔, 이소프렌 등)과의 중축합물, 페놀류와 케톤류(아세톤, 메틸에틸케톤, 메틸이소부틸케톤, 아세토페논, 벤조페논 등)와의 중축합물, 페놀류와 방향족 디메탄올류(벤젠디메탄올, α,α,α',α'-벤젠디메탄올, 비페닐디메탄올, α,α,α',α'-비페닐디메탄올 등)와의 중축합물, 페놀류와 방향족 디클로로메틸류(α,α'-디클로로크실렌, 비스클로로메틸비페닐 등)와의 중축합물, 비스페놀류와 각종 알데히드의 중축합물, 알코올류 등을 글리시딜화한 글리시딜에테르계 에폭시 수지, 지환식 에폭시 수지, 복소환식 에폭시 수지, 지방족 에폭시 수지, 글리시딜아민계 에폭시 수지, 글리시딜에스테르계 에폭시 수지 등을 들 수 있다.Epoxy compounds (I1) include, for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl substituted phenol, aromatic substituted phenol, naphthol, alkyl substituted naphthol, di Hydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, and phthalaldehyde. , crotonaldehyde, cinnamaldehyde, etc.), polycondensates with phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, dicyclopentadiene, Polycondensates with vinyl biphenyl, diisopropenyl biphenyl, butadiene, isoprene, etc.), polycondensates with phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatics. Polycondensates with dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), phenols and aromatics Polycondensates of dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins glycidylated with alcohols, etc., alicyclic Examples include epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine-based epoxy resins, and glycidyl ester-based epoxy resins.

시판품은, 예를 들면, Yuka Shell Epoxy K.K. 제조의 Epikote 807, 815, 825, 827, 828, 190P, 191P, Mitsui Chemicals, Inc. 제조의 TECHMORE VG3101L, Nippon Kayaku Co., Ltd. 제조의 EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 JER사 제조의 Epikote 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154, Daicel Corporation 제조의 CELLOXIDE 2021, EHPE-3150, Nagase Chemtex Corporation 제조의 DENACOL EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721, Nissan Chemical Industries, Ltd. 제조의 TEPIC-L, H, S 등을 들 수 있다.Commercially available products include, for example, Yuka Shell Epoxy K.K. Epikote 807, 815, 825, 827, 828, 190P, 191P, manufactured by Mitsui Chemicals, Inc. Manufactured by TECHMORE VG3101L, Nippon Kayaku Co., Ltd. EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 manufactured by JER Corporation, Epikote 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154 manufactured by Daicel Corporation, CELLOXIDE 2021, EHPE manufactured by Daicel Corporation -3150, Nagase DENACOL EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 manufactured by Chemtex Corporation, Nissan Chemical Industries, Ltd. Examples include TEPIC-L, H, S, etc. manufactured by the company.

에폭시 화합물(I1)의 함유량은, 경화막의 내열성의 관점에서, 감광성 조성물의 불휘발분 100질량％ 중, 0.5 ∼ 50질량％가 바람직하고, 1 ∼ 40질량％가 보다 바람직하다.From the viewpoint of heat resistance of the cured film, the content of the epoxy compound (I1) is preferably 0.5 to 50% by mass, and more preferably 1 to 40% by mass, based on 100% by mass of non-volatile matter of the photosensitive composition.

(옥세탄 화합물(I2))(Oxetane compound (I2))

옥세탄 화합물(I2)은, 옥세탄기를 갖는 공지된 화합물이다. 옥세탄 화합물은, 1관능 옥세탄 화합물, 2관능 옥세탄 화합물, 3관능 이상의 옥세탄 화합물을 들 수 있다.Oxetane compound (I2) is a known compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher oxetane compounds.

1관능 옥세탄 화합물은, 예를 들면, (3-에틸옥세탄-3-일)메틸아크릴레이트, (3-에틸옥세탄-3-일)메틸메타크릴레이트, 3-에틸-3-히드록시메틸옥세탄, 3-에틸-3-(2-에틸헥실옥시메틸)옥세탄, 3-에틸-3-(페녹시메틸)옥세탄, 3-에틸-3-(2-메타크릴옥시메틸)옥세탄, 3-에틸-3-{[3-(트리에톡시실릴)프로폭시]메틸}옥세탄 등을 들 수 있다.Monofunctional oxetane compounds include, for example, (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, and 3-ethyl-3-hydroxy. Methyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane Cetane, 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane, etc. can be mentioned.

시판품은, 예를 들면, OSAKA ORGANIC CHEMICAL INDUSTRY LTD. 제조의 OXE-10, 30, TOAGOSEI CO., LTD. 제조의 OXT-101, 212 등을 들 수 있다.Commercially available products include, for example, OSAKA ORGANIC CHEMICAL INDUSTRY LTD. Manufactured by OXE-10, 30, TOAGOSEI CO., LTD. Examples include OXT-101 and 212 manufactured by Manufacturer.

2관능 옥세탄 화합물은, 예를 들면, 4,4'-비스[(3-에틸-3-옥세타닐)메톡시메틸]비페닐), 1,4-비스[(3-에틸-3-옥세타닐)메톡시메틸]벤젠, 1,4-비스{[(3-에틸-3-옥세타닐)메톡시]메틸}벤젠, 디[1-에틸(3-옥세타닐)]메틸에테르, 디[1-에틸(3-옥세타닐)]메틸에테르3-에틸-3-히드록시메틸옥세탄, 3-에틸-3-(2-에틸헥실옥시메틸)옥세탄, 3-에틸-3-(2-페녹시메틸)옥세탄, 3,7-비스(3-옥세타닐)-5-옥사-노난, 1,2-비스[(3-에틸-3-옥세타닐메톡시)메틸]에탄, 1,3-비스[(3-에틸-3-옥세타닐메톡시)메틸]프로판, 에틸렌글리콜비스(3-에틸-3-옥세타닐메틸)에테르, 디시클로펜테닐비스(3-에틸-3-옥세타닐메틸)에테르, 트리에틸렌글리콜비스(3-에틸-3-옥세타닐메틸)에테르, 테트라에틸렌글리콜비스(3-에틸-3-옥세타닐메틸)에테르, 1,4-비스(3-에틸-3-옥세타닐메톡시)부탄, 1,6-비스(3-에틸-3-옥세타닐메톡시)헥산, 폴리에틸렌글리콜비스(3-에틸-3-옥세타닐메틸)에테르, 에틸렌옥사이드(EO) 변성 비스페놀A비스(3-에틸-3-옥세타닐메틸)에테르, 프로필렌옥사이드(PO) 변성 비스페놀A비스(3-에틸-3-옥세타닐메틸)에테르, EO 변성 수첨(水添) 비스페놀A비스(3-에틸-3-옥세타닐메틸)에테르, PO 변성 수첨 비스페놀A비스(3-에틸-3-옥세타닐메틸)에테르, EO 변성 비스페놀F(3-에틸-3-옥세타닐메틸)에테르 등을 들 수 있다.Bifunctional oxetane compounds include, for example, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3- oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether , di[1-ethyl(3-oxetanyl)]methyl ether3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3 -(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl] Ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenylbis(3-ethyl) -3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4- Bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether , ethylene oxide (EO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO modified hydrogenated (Water filtration) Bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO modified bisphenol F(3-ethyl- 3-oxetanylmethyl) ether, etc. can be mentioned.

시판품은, 예를 들면, Ube Industries, Ltd. 제조의 OXBP, OXTP, TOAGOSEI CO., LTD. 제조의 OXT-121, 221 등을 들 수 있다.Commercially available products include, for example, Ube Industries, Ltd. Manufactured by OXBP, OXTP, TOAGOSEI CO., LTD. Examples include OXT-121 and 221 manufactured by Manufacturer.

3관능 이상의 옥세탄 화합물은, 예를 들면, 펜타에리트리톨트리스(3-에틸-3-옥세타닐메틸)에테르, 펜타에리트리톨테트라키스(3-에틸-3-옥세타닐메틸)에테르, 디펜타에리트리톨헥사(3-에틸-3-옥세타닐메틸)에테르, 디펜타에리트리톨펜타키스(3-에틸-3-옥세타닐메틸)에테르, 디펜타에리트리톨테트라키스(3-에틸-3-옥세타닐메틸)에테르, 카프로락톤 변성 디펜타에리트리톨헥사(3-에틸-3-옥세타닐메틸)에테르, 카프로락톤 변성 디펜타에리트리톨펜타키스(3-에틸-3-옥세타닐메틸)에테르, 디트리메틸올프로판테트라키스(3-에틸-3-옥세타닐메틸)에테르, 옥세탄기를 함유하는 수지(예를 들면, 일본 특허 제3783462호 기재의 옥세탄 변성 페놀노볼락 수지 등)나 상술한 OXE-30과 같은 (메타)아크릴 모노머를 라디칼 중합시켜 얻어지는 중합체를 들 수 있다.Oxetane compounds having three or more functional groups include, for example, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, Pentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3 -Oxetanylmethyl)ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl)ether, caprolactone-modified dipentaerythritolpentakis(3-ethyl-3-oxetanylmethyl) ) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, resin containing an oxetane group (for example, oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462, etc.) Examples include polymers obtained by radical polymerization of (meth)acrylic monomers such as OXE-30 described above.

옥세탄 화합물(I2)의 함유량은, 감광성 조성물의 불휘발분 100질량％ 중, 0.5 ∼ 50질량％가 바람직하고, 1 ∼ 40질량％가 보다 바람직하다.The content of the oxetane compound (I2) is preferably 0.5 to 50% by mass, and more preferably 1 to 40% by mass, based on 100% by mass of the non-volatile matter of the photosensitive composition.

멜라민 화합물은, 멜라민환 구조를 갖는 화합물이다. 멜라민 화합물은, 메틸올형이나 에테르형의 화합물이 바람직하고, 멜라민환 1개당의 메틸올기 및／또는 에테르기 수가 평균 5.0 이상인 멜라민 화합물이 보다 바람직하다. 적당히 메틸올기나 에테르기 수를 가지면 과부족이 없는 내열성을 얻기 쉽다.A melamine compound is a compound that has a melamine ring structure. The melamine compound is preferably a methylol-type or ether-type compound, and a melamine compound in which the number of methylol groups and/or ether groups per melamine ring is 5.0 or more on average is more preferable. If it has an appropriate number of methylol groups or ether groups, it is easy to obtain heat resistance without excess or deficiency.

시판품은, 예를 들면, SANWA CHEMICAL CO., LTD. 제조의 NIKALAC MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, MX-410, Cytec Industries Inc. 제조의 CYMEL232, 235, 236, 238, 285, 300, 301, 303, 350, 370 등을 들 수 있다.Commercially available products include, for example, SANWA CHEMICAL CO., LTD. Manufactured by NIKALAC MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002 , MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, MX-410, Cytec Industries Inc. Examples include CYMEL232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 manufactured by the company.

이들 중에서도 멜라민환 1개당의 메틸올기, 및／또는, 에테르기 수가 평균 5.0 이상인, SANWA CHEMICAL CO., LTD. 제조의 NIKALAC MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MX-45, Cytec Industries Inc. 제조의 CYMEL232, 235, 236, 238, 300, 301, 303, 350 등은, 가교 밀도를 높일 수 있는 면에서 바람직하다.Among these, SANWA CHEMICAL CO., LTD., which has an average number of methylol groups and/or ether groups per melamine ring of 5.0 or more. Manufactured by NIKALAC MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MX-45, Cytec Industries Inc . Manufactured CYMEL232, 235, 236, 238, 300, 301, 303, 350, etc. are preferred in that they can increase the crosslinking density.

열경화성 화합물(I)은, 단독 또는 2종류 이상을 병용하여 사용할 수 있다.Thermosetting compound (I) can be used individually or in combination of two or more types.

[경화제(경화 촉진제)][Hardener (curing accelerator)]

본 발명의 감광성 조성물은, 열경화성 화합물(I)의 경화를 보조하기 위해, 경화제(경화 촉진제)를 병용할 수 있다.The photosensitive composition of the present invention can be used in combination with a curing agent (curing accelerator) to assist in curing the thermosetting compound (I).

경화제는, 예를 들면, 아민계 화합물, 산무수물, 활성 에스테르, 카르복시산계 화합물, 설폰산계 화합물 등을 들 수 있다. 경화제는, 예를 들면, 아민 화합물(예를 들면, 디시안디아미드, 벤질디메틸아민, 4-(디메틸아미노)-N,N-디메틸벤질아민, 4-메톡시-N,N-디메틸벤질아민, 4-메틸-N,N-디메틸벤질아민 등), 4급 암모늄염 화합물(예를 들면, 트리에틸벤질암모늄 클로라이드 등), 블록 이소시아네이트 화합물(예를 들면, 디메틸아민 등), 이미다졸 유도체 2환식 아미딘 화합물 및 그 염(예를 들면, 이미다졸, 2-메틸이미다졸, 2-에틸이미다졸, 2-에틸-4-메틸이미다졸, 2-페닐이미다졸, 4-페닐이미다졸, 1-시아노에틸-2-페닐이미다졸, 1-(2-시아노에틸)-2-에틸-4-메틸이미다졸 등), 인 화합물(예를 들면, 트리페닐포스핀 등), S-트리아진 유도체(예를 들면, 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·이소시아누르산 부가물 등) 등을 들 수 있다.Curing agents include, for example, amine-based compounds, acid anhydrides, active esters, carboxylic acid-based compounds, and sulfonic acid-based compounds. Curing agents include, for example, amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), block isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amides Dean compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimida Sol, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc. ), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2 -Vinyl-4,6-diamino-S-triazine·isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine·isocyanuric acid adduct, etc. ), etc.

경화제는, 단독 또는 2종류 이상을 병용하여 사용할 수 있다.The hardener can be used alone or in combination of two or more types.

경화제의 함유량은, 열경화성 화합물(I) 100질량부에 대하여, 0.01 ∼ 15질량부가 바람직하다.The content of the curing agent is preferably 0.01 to 15 parts by mass per 100 parts by mass of the thermosetting compound (I).

[중합 금지제(J)][Polymerization inhibitor (J)]

본 발명의 감광성 조성물은, 중합 금지제(J)를 함유할 수 있다.The photosensitive composition of the present invention may contain a polymerization inhibitor (J).

중합 금지제(J)는, 예를 들면, 카테콜, 레조르시놀, 1,4-히드로퀴논, 2-메틸카테콜, 3-메틸카테콜, 4-메틸카테콜, 2-에틸카테콜, 3-에틸카테콜, 4-에틸카테콜, 2-프로필카테콜, 3-프로필카테콜, 4-프로필카테콜, 2-n-부틸카테콜, 3-n-부틸카테콜, 4-n-부틸카테콜, 2-t-부틸카테콜, 3-t-부틸카테콜, 4-t-부틸카테콜, 3,5-디-t-부틸카테콜 등의 알킬카테콜계 화합물, 2-메틸레조르시놀, 4-메틸레조르시놀, 2-에틸레조르시놀, 4-에틸레조르시놀, 2-프로필레조르시놀, 4-프로필레조르시놀, 2-n-부틸레조르시놀, 4-n-부틸레조르시놀, 2-t-부틸레조르시놀, 4-t-부틸레조르시놀 등의 알킬레조르시놀계 화합물, 메틸히드로퀴논, 에틸히드로퀴논, 프로필히드로퀴논, t-부틸히드로퀴논, 2,5-디-t-부틸히드로퀴논 등의 알킬히드로퀴논계 화합물, 트리부틸포스핀, 트리옥틸포스핀, 트리시클로헥실포스핀, 트리페닐포스핀, 트리벤질포스핀 등의 포스핀 화합물, 트리옥틸포스핀옥사이드, 트리페닐포스핀옥사이드 등의 포스핀옥사이드 화합물, 트리페닐포스파이트, 트리스노닐페닐포스파이트 등의 포스파이트 화합물, 피로가롤, 플루오로글루신 등을 들 수 있다. Polymerization inhibitors (J) include, for example, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3 -Ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butyl Alkyl catechol compounds such as catechol, 2-t-butyl catechol, 3-t-butyl catechol, 4-t-butyl catechol, and 3,5-di-t-butyl catechol, 2-methylresorbate Nol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n- Alkylresorcinol-based compounds such as butylresorcinol, 2-t-butylresorcinol, 4-t-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, 2,5-di- Alkylhydroquinone compounds such as t-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine, trioctylphosphine oxide, triphenyl Phosphite compounds such as phosphine oxide, phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite, pyrogarol, fluoroglucine, etc. are included.

중합 금지제(J)의 함유량은, 감광성 조성물의 불휘발분 100질량％ 중, 0.01 ∼ 0.4질량％가 바람직하다.The content of the polymerization inhibitor (J) is preferably 0.01 to 0.4% by mass in 100% by mass of non-volatile matter of the photosensitive composition.

[자외선 흡수제(K)][UV absorbent (K)]

본 발명의 감광성 조성물은, 자외선 흡수제(K)를 함유할 수 있다.The photosensitive composition of the present invention may contain an ultraviolet absorber (K).

자외선 흡수제(K)는, 자외선 흡수 기능을 갖는 유기 화합물이며, 벤조트리아졸계 유기 화합물, 트리아진계 유기 화합물, 벤조페논계 유기 화합물, 살리실산에스테르계 유기 화합물, 시아노아크릴레이트계 유기 화합물, 및 살리실레이트계 유기 화합물 등을 들 수 있다.The ultraviolet absorber (K) is an organic compound having an ultraviolet ray absorption function, and includes benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylic acid ester-based organic compounds, cyanoacrylate-based organic compounds, and salicylic compounds. Rate-based organic compounds, etc. can be mentioned.

벤조트리아졸계 화합물은, 예를 들면, 2-(5메틸-2-히드록시페닐)벤조트리아졸, 2-(2-히드록시-5-tert-부틸페닐)-2H-벤조트리아졸, 2-[2-히드록시-3,5-비스(α,α-디메틸벤질)페닐]-2H-벤조트리아졸, 2-(3-t-부틸-5-메틸-2-히드록시페닐)-5-클로로벤조트리아졸, 2-(2'-히드록시-5'-t-옥틸페닐)벤조트리아졸, 5％의 2-메톡시-1-메틸에틸아세테이트와 95％의 벤젠프로판산, 3-(2H-벤조트리아졸2-일)-(1,1-디메틸에틸)-4-히드록시, C7-9 측쇄 및 직쇄 알킬에스테르의 혼합물, 2-(2H-벤조트리아졸2-일)-4,6-비스(1-메틸-1-페닐에틸)페놀, 2-(2H-벤조트리아졸2-일)-6-(1-메틸-1-페닐에틸)-4-(1,1,3,3-테트라메틸부틸)페놀, 메틸3-(3-(2H-벤조트리아졸2-일)-5-t-부틸-4-히드록시페닐)프로피오네이트／폴리에틸렌글리콜 300의 반응 생성물, 2-(2H-벤조트리아졸2-일)-4-(1,1,3,3-테트라메틸부틸)페놀, 2,2'-메틸렌비스[6-(2H-벤조트리아졸2-일)-4-(1,1,3,3-테트라메틸부틸)페놀], 2-(2H-벤조트리아졸2-일)-p-크레졸, 2-(5-클로로-2H-벤조트리아졸2-일)-6-t-부틸-4-메틸페놀, 2-(3,5-디-t-아밀-2-히드록시페닐)벤조트리아졸, 2-[2-히드록시-5-[2-(메타크릴로일옥시)에틸]페닐]-2H-벤조트리아졸, 옥틸-3-[3-tert-부틸-4-히드록시-5-(5-클로로-2H-벤조트리아졸2-일)페닐]프로피오네이트, 2-에틸헥실-3-[3-tert-부틸-4-히드록시-5-(5-클로로-2H-벤조트리아졸2-일)페닐]프로피오네이트를 들 수 있다.Benzotriazole-based compounds include, for example, 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, 2- [2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5- Chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethylacetate and 95% benzenepropanoic acid, 3-( 2H-benzotriazol2-yl)-(1,1-dimethylethyl)-4-hydroxy, mixture of C7-9 branched and straight chain alkyl esters, 2-(2H-benzotriazol2-yl)-4, 6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3, 3-Tetramethylbutyl)phenol, methyl 3-(3-(2H-benzotriazol2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/reaction product of polyethylene glycol 300, 2- (2H-benzotriazol2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol2-yl)-4 -(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol2-yl) -6-t-Butyl-4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(meta Cryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol2-yl)phenyl] Propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol2-yl)phenyl]propionate.

시판품은, 예를 들면, BASF Japan Ltd. 제조의 TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130, ADEKA CORPORATION 제조의 ADEKASTAB LA-29, LA-31RG, LA-32, LA-36, CHEMIPRO KASEI KAISHA, LTD. 제조의 KEMiSORB71, 73, 74, 79, 279, Otsuka Chemical Co., Ltd. 제조의 RUVA-93 등을 들 수 있다.Commercially available products include, for example, BASF Japan Ltd. TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130 manufactured by ADEKA CORPORATION ADEKASTAB LA-29, LA-31RG, LA-32, LA-36, CHEMIPRO KASEI KAISHA, LTD. Manufactured by KEMiSORB71, 73, 74, 79, 279, Otsuka Chemical Co., Ltd. RUVA-93 manufactured by the company, etc. can be mentioned.

트리아진계 화합물은, 예를 들면, 2,4-비스(2,4-디메틸페닐)-6-(2-히드록시-4-n-옥틸옥시페닐)-1,3,5-트리아진, 2-[4,6-비스(2,4-디메틸페닐)-1,3,5-트리아진-2-일]-5-[3-(도데실옥시)-2-히드록시프로폭시]페놀, 2-(2,4-디히드록시페닐)-4,6-비스(2,4-디메틸페닐)-1,3,5-트리아진과 (2-에틸헥실)-글리시드산에스테르의 반응 생성물, 2,4-비스「2-히드록시-4-부톡시페닐」-6-(2,4-디부톡시페닐)-1,3,5-트리아진, 2-(4,6-디페닐-1,3,5-트리아진-2-일)-5-(헥실옥시)페놀, 2-(4,6-디페닐-1,3,5-트리아진-2-일)-5-[2-(2-에틸헥사노일옥시)에톡시]페놀, 2,4,6-트리스(2-히드록시-4-헥실옥시-3-메틸페닐)-1,3,5-트리아진 등을 들 수 있다.Triazine-based compounds include, for example, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2 -[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, The reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester, 2,4-bis「2-hydroxy-4-butoxyphenyl」-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1 ,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2 -(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine, etc. there is.

시판품은, 예를 들면, CHEMIPRO KASEI KAISHA, LTD. 제조의 KEMISORB 102, BASF Japan Ltd. 제조의 TINUVIN 400, 405, 460, 477, 479, 1577 ED, ADEKA사의 ADEKASTAB LA-46, LA-F70, SUN CHEMICAL COMPANY LTD. 제조의 CYASORBUV-1164 등을 들 수 있다.Commercially available products include, for example, CHEMIPRO KASEI KAISHA, LTD. Manufactured by KEMISORB 102, BASF Japan Ltd. TINUVIN 400, 405, 460, 477, 479, 1577 ED manufactured by ADEKA, ADEKASTAB LA-46, LA-F70 manufactured by SUN CHEMICAL COMPANY LTD. CYASORBUV-1164 manufactured by the company, etc. can be mentioned.

벤조페논계 화합물은, 예를 들면, 2,4-디히드록시벤조페논, 2-히드록시-4-메톡시벤조페논, 2-히드록시-4-메톡시벤조페논5-설폰산-3수온, 2-히드록시-4-n-옥톡시벤조페논, 2,2'-디히드록시-4-메톡시벤조페논, 2,2'-디히드록시-4,4'-디메톡시벤조페논, 4-도데실옥시-2-히드록시벤조페논, 2-히드록시-4-옥타데실옥시벤조페논, 2,2'-디히드록시-4,4'-디메톡시벤조페논, 2,2',4,4'-테트라히드록시벤조페논, 2-히드록시-4-메톡시-2'-카르복시벤조페논 등을 들 수 있다.Benzophenone-based compounds include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone 5-sulfonic acid-3 water temperature , 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc. are mentioned.

시판품은, 예를 들면, CHEMIPRO KASEI KAISHA, LTD. 제조의 KEMISORB 10, 11, 11S, 12, 111, SHIPRO KASEI KAISHA, LTD. 제조의 SEESORB 101, 107, ADEKA CORPORATION 제조의 ADEKASTAB 1413, SUN CHEMICAL COMPANY LTD. 제조의 UV-12 등을 들 수 있다.Commercially available products include, for example, CHEMIPRO KASEI KAISHA, LTD. Manufactured by KEMISORB 10, 11, 11S, 12, 111, SHIPRO KASEI KAISHA, LTD. Manufactured by SEESORB 101, 107, ADEKA CORPORATION Manufactured by ADEKASTAB 1413, SUN CHEMICAL COMPANY LTD. UV-12 manufactured by Manufacturer, etc. may be mentioned.

살리실산에스테르계 화합물은, 예를 들면, 살리실산페닐, 살리실산p-옥틸페닐, 살리실산 p-tert 부틸페닐 등을 들 수 있다.Examples of salicylic acid ester-based compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

자외선 흡수제(K)의 함유량은, 광중합개시제(C)와 자외선 흡수제(K)와의 합계 100질량％ 중, 5 ∼ 70질량％가 바람직하다.The content of the ultraviolet absorber (K) is preferably 5 to 70% by mass, based on a total of 100% by mass of the photopolymerization initiator (C) and the ultraviolet absorber (K).

[산화 방지제(L)][Antioxidant (L)]

본 발명의 감광성 조성물은, 산화 방지제(L)를 함유할 수 있다.The photosensitive composition of the present invention may contain an antioxidant (L).

산화 방지제(L)는, 감광성 조성물에 포함되는 광중합개시제(C)나 열경화성 화합물(I)이, 열경화나 iTO 어닐 시의 열공정에 의해 산화에 의한 황변을 방지한다. 특히, 감광성 조성물의 착색제(E) 농도가 높은 경우, 상대적으로 중합성 화합물(B)의 함유량이 감소하기 때문에, 광중합개시제(C)의 증량이나, 열경화성 화합물(I)의 배합으로 대응하면 경화막이 황변하기 쉽다. 그 때문에, 산화 방지제를 포함함으로써, 가열 공정 시의 산화에 의한 경화막의 황변을 방지한다.The antioxidant (L) prevents the photopolymerization initiator (C) and the thermosetting compound (I) contained in the photosensitive composition from yellowing due to oxidation due to thermal curing or a thermal process during iTO annealing. In particular, when the concentration of the colorant (E) in the photosensitive composition is high, the content of the polymerizable compound (B) is relatively reduced, so if you respond by increasing the amount of the photopolymerization initiator (C) or mixing the thermosetting compound (I), the cured film It is easy to yellow. Therefore, by including an antioxidant, yellowing of the cured film due to oxidation during the heating process is prevented.

산화 방지제(L)는, 예를 들면, 힌더드페놀계, 힌더드아민계, 인계, 황계, 및 히드록시아민계의 화합물을 들 수 있다. 또, 본 명세서에서 산화 방지제는, 할로겐 원자를 함유하지 않는 화합물이 바람직하다.Antioxidants (L) include, for example, hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxyamine-based compounds. In addition, the antioxidant in this specification is preferably a compound that does not contain a halogen atom.

이들 중에서도, 힌더드페놀계 산화 방지제, 힌더드아민계 산화 방지제, 인계 산화 방지제, 황계 산화 방지제가 바람직하다.Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferable.

힌더드페놀계 산화 방지제는, 예를 들면, 1,3,5-트리스(3,5-디-t-부틸-4-히드록시벤질)-1,3,5-트리아진-2,4,6(1H,3H,5H)-트리온, 1,1,3-트리스-(2'-메틸-4'-히드록시-5'-t-부틸페닐)-부탄, 4,4'-부틸리덴-비스(2-t-부틸-5-메틸페놀), 3-(3,5-디-t-부틸-4-히드록시페닐)프로피온산스테아릴, 펜타에리트리톨테트라키스[3-(3,5-디-t-부틸-4-히드록시페닐)프로피오네이트, 3,9-비스[2-[3-(3-t-부틸-4-히드록시-5-메틸페닐)프로피오닐옥시]-1,1-디메틸에틸]-2,4,8,10-테트라옥사스피로[5.5]운데칸, 1,3,5-트리스(3,5-디-t-부틸-4-히드록시페닐메틸)-2,4,6-트리메틸벤젠, 1,3,5-트리스(3-히드록시-4-t-부틸-2,6-디메틸벤질)-1,3,5-트리아진-2,4,6(1H,3H,5H)-트리온, 2,2'-메틸렌비스(6-t-부틸-4-에틸페놀), 2,2'-티오디에틸비스-(3,5-디-t-부틸-4-히드록시페닐)-프로피오네이트, N,N-헥사메틸렌비스(3,5-디-t-부틸-4-히드록시-히드로신남아미드), i-옥틸-3-(3,5-디-t-부틸-4-히드록시페닐)프로피오네이트, 4,6-비스(도데실티오메틸)-o-크레졸, 3,5-디-t-부틸-4-히드록시벤질포스폰산모노에틸에스테르의 칼슘염, 4,6-비스(옥틸티오메틸)-o-크레졸, 비스[3-(3-메틸-4-히드록시-5-t-부틸페닐)프로피온산]에틸렌비스옥시비스에틸렌, 1,6-헥산디올비스[3-(3,5-디-t-부틸-4-히드록시페닐)프로피오네이트, 2,4-비스-(n-옥틸티오)-6-(4-히드록시-3,5-디-t-부틸아닐리노)-1,3,5-트리아진, 2,2'-티오-비스-(6-t-부틸-4-메틸페놀), 2,5-디-t-아밀-히드로퀴논, 2,6-디-t-부틸-4-노닐페놀, 2,2'-이소부틸리덴-비스(4,6-디메틸-페놀), 2,2'-메틸렌-비스(6-(1-메틸-시클로헥실)-p-크레졸), 2,4-디메틸-6-(1-메틸-시클로헥실)-페놀 등을 들 수 있다.Hindered phenol-based antioxidants include, for example, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4, 6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butyly den-bis(2-t-butyl-5-methylphenol), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearyl propionate, pentaerythritol tetrakis[3-(3, 5-di-t-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]- 1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl) -2,4,6-trimethylbenzene, 1,3,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4, 6(1H,3H,5H)-trione, 2,2'-methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di-t -Butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl-3-(3 ,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, 3,5-di-t-butyl-4-hydroxybenzyl Calcium salt of phosphonic acid monoethyl ester, 4,6-bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid]ethylenebisoxy Bisethylene, 1,6-hexanediolbis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-( 4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,2'-thio-bis-(6-t-butyl-4-methylphenol), 2 ,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis(4,6-dimethyl-phenol), 2,2' -methylene-bis(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, etc.

시판품은, 예를 들면, ADEKA CORPORATION 제조의 ADEKASTAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330, CHEMIPRO KASEI KAISHA, LTD. 제조의 KEMINOX101, 179, 76, 9425, BASF Japan Ltd. 제조의 IRGANOX1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, SUN CHEMICAL COMPANY LTD. 제조의 Cyanox CY-1790, CY-2777 등을 들 수 있다.Commercially available products include, for example, ADEKASTAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 manufactured by ADEKA CORPORATION, CHEMIPRO KASEI KAISHA, LTD. Manufactured by KEMINOX101, 179, 76, 9425, BASF Japan Ltd. Manufactured by IRGANOX1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, SUN CHEMICAL COMPANY LTD. Examples include Cyanox CY-1790 and CY-2777.

힌더드아민계 산화 방지제는, 예를 들면, 테트라키스(1,2,2,6,6-펜타메틸-4-피페리딜)-1,2,3,4-부탄테트라카복실레이트, 테트라키스(2,2,6,6-테트라메틸-4-피페리딜)-1,2,3,4-부탄테트라카복실레이트, 비스(1,2,2,6,6-펜타메틸-4-피페리딜)세바케이트, 비스(2,2,6,6-테트라메틸-4-피페리딜)세바케이트, 비스(1-운데칸옥시-2,2,6,6-테트라메틸피페리딘-4-일)카르보네이트, 1,2,2,6,6-펜타메틸-4-피페리딜메타크릴레이트, 2,2,6,6-테트라메틸-4-피페리딜메타크릴레이트, 숙신산디메틸과 1-(2-히드록시에틸)-4-히드록시-2,2,6,6-테트라메틸피페리딘과의 중축합물, 폴리[[6-[(1,1,3,3-테트라메틸부틸)아미노]-s-트리아진-2,4-디일]-[(2,2,6,6-테트라메틸-4-피페리딜)이미노]-헥사메틸렌-[(2,2,6,6-테트라메틸-4-피페리딜)이미노]], 4-히드록시-2,2,6,6-테트라메틸-1-피페리딘에탄올과 3,5,5-트리메틸헥산산의 에스테르, N,N'-4,7-테트라키스〔4,6-비스{N-부틸-N-(1,2,2,6,6-펜타메틸-4-피페리딜)아미노}-1,3,5-트리아진-2-일〕-4,7-디아자데칸-1,10-디아민, 데칸이산비스(2,2,6,6-테트라메틸-1-(옥틸옥시)-4-피페리디닐)에스테르, 1,1-디메틸에틸히드로퍼옥사이드와 옥탄의 반응 생성물, 비스(1,2,2,6,6-펜타메틸-4-피리페리딜)[[3,5-비스(1,1디메틸에틸)-4-히드록시페닐]메틸]부틸말로네이트메틸1,2,2,6,6-펜타메틸-4-피리페리딜세바케이트, 폴리[[6-모르폴리노-s-트리아진-2,4-디일]-[(2,2,6,6-테트라메틸-4-피페리딜)이미노]-헥사메틸렌-[(2,2,6,6-테트라메틸-4-피페리딜)이미노]], 2,2,6,6-테트라메틸-4-피페리딜-C12-21 및 C18 불포화 지방산 에스테르, N,N'-비스(2,2,6,6-테트라메틸-4-피페리딜)-1,6-헥사메틸렌디아민, 2-메틸-2-(2,2,6,6-테트라메틸-4-피페리딜)아미노-N-(2,2,6,6-테트라메틸-4-피페리딜)프로피온아미드 등을 들 수 있다.Hindered amine antioxidants include, for example, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-p) Peridyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidine- 4-yl) carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, Polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[[6-[(1,1,3,3 -Tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2, 2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3,5,5-trimethyl Ester of hexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino }-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, decane bisoxide (2,2,6,6-tetramethyl-1-(octyloxy )-4-piperidinyl) ester, reaction product of 1,1-dimethylethylhydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyriperidyl)[[3, 5-bis(1,1dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonatemethyl1,2,2,6,6-pentamethyl-4-pyriperidylsebacate, poly[[6-mor polyno-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6 -tetramethyl-4-piperidyl)imino]], 2,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid ester, N,N'-bis(2, 2,6,6-Tetramethyl-4-piperidyl)-1,6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino- N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, etc. can be mentioned.

시판품은, 예를 들면, ADEKA CORPORATION 제조의 ADEKASTAB LA-52, LA-57, LA-63 P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, LA-502XP, CHEMIPRO KASEI KAISHA, LTD. 제조의 KAMISTAB29, 62, 77, 94, BASF Japan Ltd. 제조의 Tinuvin111FDL, 123, 144, 249, 292, 5100, SUN CHEMICAL COMPANY LTD. 제조의 CYASORB UV-3346, UV-3529, UV-3853 등을 들 수 있다.Commercial products include, for example, ADEKASTAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA manufactured by ADEKA CORPORATION. -87, LA-402F, LA-502XP, CHEMIPRO KASEI KAISHA, LTD. Manufactured by KAMISTAB29, 62, 77, 94, BASF Japan Ltd. Manufactured by Tinuvin111FDL, 123, 144, 249, 292, 5100, SUN CHEMICAL COMPANY LTD. Examples include CYASORB UV-3346, UV-3529, and UV-3853 manufactured by CYASORB.

인계 산화 방지제는, 예를 들면, 디(2,6-디-t-부틸-4-메틸페닐)펜타에리트리톨디포스파이트, 디스테아릴펜타에리트리톨디포스파이트, 2,2'-메틸렌비스(4,6-디-t-부틸페닐)2-에틸헥실포스파이트, 트리스(2,4-디-t-부틸페닐)포스파이트, 트리스(노닐페닐)포스파이트, 테트라(C12 ∼ C15 알킬)-4,4'-이소프로필리덴디페닐디포스파이트, 디페닐모노(2-에틸헥실)포스파이트, 디페닐이소데실포스파이트, 트리스(이소데실)포스파이트, 트리페닐포스파이트, 트리스(트리데실)포스파이트, 페닐이소옥틸포스파이트, 페닐이소데실포스파이트, 페닐디(트리데실)포스파이트, 디페닐이소옥틸포스파이트, 디페닐트리데실포스파이트, 4,4'-이소프로필리덴디페놀알킬포스파이트, 트리스노닐페닐포스파이트, 트리스디노닐페닐포스파이트, 트리스(비페닐)포스파이트, 디(2,4-디-t-부틸페닐)펜타에리트리톨디포스파이트, 디(노닐페닐)펜타에리트리톨디포스파이트, 페닐비스페놀A펜타에리트리톨디포스파이트, 테트라트리데실4,4'-부틸리덴비스(3-메틸-6-t-부틸페놀)디포스파이트, 헥사트리데실1,1,3-트리스(2-메틸-4-히드록시-5-t-부틸페닐)부탄트리포스파이트, 3,5-디-t-부틸-4-히드록시벤질포스파이트디에틸에스테르, 소듐비스(4-t-부틸페닐)포스파이트, 소듐-2,2-메틸렌-비스(4,6-디-t-부틸페닐)-포스파이트, 1,3-비스(디페녹시포스포닐록시)-벤젠, 아인산에틸비스(2,4-디-t-부틸-6-메틸페닐) 등을 들 수 있다.Phosphorus-based antioxidants include, for example, di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, and 2,2'-methylenebis(4, 6-di-t-butylphenyl)2-ethylhexyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tetra (C12 to C15 alkyl)-4, 4'-Isopropylidenediphenyl diphosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl isodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, tris(tridecyl) phosphite , phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl tridecyl phosphite, 4,4'-isopropylidenediphenol alkyl phosphite, Trisnonylphenylphosphite, trisdinonylphenylphosphite, tris(biphenyl)phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite Spite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris(2) -methyl-4-hydroxy-5-t-butylphenyl)butanetriphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis(4-t-butylphenyl) ) Phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethylbisphosphite (2 , 4-di-t-butyl-6-methylphenyl), etc.

시판품은, 예를 들면, ADEKA CORPORATION 제조의 ADEKASTAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, 135A, 3010, TPP, BASF Japan Ltd. 제조의 IRGAFOS168, Clariant Chemicals Ltd. 제조의 HostanoxP-EPQ 등을 들 수 있다.Commercially available products include, for example, ADEKASTAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, 135A, 3010, TPP, and BASF Japan Ltd. manufactured by ADEKA CORPORATION. Manufactured by IRGAFOS168, Clariant Chemicals Ltd. HostanoxP-EPQ manufactured by the company, etc. can be mentioned.

황계 산화 방지제는, 예를 들면, 2,2-비스{〔3-(도데실티오)-1-옥소프로폭시〕메틸}프로판-1,3-디일비스〔3-(도데실티오)프로피오네이트〕, 3,3'-티오비스프로피온산디트리데실, 2,2-티오-디에틸렌비스〔3-(3,5-디-t-부틸-4-히드록시페닐)프로피오네이트〕, 2,4-비스〔(옥틸티오)메틸〕-o-크레졸, 2,4-비스〔(라우릴티오)메틸〕-o-크레졸 등을 들 수 있다.Sulfur-based antioxidants include, for example, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propio nate], 3,3'-thiobispropionate ditridecyl, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2 , 4-bis[(octylthio)methyl]-o-cresol, 2,4-bis[(laurylthio)methyl]-o-cresol, etc.

시판품은, 예를 들면, ADEKA CORPORATION 제조의 ADEKASTAB AO-412S, AO-503, CHEMIPRO KASEI KAISHA, LTD. 제조의 KEMINOXPLS 등을 들 수 있다.Commercially available products include, for example, ADEKASTAB AO-412S, AO-503 manufactured by ADEKA CORPORATION, CHEMIPRO KASEI KAISHA, LTD. Manufactured by KEMINOXPLS, etc. may be mentioned.

산화 방지제(L)는, 단독 또는 2종류 이상을 병용하여 사용할 수 있다.Antioxidants (L) can be used individually or in combination of two or more types.

산화 방지제(L)의 함유량은, 감광성 조성물의 불휘발분 100질량％ 중, 0.5 ∼ 5.0질량％가 바람직하다. 적량 함유하면 투과율, 분광 특성, 및 감도가 향상된다.The content of antioxidant (L) is preferably 0.5 to 5.0% by mass in 100% by mass of non-volatile matter of the photosensitive composition. Containing an appropriate amount improves transmittance, spectral characteristics, and sensitivity.

[레벨링제(M)][Leveling Agent (M)]

본 발명의 감광성 조성물은, 레벨링제(M)를 함유할 수 있다. 이에 따라, 도공 시의 기판에 대한 젖음성, 및 건조성이 보다 향상된다.The photosensitive composition of the present invention may contain a leveling agent (M). Accordingly, the wettability and dryness of the substrate during coating are further improved.

레벨링제(M)는, 예를 들면, 실리콘계 계면활성제, 불소계 계면활성제, 비이온성 계면활성제, 양이온성 계면활성제, 음이온성 계면활성제, 양성 계면활성제 등을 들 수 있다.Examples of the leveling agent (M) include silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

실리콘계 계면활성제는, 예를 들면, 실록산 결합으로 이루어지는 직쇄상 폴리머나, 측쇄나 말단에 유기기를 도입한 변성 실록산 폴리머를 들 수 있다.Silicone-based surfactants include, for example, linear polymers composed of siloxane bonds and modified siloxane polymers with organic groups introduced into side chains or terminals.

시판품은, 예를 들면, BYK-Chemie Inc. 제조의 BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570, Dow Corning Toray Co., Ltd. 제조의 FZ-7002, 2110, 2122, 2123, 2191, 5609, Shin-Etsu Chemical Co., Ltd. 제조의 X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341 등을 들 수 있다.Commercially available products include, for example, BYK-Chemie Inc. Manufactured by BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 , Dow Corning Toray Co., Ltd. Manufactured by FZ-7002, 2110, 2122, 2123, 2191, 5609, Shin-Etsu Chemical Co., Ltd. Manufactured by X-22-4952, X-22-4272, 22-4515, KF-6004, KP-341, etc.

불소계 계면활성제는, 예를 들면, 플루오로카본쇄를 갖는 계면활성제 또는 레벨링제를 들 수 있다.Examples of the fluorine-based surfactant include a surfactant or leveling agent having a fluorocarbon chain.

시판품은, 예를 들면, AGC SEIMI CHEMICAL CO., LTD. 제조의 SURFLON S-242, 243, 420, 611, 651, 386, DIC Corporation 제조의 MEGAFACE F-253, 477, 551, 552, 555, 558, 560, 570, 575, 576, R-40-LM, R-41, RS-72-K, DS-21, Sumitomo 3M Limited 제조의 FC-4430, 4432, Mitsubishi Materials Electronic Chemicals Co., Ltd. 제조의 EF-PP31N09, EF-PP33G1, EF-PP32C1, NEOS COMPANY LIMITED 제조 FTERGENT의 602A 등을 들 수 있다.Commercially available products include, for example, AGC SEIMI CHEMICAL CO., LTD. SURFLON S-242, 243, 420, 611, 651, 386 manufactured by DIC Corporation, MEGAFACE F-253, 477, 551, 552, 555, 558, 560, 570, 575, 576, R-40-LM manufactured by DIC Corporation, R-41, RS-72-K, DS-21, FC-4430, 4432 manufactured by Sumitomo 3M Limited, Mitsubishi Materials Electronic Chemicals Co., Ltd. EF-PP31N09, EF-PP33G1, EF-PP32C1 manufactured by NEOS COMPANY LIMITED, 602A manufactured by FTERGENT, etc.

비이온성 계면활성제는, 예를 들면, 폴리옥시에틸렌라우릴에테르, 폴리옥시에틸렌세틸에테르, 폴리옥시에틸렌스테아릴에테르, 폴리옥시에틸렌올레일에테르, 폴리옥시에틸렌알킬에테르, 폴리옥시에틸렌미리스테르에테르, 폴리옥시에틸렌옥틸도데실에테르, 폴리옥시알킬렌알킬에테르, 폴리옥시페닐렌디스티렌화페닐에테르, 폴리옥시에틸렌트리벤질페닐에테르, 폴리옥시에틸렌폴리옥시프로필렌글리콜, 폴리옥시알킬렌알케닐에테르, 폴리옥시에틸렌노닐페닐에테르, 폴리옥시에틸렌알킬에테르인산에스테르, 소르비탄모노라우레이트, 소르비탄모노팔미테이트, 소르비탄모노스테아레이트, 소르비탄디스테아레이트, 소르비탄트리스테아레이트, 소르비탄모노올레이트, 소르비탄트리올레이트, 소르비탄세스퀴올레이트, 폴리옥시에틸렌소르비탄모노라우레이트, 폴리옥시에틸렌소르비탄모노팔미테이트, 폴리옥시에틸렌소르비탄모노스테아레이트, 폴리옥시에틸렌소르비탄트리스테아레이트, 폴리옥시에틸렌소르비탄모노올레이트, 폴리옥시에틸렌소르비탄트리이소스테아레이트, 테트라올레인산폴리옥시에틸렌소르비트, 글리세롤모노스테아레이트, 글리세롤모노올레이트, 폴리에틸렌글리콜모노라우레이트, 폴리에틸렌글리콜모노스테아레이트, 폴리에틸렌글리콜디스테아레이트, 폴리에틸렌글리콜모노올레이트, 폴리옥시에틸렌 경화 피마자유, 폴리옥시에틸렌알킬아민, 알킬알칸올아미드, 알킬이미다졸린 등을 들 수 있다.Nonionic surfactants are, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrister ether. , polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxy Ethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan Bitane trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene Sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitate tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distear. salt, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkylalkanolamide, alkylimidazoline, etc.

시판품은, 예를 들면, Kao Corporation 제조의 EMULGEN 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, LATEMUL PD-420, PD-430, PD-430S, PD-450, RHEODOL SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, SUPER SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-iS399C, SUPER TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, EMANON 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), AMIET 102, 105, 105A, 302, 320, Aminon PK-02S, L-02, Homogenol L-95, ADEKA CORPORATION 제조의 ADEKA Pluronic(등록상표) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, kyoeisha chemical co., ltd. 제조의 (메타)아크릴산계 (공)중합체 폴리플로우 No.75, No.90, No.95 등을 들 수 있다.Commercially available products include, for example, EMULGEN 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, manufactured by Kao Corporation. 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A- 90, B-66, PP-290, LATEMUL PD-420, PD-430, PD-430S, PD-450, RHEODOL SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP- O10V, SP-O30V, SUPER SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V , TW-iS399C, SUPER TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, EMANON 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40 , CH-60(K), AMIET 102, 105, 105A, 302, 320, Aminon PK-02S, L-02, Homogenol L-95, ADEKA Pluronic (registered trademark) L-23, 31, 44 manufactured by ADEKA CORPORATION. , 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, kyoeisha chemical co., ltd. Examples include (meth)acrylic acid-based (co)polymer polyflow No. 75, No. 90, and No. 95.

양이온성 계면활성제는, 예를 들면 알킬아민염이나 라우릴트리메틸암모늄 클로라이드, 스테아릴트리메틸암모늄 클로라이드, 세틸트리메틸암모늄 클로라이드 등의 알킬 4급 암모늄염이나 그들 에틸렌옥사이드 부가물을 들 수 있다.Cationic surfactants include, for example, alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

시판품은, 예를 들면, Kao Corporation 제조의 ACETAMlN 24, QUARTAMIN 24P, 60W, 86P CONC 등을 들 수 있다.Commercially available products include, for example, ACETAMlN 24, QUARTAMIN 24P, 60W, and 86P CONC manufactured by Kao Corporation.

음이온성 계면활성제는, 예를 들면, 폴리옥시에틸렌알킬에테르황산염, 도데실벤젠설폰산나트륨, 스티렌-아크릴산 공중합체의 알칼리염, 알킬나프탈렌설폰산나트륨, 알킬디페닐에테르디설폰산나트륨, 라우릴황산모노에탄올아민, 라우릴황산트리에탄올아민, 라우릴황산암모늄, 스테아르산모노에탄올아민, 스테아르산나트륨, 라우릴황산나트륨, 스티렌-아크릴산 공중합체의 모노에탄올아민, 폴리옥시에틸렌알킬에테르인산에스테르 등을 들 수 있다.Anionic surfactants include, for example, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkaline salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyl ether disulfonate, and lauryl sulfonate. Monoethanolamine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, etc. there is.

시판품은, 예를 들면, NEOS COMPANY LIMITED 제조의 FTERGENT 100, 150, ADEKA CORPORATION 제조의 ADEKA HOPE YES-25, ADEKA COL TS-230E, PS-440E, EC-8600 등을 들 수 있다.Commercially available products include, for example, FTERGENT 100 and 150 manufactured by NEOS COMPANY LIMITED, ADEKA HOPE YES-25 manufactured by ADEKA CORPORATION, ADEKA COL TS-230E, PS-440E and EC-8600.

양성 계면활성제는, 예를 들면, 라우린산아미드프로필 베타인, 라우릴 베타인, 코카미도프로필 베타인, 스테아릴 베타인, 알킬디메틸아미노아세트산 베타인 등의 알킬 베타인, 라우릴디메틸아민옥사이드 등의 알킬아민옥사이드 등을 들 수 있다.Amphoteric surfactants include, for example, alkyl betaines such as propyl laurate amide betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine, and lauryl dimethylamine oxide. and alkylamine oxide.

시판품은, Kao Corporation 제조의 AMPHITOL 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, 20N 등을 들 수 있다.Commercially available products include AMPHITOL 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, and 20N manufactured by Kao Corporation.

레벨링제(M)는, 단독 또는 2종류 이상을 병용하여 사용할 수 있다. The leveling agent (M) can be used individually or in combination of two or more types.

레벨링제(M)의 함유량은, 감광성 조성물의 불휘발분 100질량％ 중, 0.001 ∼ 2.0질량％가 바람직하고, 0.005 ∼ 1.0질량％가 보다 바람직하다. 이 범위 내임으로써, 감광성 조성물의 도포성과 밀착성의 밸런스가 보다 향상된다.The content of the leveling agent (M) is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, based on 100% by mass of non-volatile matter of the photosensitive composition. By falling within this range, the balance between the applicability and adhesion of the photosensitive composition is further improved.

[저장 안정제(N)][Storage stabilizer (N)]

본 발명의 감광성 조성물은, 저장 안정제(N)를 함유할 수 있다. 이에 따라, 감광성 조성물의 경시(經時) 점도가 안정화된다.The photosensitive composition of the present invention may contain a storage stabilizer (N). Accordingly, the viscosity of the photosensitive composition over time is stabilized.

저장 안정제(N)는, 예를 들면, 벤질트리메틸 클로라이드, 디에틸히드록시아민 등의 4급 암모늄 클로라이드, 젖산, 옥살산 등의 유기산 및 그 메틸에테르, t-부틸피로카테콜, 테트라에틸포스핀, 테트라페닐 등의 유기 포스핀, 아인산염 등을 들 수 있다.Storage stabilizers (N) include, for example, quaternary ammonium chloride such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, Organic phosphine such as tetraphenyl, phosphite, etc. can be mentioned.

저장 안정제(N)는, 단독 또는 2종류 이상을 병용하여 사용할 수 있다.The storage stabilizer (N) can be used individually or in combination of two or more types.

저장 안정제(N)의 함유량은, 감광성 조성물의 불휘발분 100질량％ 중, 0.1 ∼ 10질량부가 바람직하다.The content of the storage stabilizer (N) is preferably 0.1 to 10 parts by mass based on 100% by mass of non-volatile matter of the photosensitive composition.

[밀착 향상제(O)][Adhesion improver (O)]

본 발명의 감광성 조성물은, 밀착 향상제(O)를 함유할 수 있다. 이에 따라 피막과 기재(基材)의 밀착성이 향상된다. 또한, 포트리소그래피법으로 폭이 좁은 패턴을 형성하기 쉬워진다.The photosensitive composition of the present invention may contain an adhesion improver (O). Accordingly, the adhesion between the film and the substrate is improved. Additionally, it becomes easier to form narrow patterns using the photolithography method.

밀착 향상제(O)는, 예를 들면, 실란커플링제 등을 들 수 있다. 실란커플링제는, 예를 들면, 비닐트리메톡시실란, 비닐트리에톡시실란 등의 비닐실란류, 3-메타크릴옥시프로필메틸디메톡시실란, 3-메타크릴옥시프로필트리메톡시실란, 3-메타크릴옥시프로필메틸디에톡시실란, 3-메타크릴옥시프로필트리에톡시실란, 3-아크릴옥시프로필트리메톡시실란 등의 (메타)아크릴실란류, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란, 3-글리시독시프로필메틸디메톡시실란, 3-글리시독시프로필트리메톡시실란, 3-글리시독시프로필메틸디에톡시실란, 3-글리시독시프로필트리에톡시실란 등의 에폭시실란류, N-2-(아미노에틸)-3-아미노프로필메틸디메톡시실란, N-2-(아미노에틸)-3-아미노프로필트리메톡시실란, 3-아미노프로필트리메톡시실란, 3-아미노프로필트리에톡시실란, 3-트리에톡시실릴-N-(1,3-디메틸-부틸리덴)프로필아민, N-페닐-3-아미노프로필트리메톡시실란, N-(비닐벤질)-2-아미노에틸-3-아미노프로필트리메톡시실란의 염산염 등의 아미노실란류, 3-메르캅토프로필메틸디메톡시실란, 3-메르캅토프로필트리메톡시실란 등의 메르캅토류, p-스티릴트리메톡시실란 등의 스티릴류, 3-우레이도프로필트리에톡시실란 등의 우레이도류, 비스(트리에톡시실릴프로필)테트라설파이드 등의 설파이드류, 3-이소시아네이트프로필트리에톡시실란 등의 이소시아네이트류 등의 실란커플링제를 들 수 있다.Examples of the adhesion improver (O) include silane coupling agents. Silane coupling agents include, for example, vinyl silanes such as vinyl trimethoxysilane and vinyl triethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyldimethoxysilane. (meth)acrylic silanes such as methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl Trimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. Epoxysilanes, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl) Aminosilanes such as hydrochloride of -2-aminoethyl-3-aminopropyltrimethoxysilane, mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, and p-sti. Styryls such as ryltrimethoxysilane, ureidos such as 3-ureidopropyltriethoxysilane, sulfides such as bis(triethoxysilylpropyl)tetrasulfide, and isocyanates such as 3-isocyanatepropyltriethoxysilane. Silane coupling agents such as Ryu and the like can be mentioned.

밀착 향상제(O)는, 단독 또는 2종류 이상을 병용하여 사용할 수 있다.The adhesion improver (O) can be used individually or in combination of two or more types.

밀착 향상제(O)의 함유량은, 감광성 조성물의 불휘발분 100질량％ 중, 0.01 ∼ 10질량부가 바람직하고, 0.05 ∼ 5질량부가 보다 바람직하다.The content of the adhesion improver (O) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100% by mass of non-volatile matter of the photosensitive composition.

[유기 용제(P)][Organic solvent (P)]

본 발명의 감광성 조성물은, 유기 용제(P)를 함유할 수 있다.The photosensitive composition of the present invention may contain an organic solvent (P).

유기 용제(P)는, 예를 들면, 1,2,3-트리클로로프로판, 1-메톡시-2-프로판올, 젖산에틸, 1,3-부탄디올, 1,3-부틸렌글리콜, 1,3-부틸렌글리콜디아세테이트, 1,4-디옥산, 2-헵타논, 2-메틸-1,3-프로판디올, 3,5,5-트리메틸-2-시클로헥센-1-온, 3,3,5-트리메틸시클로헥산온, 3-에톡시프로피온산에틸, 3-메틸-1,3-부탄디올, 3-메톡시-3-메틸-1-부탄올, 3-메톡시-3-메틸부틸아세테이트, 3-메톡시부탄올, 3-메톡시부틸아세테이트, 4-헵타논, m-크실렌, m-디에틸벤젠, m-디클로로벤젠, N,N-디메틸아세트아미드, N,N-디메틸포름아미드, n-부틸알코올, n-부틸벤젠, n-프로필아세테이트, N-메틸피롤리돈, o-크실렌, o-클로로톨루엔, o-디에틸벤젠, o-디클로로벤젠, p-클로로톨루엔, p-디에틸벤젠, sec-부틸벤젠, tert-부틸벤젠, γ-부티로락톤, 이소부틸알코올, 이소포론, 에틸렌글리콜디에틸에테르, 에틸렌글리콜디부틸에테르, 에틸렌글리콜모노이소프로필에테르, 에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노에틸에테르아세테이트, 에틸렌글리콜모노tert-부틸에테르, 에틸렌글리콜모노부틸에테르, 에틸렌글리콜모노부틸에테르아세테이트, 에틸렌글리콜모노프로필에테르, 에틸렌글리콜모노헥실에테르, 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노메틸에테르아세테이트, 디이소부틸케톤, 디에틸렌글리콜디에틸에테르, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜모노이소프로필에테르, 디에틸렌글리콜모노에틸에테르아세테이트, 디에틸렌글리콜모노부틸에테르, 디에틸렌글리콜모노부틸에테르아세테이트, 디에틸렌글리콜모노메틸에테르, 시클로헥산올, 시클로헥산올아세테이트, 시클로헥산온, 디프로필렌글리콜디메틸에테르, 디프로필렌글리콜메틸에테르아세테이트, 디프로필렌글리콜모노에틸에테르, 디프로필렌글리콜모노부틸에테르, 디프로필렌글리콜모노프로필에테르, 디프로필렌글리콜모노메틸에테르, 다이아세톤알코올, 트리아세틴, 트리프로필렌글리콜모노부틸에테르, 트리프로필렌글리콜모노메틸에테르, 프로필렌글리콜디아세테이트, 프로필렌글리콜페닐에테르, 프로필렌글리콜모노에틸에테르, 프로필렌글리콜모노에틸에테르아세테이트, 프로필렌글리콜모노부틸에테르, 프로필렌글리콜모노프로필에테르, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노메틸에테르프로피오네이트, 벤질알코올, 메틸이소부틸케톤, 메틸시클로헥산올, 아세트산n-아밀, 아세트산n-부틸, 아세트산이소아밀, 아세트산이소부틸, 아세트산프로필, 이염기산에스테르 등을 들 수 있다. 이들 중에서도, 안료의 분산성, 알칼리 가용성 수지의 용해성의 관점에서, 젖산에틸, 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노에틸에테르아세테이트, 에틸렌글리콜모노메틸에테르아세테이트, 에틸렌글리콜모노에틸에테르아세테이트 등의 글리콜아세테이트류, 벤질알코올, 다이아세톤알코올 등의 알코올류나 시클로헥산온 등의 케톤류가 바람직하다.The organic solvent (P) is, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3 -Butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3 , 5-trimethylcyclohexanone, 3-ethoxyethyl propionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3 -Methoxybutanol, 3-methoxybutylacetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n- Butyl alcohol, n-butylbenzene, n-propylacetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene , sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene Glycol monoethyl ether acetate, ethylene glycol monotert-butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether Acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene. Glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene Glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclo Hexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester, etc. Among these, from the viewpoint of the dispersibility of the pigment and the solubility of the alkali-soluble resin, glycols such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate. Alcohols such as acetates, benzyl alcohol, and diacetone alcohol, and ketones such as cyclohexanone are preferable.

유기 용제(P)는, 단독 또는 2종류 이상을 병용하여 사용할 수 있다.The organic solvent (P) can be used individually or in combination of two or more types.

[감광성 조성물의 제조 방법][Method for producing photosensitive composition]

본 발명의 감광성 조성물은, 예를 들면, 착색제(E), 알칼리 가용성 수지(A), 분산 수지(G), 색소 유도체(F), 및 유기 용제(P) 등을 더하여 분산 처리를 행함으로써, 분산체를 제조한다. 그 후, 상기 분산체에, 중합성 화합물(B), 광중합개시제(C) 등을 배합하고 혼합함으로써 제조할 수 있다. 또, 각 재료를 배합하는 타이밍은, 임의이다. 또한, 분산 공정을 복수 회 행할 수도 있다.The photosensitive composition of the present invention is subjected to dispersion treatment by adding, for example, a colorant (E), an alkali-soluble resin (A), a dispersing resin (G), a dye derivative (F), and an organic solvent (P), etc. Prepare the dispersion. Thereafter, the dispersion can be prepared by mixing and mixing a polymerizable compound (B), a photopolymerization initiator (C), and the like. Additionally, the timing for mixing each material is arbitrary. Additionally, the dispersion process may be performed multiple times.

분산 처리를 행하는 분산기는, 예를 들면, 2개 롤 밀, 3개 롤 밀, 볼 밀, 횡형 샌드 밀, 종형 샌드 밀, 애뉼러형 비드 밀, 또는 어트리터 등을 들 수 있다.Dispersing machines that perform dispersion treatment include, for example, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor.

분산체 중의 착색제의 평균 분산 입자경(이차 입자경)은, 30 ∼ 200㎚가 바람직하고, 40 ∼ 200㎚가 보다 바람직하다. 적당한 입자경을 가지면 분산 안정성이 높은 감광성 조성물을 얻기 쉽다.The average dispersed particle diameter (secondary particle diameter) of the colorant in the dispersion is preferably 30 to 200 nm, and more preferably 40 to 200 nm. Having an appropriate particle size makes it easy to obtain a photosensitive composition with high dispersion stability.

평균 분산 입자경(이차 입자경)의 측정 방법은, 예를 들면, 동적 광산란법(FFT 파워 스펙트럼법)을 채용한 Nikkiso Co., Ltd.의 Microtrac UPA-EX150을 이용하여, 입자 투과성을 흡수 모드, 입자 형상을 비구형으로 하고, D50 입자경을 평균경으로 한다. 측정용의 희석 용제는 분산에 사용한 유기 용제를 각각 이용하여, 초음파로 처리한 샘플에 대해서 샘플 조정 직후에 측정하면 불균일이 적은 결과가 얻어지기 쉬워 바람직하다.The method of measuring the average distributed particle size (secondary particle size) is, for example, using Microtrac UPA-EX150 from Nikkiso Co., Ltd., which employs a dynamic light scattering method (FFT power spectrum method), and determines the particle permeability by absorption mode, particle The shape is non-spherical, and the D50 particle diameter is taken as the average diameter. The diluting solvent for measurement is preferably one of the organic solvents used for dispersion, and measuring a sample treated with ultrasonic waves immediately after sample adjustment is easy to obtain results with less unevenness.

감광성 조성물은, 원심 분리, 소결 필터나 멤브레인 필터에 의한 여과 등의 수단으로, 5㎛ 이상의 조대 입자, 바람직하게는 1㎛ 이상의 조대 입자, 더 바람직하게는 0.5㎛ 이상의 조대 입자, 및 혼입된 티끌의 제거를 행하는 것이 바람직하다. 본 발명의 감광성 조성물은, 실질적으로 0.5㎛ 이상의 입자를 포함하지 않는 것이 바람직하고, 0.3㎛ 이하의 입자를 포함하지 않는 것이 보다 바람직하다.The photosensitive composition is separated from coarse particles of 5 ㎛ or larger, preferably of 1 ㎛ or larger, more preferably of 0.5 ㎛ or larger, and mixed dust by centrifugation, filtration using a sintered filter, or membrane filter. It is desirable to perform removal. It is preferable that the photosensitive composition of the present invention does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

<광학 필터><Optical filter>

본 발명의 광학 필터는, 기판, 및 본 발명의 감광성 조성물로 형성되는 필터 세그먼트를 구비한다. 광학 필터는, 다양한 용도에 사용할 수 있다. 본 명세서에서 광학 필터는, 컬러 필터가 바람직하다.The optical filter of the present invention includes a substrate and a filter segment formed from the photosensitive composition of the present invention. Optical filters can be used for various purposes. In this specification, the optical filter is preferably a color filter.

필터 세그먼트는, 컬러 필터의 경우에는, 사용하는 착색제(E)의 종류를 적절히 선택함으로써, 적색 필터 세그먼트, 녹색 필터 세그먼트, 및 청색 필터 세그먼트를 갖는다. 상기 필터 세그먼트를 대신하거나 또는 더하여, 마젠타색 필터 세그먼트, 시안색 필터 세그먼트, 옐로우색 필터 세그먼트, 화이트 필터 세그먼트, 블랙 필터 세그먼트를 가질 수도 있다. 또한, 착색제(E)를 사용하지 않는 클리어의 필터를 가질 수 있다.In the case of a color filter, the filter segment has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of colorant (E) to be used. Instead of or in addition to the filter segment, it may have a magenta filter segment, a cyan filter segment, a yellow filter segment, a white filter segment, and a black filter segment. Additionally, it is possible to have a clear filter that does not use a colorant (E).

상기 기판은, 투명 기판, 및 반사 기판을 들 수 있다. 상기 투명 기판은, 예를 들면, 유리 기판을 들 수 있다. 상기 반사 기판은, 예를 들면 알루미늄 전극이나 금속 박막을 반사면으로서 사용하는 기판을 들 수 있다.The substrate may include a transparent substrate and a reflective substrate. The transparent substrate may be, for example, a glass substrate. Examples of the reflective substrate include a substrate using an aluminum electrode or a thin metal film as a reflective surface.

[광학 필터의 제조 방법][Method of manufacturing optical filter]

광학 필터의 제조 방법은, 예를 들면, 기판 상에 감광성 조성물을 도포하여 조성물의 층(피막)을 형성하는 공정(1), 상기 층에, 마스크를 개재하여 패턴상으로 노광하는 공정(2), 미노광 부분을 알칼리 현상하여 패턴상의 경화막을 형성하는 공정(3), 상기 패턴을 가열 처리(포스트 베이크)하는 공정(4)을 행하여 제작할 수 있다.The manufacturing method of an optical filter includes, for example, a step of applying a photosensitive composition on a substrate to form a layer (film) of the composition (1), and a step of exposing the layer to light in a pattern through a mask (2). , it can be produced by performing a step (3) of alkali developing the unexposed portion to form a pattern-shaped cured film, and a step (4) of heat treating (post-baking) the pattern.

이하, 광학 필터의 제조 방법을 상세하게 설명한다.Hereinafter, the manufacturing method of the optical filter will be described in detail.

(공정(1))(Process (1))

조성물의 층을 형성하는 공정(1)은, 감광성 조성물을 기판 상에, 예를 들면, 회전 도포, 롤 도포, 슬릿 도포, 유연(流延) 도포, 또는 잉크젯 도포 등의 방법으로 도포하고, 필요에 따라 오븐, 핫플레이트 등을 이용하여, 50 ∼ 120℃의 온도에서 10 ∼ 120초 건조(프리 베이크)한다.In the step (1) of forming a layer of the composition, the photosensitive composition is applied to the substrate by, for example, rotation coating, roll coating, slit coating, flexible coating, or inkjet coating, and requires Depending on the conditions, dry (pre-bake) for 10 to 120 seconds at a temperature of 50 to 120°C using an oven, hot plate, etc.

상기 기판은, 예를 들면, 유리 기판, 실리콘 기판 등을 들 수 있다. 실리콘 기판은, 예를 들면, 표면에 CCD, CMOS 등의 촬상 소자가 형성되어 있어도 된다. 또한, 기판 상에는, 필요에 따라, 상부와의 층과의 밀착 개량, 물질의 확산 방지, 기판 표면의 평탄화를 위해 밑칠층을 마련해도 된다.The substrate may be, for example, a glass substrate or a silicon substrate. For example, the silicon substrate may have an imaging device such as CCD or CMOS formed on its surface. Additionally, if necessary, an undercoating layer may be provided on the substrate to improve adhesion between the upper layer and the layer, prevent diffusion of substances, and flatten the substrate surface.

층의 막두께는, 0.05 ∼ 10.0㎛가 바람직하고, 0.3 ∼ 5㎛가 보다 바람직하다.The film thickness of the layer is preferably 0.05 to 10.0 μm, and more preferably 0.3 to 5 μm.

(공정(2))(Process (2))

노광 공정은, 공정(1)에서 얻어진 층을, 예를 들면, 스테퍼 등의 노광 장치를 이용하고, 마스크를 개재하여 특정의 패턴을 노광한다. 이에 따라 경화막이 얻어진다.In the exposure process, the layer obtained in process (1) is exposed to a specific pattern through a mask using an exposure device such as a stepper. Accordingly, a cured film is obtained.

노광에 이용하는 방사선은, 예를 들면, g선, h선, i선 등의 자외선을 들 수 있다.Radiation used for exposure includes, for example, ultraviolet rays such as g-rays, h-rays, and i-rays.

(공정(3))(Process (3))

공정(2)에서 얻어진 경화막은, 알칼리 현상 처리를 행함으로써, 미노광 부분의 조성물의 층이 알칼리 수용액에 용출되어, 경화 부분만이 남아 패턴상의 경화막이 얻어진다.When the cured film obtained in step (2) is subjected to alkali development, the layer of the composition in the unexposed portion is eluted into the aqueous alkaline solution, and only the cured portion remains, thereby obtaining a patterned cured film.

현상액은, 예를 들면, 수산화나트륨, 수산화칼륨, 탄산나트륨, 규산나트륨, 메타규산나트륨, 암모니아수, 에틸아민, 디에틸아민, 디메틸에탄올아민, 테트라메틸암모늄히드록시드, 테트라에틸암모늄히드록시드, 콜린, 피롤, 피페리딘, 1,8-디아자비시클로-〔5.4.0〕-7-운데센 등의 알칼리성 화합물을 들 수 있다.Developers include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline. , pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene.

현상액의 농도는, 0.001 ∼ 10질량％가 바람직하고, 0.01 ∼ 1질량％가 보다 바람직하다.The concentration of the developing solution is preferably 0.001 to 10 mass%, and more preferably 0.01 to 1 mass%.

알칼리 현상액의 pH는, 11 ∼ 13이 바람직하고, 11.5 ∼ 12.5가 보다 바람직하다. 적당한 pH로 사용하면 패턴의 거칠기나 박리를 억제하여, 현상 후의 잔막률이 향상된다.The pH of the alkaline developing solution is preferably 11 to 13, and more preferably 11.5 to 12.5. When used at an appropriate pH, pattern roughness and peeling are suppressed, and the remaining film rate after development is improved.

현상 방법은, 예를 들면, 딥법, 스프레이법, 패들법 등을 들 수 있다. 현상 온도는 15 ∼ 40℃가 바람직하다. 또, 알칼리 현상 후는, 순수(純水)로 세정하는 것이 바람직하다.Development methods include, for example, a dip method, a spray method, and a paddle method. The developing temperature is preferably 15 to 40°C. Additionally, after alkali development, it is preferable to wash with pure water.

(공정(4))(Process (4))

가열 처리(포스트 베이크)는, 공정(3)에서 얻어진 패턴상의 경화막을 가열에 의해 충분히 경화시킨다. 포스트 베이크의 가열 온도는, 100 ∼ 300℃가 바람직하고, 150 ∼ 250℃가 보다 바람직하다. 또한, 가열 시간은, 2분간 ∼ 1시간 정도가 바람직하고, 3분간 ∼ 30분간 정도가 보다 바람직하다.Heat treatment (post-bake) sufficiently cures the patterned cured film obtained in step (3) by heating. The post-bake heating temperature is preferably 100 to 300°C, and more preferably 150 to 250°C. In addition, the heating time is preferably about 2 minutes to 1 hour, and more preferably about 3 minutes to 30 minutes.

<화상 표시 장치><Image display device>

본 발명의 화상 표시 장치는, 본 발명의 광학 필터를 구비한다. 화상 표시 장치는, 예를 들면, 액정 디스플레이, 유기 EL 디스플레이 등을 들 수 있다.The image display device of the present invention includes the optical filter of the present invention. Examples of image display devices include liquid crystal displays and organic EL displays.

화상 표시 장치에 이용하는 형태는, 화상 표시 장치로서 기능하면 되고, 특별히 제한되지 않는다. 예를 들면, 「차세대 액정 디스플레이 기술(Uchida Tatsuo저, Kogyo Chosakai Publishing Co., Ltd., 1994년 발행)에 기재되어 있는 구성 등을 들 수 있다.The form used in the image display device is not particularly limited as long as it functions as an image display device. For example, the configuration described in “Next-Generation Liquid Crystal Display Technology” (written by Tatsuo Uchida, published by Kogyo Chosakai Publishing Co., Ltd., 1994).

화상 표시 장치의 정의나 각 화상 표시 장치의 상세에 대해서는, 예를 들면, 「전자 디스플레이 디바이스(Sasaki Akio저, Kogyo Chosakai Publishing Co., Ltd., 1990년 발행)」, 「디스플레이 디바이스(Ibuki Sumiaki저, Sangyo Tosho Publishing Co., Ltd., 1989년 발행)」 등에 기재되어 있다.For definitions of image display devices and details of each image display device, see, for example, “Electronic Display Devices (by Sasaki Akio, published by Kogyo Chosakai Publishing Co., Ltd., 1990)” and “Display Devices (by Ibuki Sumiaki). , published by Sangyo Tosho Publishing Co., Ltd., 1989).

<고체 촬상 소자><Solid-state imaging device>

본 발명의 고체 촬상 소자는, 본 발명의 광학 필터를 구비한다.The solid-state imaging device of the present invention includes the optical filter of the present invention.

고체 촬상 소자에 이용하는 형태는, 특별히 제한되지 않지만, 예를 들면, 기재 상에, 고체 촬상 소자(CCD 이미지 센서, CMOS 이미지 센서 등)의 수광 에어리어를 구성하는 복수의 포토다이오드 및 폴리실리콘 등으로 이루어지는 전송 전극을 갖고, 포토다이오드 및 전송 전극 상에 포토다이오드의 수광부만 개구된 차광막을 갖고, 차광막 상에 차광막 전면(全面) 및 포토다이오드 수광부를 덮도록 형성된 질화실리콘 등으로 이루어지는 디바이스 보호막을 갖고, 디바이스 보호막 상에, 필터를 갖는 구성이다. 또한, 디바이스 보호막 상이며 필터 하(기재에 가까운 측)에 집광 수단(예를 들면, 마이크로 렌즈 등. 이하 같음)을 갖는 구성이나, 필터 상에 집광 수단을 갖는 구성 등이어도 된다. 또한, 필터는, 격벽에 의해 예를 들면 격자상으로 구분된 공간에, 각 착색 화소를 형성하는 경화막이 매립된 구조를 갖고 있어도 된다. 이 경우의 격벽은, 각 착색 화소에 대하여 저굴절률이 바람직하다.The form used in the solid-state imaging device is not particularly limited, but for example, it consists of a plurality of photodiodes and polysilicon that constitute the light-receiving area of the solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) on a substrate. It has a transfer electrode, has a photodiode and a light-shielding film on the transfer electrode with only the light-receiving part of the photodiode open, and has a device protective film made of silicon nitride or the like formed on the light-shielding film to cover the entire light-shielding film and the light-receiving part of the photodiode, and has a device protective film made of silicon nitride or the like. It is configured to have a filter on the protective film. Additionally, it may be configured to have a light condensing means (e.g., micro lens, etc., hereinafter the same) on the device protective film and below the filter (closer to the substrate), or may have a light condensing means on the filter. In addition, the filter may have a structure in which the cured film forming each colored pixel is embedded in a space divided by partitions, for example, in a grid shape. The partition in this case preferably has a low refractive index for each colored pixel.

본 발명의 고체 촬상 소자를 구비한 촬상 장치는, 예를 들면, 디지털 카메라, 촬상 기능을 갖는 전자 기기(휴대 전화, 스마트폰 등), 차재 카메라, 감시 카메라 등 다양한 용도에 사용할 수 있다.The imaging device equipped with the solid-state imaging element of the present invention can be used for various purposes, such as digital cameras, electronic devices with imaging functions (mobile phones, smartphones, etc.), in-vehicle cameras, and surveillance cameras.

[실시예][Example]

이하, 실시예에서 본 발명을 보다 구체적으로 설명한다. 단, 본 발명은 이들에 한정되지 않는다. 또, 「부」는 「질량부」, 「％」는 「질량％」이다.Hereinafter, the present invention will be described in more detail in examples. However, the present invention is not limited to these. In addition, “part” means “part by mass,” and “%” means “% by mass.”

또한, 본 발명에 있어서, 불휘발분 혹은 불휘발분 농도는, 280℃에서 30분간 오븐 정치 후의, 질량 잔분(殘分)을 말한다.In addition, in the present invention, the non-volatile matter or non-volatile matter concentration refers to the mass residue after standing in an oven at 280°C for 30 minutes.

실시예에 앞서, 각 측정 방법에 대해서 설명한다.Prior to the examples, each measurement method will be explained.

수지의 중량 평균 분자량(Mw), 수평균 분자량(Mn), 산가(㎎KOH／g)는, 이하와 같다.The weight average molecular weight (Mw), number average molecular weight (Mn), and acid value (mgKOH/g) of the resin are as follows.

(알칼리 가용성 수지, 및 분산 수지의 평균 분자량)(Average molecular weight of alkali-soluble resin and dispersion resin)

알칼리 가용성 수지, 및 분산 수지의 수평균 분자량(Mn), 중량 평균 분자량(Mw)은, RI 검출기를 장비한 겔퍼미에이션 크로마토그래피(GPC)로 측정했다. 장치로서 HLC-8220GPC(TOSOH CORPORATION 제조)를 이용하고, 분리 컬럼을 2개 직렬로 연결하고, 양쪽의 충전제에는 「TSK-GEL SUPER HZM-N」을 2련으로 연결하여 사용하고, 오븐 온도 40℃, 용리액으로서 테트라히드로퓨란(THF) 용액을 이용하고, 유속 0.35ml／min으로 측정했다. 샘플은 1질량％의 상기 용리액으로 이루어지는 용제에 용해하여, 20마이크로리터 주입했다. 평균 분자량은, 폴리스티렌 환산치이다.The number average molecular weight (Mn) and weight average molecular weight (Mw) of the alkali-soluble resin and the dispersion resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. As a device, HLC-8220GPC (manufactured by TOSOH CORPORATION) is used, two separation columns are connected in series, and “TSK-GEL SUPER HZM-N” is connected in series to the fillers on both sides, and the oven temperature is 40°C. , a tetrahydrofuran (THF) solution was used as an eluent, and measurement was performed at a flow rate of 0.35 ml/min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters were injected. The average molecular weight is polystyrene conversion value.

(알칼리 가용성 수지, 및 분산 수지의 산가)(Acid value of alkali soluble resin and dispersion resin)

알칼리 가용성 수지, 및 분산 수지 용액 0.5 ∼ 1g에, 아세톤 80ml 및 물 10ml를 더해 교반하여 균일하게 용해시키고, 0.1mol／L의 KOH 수용액을 적정액으로 하여, 자동 적정 장치(「COM-555」 HIRANUMA Co., Ltd. 제조)를 이용하여 적정하고, 산가(㎎KOH／g)를 측정했다. 그리고, 수지 용액의 산가와 수지 용액의 불휘발분 농도로부터, 수지의 불휘발분당의 산가를 산출했다.To 0.5 to 1 g of alkali-soluble resin and dispersed resin solution, 80 ml of acetone and 10 ml of water were added and stirred to uniformly dissolve, and 0.1 mol/L KOH aqueous solution was used as a titrant, using an automatic titrator (“COM-555” HIRANUMA). Co., Ltd.) was used to titrate and the acid value (mg KOH/g) was measured. Then, the acid value per nonvolatile content of the resin was calculated from the acid value of the resin solution and the nonvolatile content concentration of the resin solution.

(분산 수지의 아민가)(Amine value of dispersion resin)

분산 수지의 아민가는, ASTM D 2074의 방법에 준거하여, 측정한 전체 아민가(㎎KOH／g)를 불휘발분 환산한 값이다.The amine titer of the dispersion resin is a value obtained by converting the total amine titer (mg KOH/g) measured according to the method of ASTM D 2074 into non-volatile matter.

<착색제(E)의 제조><Preparation of colorant (E)>

(미세화한 적색 안료(E-1))(Micronised red pigment (E-1))

C.I. Pigment Red 254를 100부, 염화나트륨 1,200부, 및 디에틸렌글리콜 120부를 스테인리스제 1갤런 니더(Inoue Seisakusho Co., Ltd. 제조) 중에 투입하고, 60℃에서 6시간 혼련했다. 다음으로, 혼련한 혼합물을 온수에 투입하고, 약 80℃로 가열하면서 하이스피드 믹서로 1시간 교반하여 슬러리상으로 하고, 여과·수세를 하여 염화나트륨 및 디에틸렌글리콜을 제거한 후, 80℃에서 일주야(一晝夜) 건조시키고, 분쇄함으로써 미세화한 적색 안료(E-1)를 얻었다.C.I. 100 parts of Pigment Red 254, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 6 hours. Next, the kneaded mixture is put into hot water, heated to about 80℃ and stirred for 1 hour with a high-speed mixer to form a slurry, filtered and washed to remove sodium chloride and diethylene glycol, and kept at 80℃ for one week. (One day and night) It was dried and pulverized to obtain a fine red pigment (E-1).

(미세화한 적색 안료(E-2))(Micronised red pigment (E-2))

C.I. Pigment Red 177을 100부, 염화나트륨 1,200부, 및 디에틸렌글리콜 120부를 스테인리스제 1갤런 니더(Inoue Seisakusho Co., Ltd. 제조) 중에 투입하고, 60℃에서 6시간 혼련했다. 다음으로, 혼련한 혼합물을 온수에 투입하고, 약 80℃로 가열하면서 하이스피드 믹서로 1시간 교반하여 슬러리상으로 하고, 여과·수세를 하여 염화나트륨 및 디에틸렌글리콜을 제거한 후, 80℃에서 일주야 건조시키고, 분쇄함으로써 미세화한 적색 안료(E-2)를 얻었다.C.I. 100 parts of Pigment Red 177, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 6 hours. Next, the kneaded mixture is put into hot water, heated to about 80℃ and stirred for 1 hour with a high-speed mixer to form a slurry, filtered and washed to remove sodium chloride and diethylene glycol, and kept at 80℃ for one week. By drying and pulverizing, a fine red pigment (E-2) was obtained.

(미세화한 청색 안료(E-3))(Micronised blue pigment (E-3))

C.I. Pigment Blue 15:6을 100부, 염화나트륨 1,000부, 및 디에틸렌글리콜 100부를 스테인리스제 1갤런 니더(Inoue Seisakusho Co., Ltd. 제조)에 투입하고, 50℃에서 12시간 혼련했다. 이 혼합물을 온수 3,000부에 투입하고, 약 70℃로 가열하면서 하이스피드 믹서로 약 1시간 교반하여 슬러리상으로 하고, 여과, 수세를 반복하여 식염 및 용제를 제거한 후, 80℃에서 24시간 건조하고, 분쇄함으로써 미세화한 청색 안료(E-3)를 얻었다.C.I. 100 parts of Pigment Blue 15:6, 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were added to a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 50°C for 12 hours. This mixture was poured into 3,000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then dried at 80°C for 24 hours. , a micronized blue pigment (E-3) was obtained by grinding.

(미세화한 자색 안료(E-4))(Miniaturized purple pigment (E-4))

C.I. Pigment Violet 23을 100부, 염화나트륨 1,200부, 및 디에틸렌글리콜 100부를 스테인리스제 1갤런 니더(Inoue Seisakusho Co., Ltd. 제조)에 투입하고, 80℃에서 6시간 혼련했다. 다음으로, 이 혼련물을 8,000부의 온수에 투입하고, 80℃로 가열하면서 하이스피드 믹서로 2시간 교반하여 슬러리상으로 하고, 여과, 수세를 반복하여 염화나트륨, 및 디에틸렌글리콜을 제거한 후, 85℃에서 24시간 건조하고, 분쇄함으로써 미세화한 자색 안료(E-4)를 얻었다.C.I. 100 parts of Pigment Violet 23, 1,200 parts of sodium chloride, and 100 parts of diethylene glycol were added to a 1 gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. Next, this kneaded product was poured into 8,000 parts of warm water, heated to 80°C and stirred for 2 hours with a high-speed mixer to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then cooled to 85°C. After drying for 24 hours and pulverizing, a finely divided purple pigment (E-4) was obtained.

(미세화한 녹색 안료(E-5))(Micronised green pigment (E-5))

C.I. Pigment Green 58을 100부, 염화나트륨 1,200부, 및 디에틸렌글리콜 120부를 스테인리스제 1갤런 니더(Inoue Seisakusho Co., Ltd. 제조)에 투입하고, 70℃에서 6시간 혼련했다. 이 혼련물을 3,000부의 온수에 투입하고, 70℃로 가열하면서 하이스피드 믹서로 1시간 교반하여 슬러리상으로 하고, 여과, 수세를 반복하여 염화나트륨 및 디에틸렌글리콜을 제거한 후, 80℃에서 일주야 건조하고, 분쇄함으로써 미세화한 녹색 안료(E-5)를 얻었다.C.I. 100 parts of Pigment Green 58, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were added to a 1 gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70°C for 6 hours. This kneaded product is poured into 3,000 parts of warm water, heated to 70°C and stirred for 1 hour with a high-speed mixer to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C for one day and night. and pulverized to obtain a micronized green pigment (E-5).

(미세화한 녹색 안료(E-6)(Micronised green pigment (E-6)

일본 특허공개 2017-111398호 공보의 실시예에 따라서, 하기 화학식(20)의 녹색 안료(E-6)를 얻었다. 녹색 안료(E-6)를 100부, 염화나트륨 1,200부, 및 디에틸렌글리콜 120부를 스테인리스제 1갤런 니더(Inoue Seisakusho Co., Ltd. 제조)에 투입하고, 70℃에서 6시간 혼련했다. 이 혼련물을 3,000부의 온수에 투입하고, 70℃로 가열하면서 하이스피드 믹서로 1시간 교반하여 슬러리상으로 하고, 여과, 수세를 반복하여 염화나트륨 및 디에틸렌글리콜을 제거한 후, 80℃에서 일주야 건조하고, 분쇄함으로써 미세화한 녹색 안료(E-6)를 얻었다.According to the examples of Japanese Patent Application Laid-Open No. 2017-111398, a green pigment (E-6) of the following formula (20) was obtained. 100 parts of the green pigment (E-6), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were added to a 1 gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70°C for 6 hours. This kneaded product is poured into 3,000 parts of warm water, heated to 70°C and stirred for 1 hour with a high-speed mixer to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C for one day and night. and pulverized to obtain a micronized green pigment (E-6).

화학식(20)Chemical formula (20)

[화 11][Tuesday 11]

(미세화한 황색 안료(E-7))(Micronised yellow pigment (E-7))

C.I. Pigment Yellow 150을 100부, 염화나트륨 700부, 및 디에틸렌글리콜 180부를 스테인리스제 1갤런 니더(Inoue Seisakusho Co., Ltd. 제조)에 투입하고, 80℃에서 6시간 혼련했다. 이 혼합물을 온수 2,000부에 투입하고, 80℃로 가열하면서 하이스피드 믹서로 1시간 교반하여 슬러리상으로 하고, 여과, 수세를 반복하여 염화나트륨 및 디에틸렌글리콜을 제거한 후, 80℃에서 일주야 건조하고, 분쇄함으로써 미세화한 황색 안료(E-7)를 얻었다.C.I. 100 parts of Pigment Yellow 150, 700 parts of sodium chloride, and 180 parts of diethylene glycol were added to a 1 gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. This mixture was poured into 2,000 parts of warm water, heated to 80°C and stirred with a high-speed mixer for 1 hour to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C for one day. , a finely divided yellow pigment (E-7) was obtained by grinding.

(미세화한 황색 안료(E-8))(Micronised yellow pigment (E-8))

C.I. Pigment Yellow 139(Clariant Ltd. 제조 「Novoperm Yellow P-M3R」) 100부, 분쇄한 염화나트륨 800부, 및 디에틸렌글리콜 100부를 스테인리스제 1갤런 니더(Inoue Seisakusho Co., Ltd. 제조)에 투입하고, 70℃에서 12시간 혼련했다. 이 혼합물을 온수 3,000부에 투입하고, 약 70℃로 가열하면서 하이스피드 믹서로 약 1시간 교반하여 슬러리상으로 하고, 여과, 수세를 반복하여 염화나트륨 및 디에틸렌글리콜을 제거한 후, 80℃에서 일주야 건조하고, 분쇄함으로써 미세화한 황색 안료(E-8)를 얻었다.C.I. 100 parts of Pigment Yellow 139 (“Novoperm Yellow P-M3R” manufactured by Clariant Ltd.), 800 parts of pulverized sodium chloride, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), It was kneaded at 70°C for 12 hours. This mixture was poured into 3,000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and kept at 80°C for one week. By drying and pulverizing, a finely divided yellow pigment (E-8) was obtained.

(미세화한 황색 안료(E-9))(Micronised yellow pigment (E-9))

C.I. Pigment Yellow 185(BASF Japan Ltd. 제조 「Palitol Yellow D1155」) 100부, 분쇄한 염화나트륨 700부, 및 디에틸렌글리콜 180부를 스테인리스제 1갤런 니더(Inoue Seisakusho Co., Ltd. 제조)에 투입하고, 80℃에서 6시간 혼련했다. 다음으로 이 혼련물을 8리터의 온수에 투입하고, 80℃로 가열하면서 하이스피드 믹서로 2시간 교반하여 슬러리상으로 하고, 여과, 수세를 반복하여 염화나트륨 및 디에틸렌글리콜을 제거한 후, 85℃에서 일주야 건조하고, 분쇄함으로써 미세화한 황색 안료(E-9)를 얻었다.C.I. 100 parts of Pigment Yellow 185 (“Palitol Yellow D1155” manufactured by BASF Japan Ltd.), 700 parts of pulverized sodium chloride, and 180 parts of diethylene glycol were added to a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), and 80 parts were added. It was kneaded for 6 hours at ℃. Next, pour this kneaded product into 8 liters of hot water, heat it to 80°C and stir for 2 hours with a high-speed mixer to form a slurry, repeat filtering and washing with water to remove sodium chloride and diethylene glycol, and then mix at 85°C. It was dried for a day and a night and pulverized to obtain a finely divided yellow pigment (E-9).

(미세화한 황색 안료(E-10)(Micronised yellow pigment (E-10)

일본 특허공개 2012-226110호 공보의 실시예에 따라서, 하기 화학식(21)의 황색 안료(E-10)를 얻었다. 황색 안료(E-10) 100부, 분쇄한 염화나트륨 700부, 및 디에틸렌글리콜 180부를 스테인리스제 1갤런 니더(Inoue Seisakusho Co., Ltd. 제조)에 투입하고, 80℃에서 6시간 혼련했다. 다음으로 이 혼련물을 8리터의 온수에 투입하고, 80℃로 가열하면서 하이스피드 믹서로 2시간 교반하여 슬러리상으로 하고, 여과, 수세를 반복하여 염화나트륨 및 디에틸렌글리콜을 제거한 후, 85℃에서 일주야 건조하고, 분쇄함으로써 미세화한 황색 안료(E-10)를 얻었다.According to the examples of Japanese Patent Application Laid-Open No. 2012-226110, a yellow pigment (E-10) of the following formula (21) was obtained. 100 parts of yellow pigment (E-10), 700 parts of pulverized sodium chloride, and 180 parts of diethylene glycol were added to a 1 gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. Next, pour this kneaded product into 8 liters of hot water, heat it to 80°C and stir for 2 hours with a high-speed mixer to form a slurry, repeat filtering and washing with water to remove sodium chloride and diethylene glycol, and then mix at 85°C. It was dried for a day and a night and pulverized to obtain a finely divided yellow pigment (E-10).

화학식(21)Chemical formula (21)

[화 12][Tuesday 12]

상기 미세화된 안료의 평균 일차 입자경은, 5 ∼ 120㎚의 범위 내였다.The average primary particle diameter of the micronized pigment was within the range of 5 to 120 nm.

(염료(E-11))(Dye(E-11))

하기의 순서로 C.I. Acid Red 52와 측쇄에 양이온성기를 갖는 수지 1로 이루어지는 조염 화합물인 염료(E-11)를 제조했다.C.I. in the following order. Dye (E-11), a salt-forming compound consisting of Acid Red 52 and Resin 1 having a cationic group in the side chain, was prepared.

온도계, 교반기, 증류관, 냉각기를 구비한 4구 세퍼러블 플라스크에, 메틸에틸케톤 67.3부를 투입하고 질소 기류 하에서 75℃로 승온했다. 별도로, 메틸메타크릴레이트 34.0부, n-부틸메타크릴레이트 28.0부, 2-에틸헥실메타크릴레이트 28.0부, 디메틸아미노에틸메타크릴레이트 10.0부, 2,2'-아조비스(2,4-디메틸발레로니트릴) 6.5부, 및 메틸에틸케톤 25.1부를 균일하게 한 후, 적하 로트에 투입하고, 4구 세퍼러블 플라스크에 부착하고, 2시간 걸쳐 적하했다. 적하 종료 2시간 후, 불휘발분으로부터 중합 수율이 98％ 이상이며, 중량 평균 분자량(Mw)이 6,830인 것을 확인하고, 50℃로 냉각했다. 여기에, 염화메틸 3.2부, 에탄올 22.0부를 추가하고, 50℃에서 2시간 반응시킨 후, 1시간 걸쳐 80℃까지 가온하고, 2시간 더 반응시켰다. 이와 같이 하여 수지 성분이 47질량％인 암모늄기를 갖는 측쇄에 양이온성기를 갖는 수지 1을 얻었다. 얻어진 수지의 암모늄염가는 34㎎KOH／g이었다.67.3 parts of methyl ethyl ketone was added to a four-neck separable flask equipped with a thermometer, stirrer, distillation tube, and condenser, and the temperature was raised to 75°C under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2'-azobis(2,4-dimethyl After equalizing 6.5 parts of valeronitrile and 25.1 parts of methyl ethyl ketone, they were added to a dropping lot, attached to a four-necked separable flask, and added dropwise over 2 hours. Two hours after the end of dropping, it was confirmed that the polymerization yield was 98% or more and the weight average molecular weight (Mw) was 6,830 based on the non-volatile content, and the mixture was cooled to 50°C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added and reacted at 50°C for 2 hours, then heated to 80°C over 1 hour and allowed to react for an additional 2 hours. In this way, Resin 1 having a cationic group in the side chain having an ammonium group with a resin component of 47% by mass was obtained. The ammonium salt value of the obtained resin was 34 mgKOH/g.

다음으로, 물 2,000부에 불휘발분 환산으로 30부의 측쇄에 양이온성기를 갖는 수지 1을 첨가하고, 충분히 교반 혼합을 행한 후, 60℃로 가열했다. 한편, 90부의 물에 10부의 C.I. Acid Red 52를 용해시킨 수용액을 조제하고, 이전의 수지 용액에 조금씩 적하했다. 적하 후, 60℃에서 120분간 교반하고, 충분히 반응을 행했다. 반응의 종점 확인으로서는 여과지에 반응액을 적하하여, 번짐이 없어진 곳을 종점으로 하여, 조염 화합물이 얻어진 것으로 판단했다. 교반하면서 실온까지 방랭(放冷)한 후, 흡인 여과를 행하고, 수세 후, 여과지 상에 남은 조염 화합물을 건조기에서 수분을 제거하여 건조하고, 32부의 C.I. Acid Red 52와 측쇄에 양이온성기를 갖는 수지 1과의 조염 화합물인 염료(E-11)를 얻었다. 이때 염료(E-11) 중의 C.I. Acid Red 52에서 유래된 성분의 함유량은 25질량％였다.Next, 30 parts of Resin 1 having a cationic group in the side chain (in terms of non-volatile content) was added to 2,000 parts of water, and after sufficient stirring and mixing, it was heated to 60°C. Meanwhile, 10 parts C.I. to 90 parts water. An aqueous solution in which Acid Red 52 was dissolved was prepared, and it was added dropwise little by little to the previous resin solution. After dropwise addition, the mixture was stirred at 60°C for 120 minutes to sufficiently react. To confirm the end point of the reaction, the reaction solution was added dropwise to the filter paper, and the point where bleeding disappeared was set as the end point, and it was judged that the salt-forming compound was obtained. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture in a dryer, and 32 parts of C.I. A dye (E-11), a salt-forming compound of Acid Red 52 and Resin 1 having a cationic group in the side chain, was obtained. At this time, C.I in the dye (E-11). The content of components derived from Acid Red 52 was 25% by mass.

<알칼리 가용성 수지(A)의 제조><Manufacture of alkali-soluble resin (A)>

(알칼리 가용성 수지(A1-1) 용액)(Alkali-soluble resin (A1-1) solution)

교반기, 온도계, 환류 냉각관, 적하 로트 및 질소 도입관을 구비한 플라스크에, 프로필렌글리콜모노메틸에테르아세테이트(이하, PGMAc) 333부를 도입하고, 플라스크 내 분위기를 공기로부터 질소로 한 후, 100℃로 승온 후, 벤질메타크릴레이트 70.5부(0.40몰), 글리시딜메타크릴레이트 71.1부(0.50몰), 디시클로펜타닐메타크릴레이트 22.0부(0.10몰) 및, PGMAc 164부로 이루어지는 혼합물에 아조비스이소부티로니트릴 3.6부를 첨가한 용액을 적하 로트로부터 2시간 걸쳐 플라스크에 적하하고, 추가로 100℃에서 5시간 계속 교반했다. 다음으로, 플라스크 내 분위기를 질소로부터 공기로 하고, 메타크릴산 43.0부[0.5몰, (본 반응에 이용한 글리시딜메타크릴레이트의 글리시딜기에 대하여 100몰％)], 트리스디메틸아미노메틸페놀 0.9부 및 하이드로퀴논 0.145부를 플라스크 내에 투입하고, 110℃에서 6시간 반응을 계속하여 불휘발분 산가가 1㎎KOH／g이 된 곳에서 반응을 종료했다. 다음으로, 테트라히드로프탈 무수프탈산 60.9부(0.40몰), 트리에틸아민 0.8부를 더하고, 120℃에서 3.5시간 반응시켜 산가 80㎎KOH／g의 감광성의 수지 용액을 얻었다. 실온까지 냉각한 후, 감광성의 수지 용액 약 2부를 샘플링하여 180℃, 20분 가열 건조하여 불휘발분을 측정하고, 먼저 합성한 감광성의 수지 용액에 불휘발분이 20질량％가 되도록 PGMAc를 첨가하여, 지환식 탄화수소 함유 단량체 단위(a1), 및 카르복시기 함유 단량체 단위(a2)를 함유하는 감광성의 알칼리 가용성 수지(A1-1) 용액을 조제했다. 중량 평균 분자량(Mw)은 12,000이었다.333 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) was introduced into a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introduction tube, the atmosphere in the flask was changed from air to nitrogen, and then the temperature was adjusted to 100°C. After raising the temperature, azobisiso is added to a mixture consisting of 70.5 parts (0.40 mol) of benzyl methacrylate, 71.1 parts (0.50 mol) of glycidyl methacrylate, 22.0 parts (0.10 mol) of dicyclopentanyl methacrylate, and 164 parts of PGMAc. A solution containing 3.6 parts of butyronitrile was added dropwise to the flask over 2 hours from the dropping funnel, and stirring was continued at 100°C for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, 43.0 parts of methacrylic acid (0.5 mol, (100 mol% based on the glycidyl group of the glycidyl methacrylate used in this reaction)), and trisdimethylaminomethylphenol. 0.9 part and 0.145 part of hydroquinone were added into the flask, reaction was continued at 110°C for 6 hours, and the reaction was terminated when the non-volatile acid value reached 1 mgKOH/g. Next, 60.9 parts (0.40 mol) of tetrahydrophthalic anhydride and 0.8 part of triethylamine were added, and the mixture was reacted at 120°C for 3.5 hours to obtain a photosensitive resin solution with an acid value of 80 mgKOH/g. After cooling to room temperature, approximately 2 parts of the photosensitive resin solution were sampled, heated and dried at 180°C for 20 minutes to measure the non-volatile content, and PGMAc was added to the previously synthesized photosensitive resin solution so that the non-volatile content was 20% by mass. A solution of a photosensitive alkali-soluble resin (A1-1) containing an alicyclic hydrocarbon-containing monomer unit (a1) and a carboxyl group-containing monomer unit (a2) was prepared. The weight average molecular weight (Mw) was 12,000.

(알칼리 가용성 수지(A1-2) 용액)(Alkali soluble resin (A1-2) solution)

교반기, 온도계, 환류 냉각관, 적하 로트 및 질소 도입관을 구비한 플라스크에, PGMAc 182부를 도입하고, 플라스크 내 분위기를 공기로부터 질소로 한 후, 100℃로 승온 후, 벤질메타크릴레이트 70.5부(0.40몰), 메타크릴산 43.0부(0.5몰), 디시클로펜타닐메타크릴레이트 22.0부(0.10몰) 및 PGMAc 136부로 이루어지는 혼합물에 아조비스이소부티로니트릴 3.6부를 첨가한 용액을 적하 로트로부터 2시간 걸쳐 플라스크에 적하하고, 추가로 100℃에서 5시간 계속 교반했다. 다음으로, 플라스크 내 분위기를 질소로부터 공기로 하고, 글리시딜메타크릴레이트 35.5부[0.25몰, (본 반응에 이용한 메타크릴산의 카르복시기에 대하여 50몰％)], 트리스디메틸아미노메틸페놀 0.9부 및 하이드로퀴논 0.145부를 플라스크 내에 투입하고, 110℃에서 6시간 반응을 계속하여, 산가가 79㎎KOH／g인 감광성의 수지 용액을 얻었다. 실온까지 냉각한 후, 감광성의 수지 용액 약 2부를 샘플링하여 180℃, 20분 가열 건조하여 불휘발분을 측정하고, 먼저 합성한 감광성의 투명 수지 용액에 불휘발분이 20질량％가 되도록 PGMAc를 첨가하여, 지환식 탄화수소 함유 단량체 단위(a1), 및 카르복시기 함유 단량체 단위(a2)를 함유하는 감광성의 알칼리 가용성 수지(A1-2) 용액을 조제했다. 중량 평균 분자량(Mw)은 13,000이었다.182 parts of PGMAc were introduced into a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen introduction tube, the atmosphere in the flask was changed from air to nitrogen, and then the temperature was raised to 100°C, and then 70.5 parts of benzyl methacrylate ( 0.40 mol), 43.0 parts (0.5 mol) of methacrylic acid, 22.0 parts (0.10 mol) of dicyclopentanyl methacrylate, and 136 parts of PGMAc. A solution of 3.6 parts of azobisisobutyronitrile was added for 2 hours from the dropping lot. It was added dropwise to the flask, and stirring was continued at 100°C for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, 35.5 parts of glycidyl methacrylate (0.25 mol, (50 mol% based on the carboxyl group of methacrylic acid used in this reaction)), and 0.9 parts of trisdimethylaminomethylphenol. and 0.145 parts of hydroquinone were added into the flask, reaction was continued at 110°C for 6 hours, and a photosensitive resin solution with an acid value of 79 mgKOH/g was obtained. After cooling to room temperature, approximately 2 parts of the photosensitive resin solution were sampled and dried at 180°C for 20 minutes to measure the non-volatile content. PGMAc was added to the previously synthesized photosensitive transparent resin solution so that the non-volatile content was 20% by mass. A photosensitive alkali-soluble resin (A1-2) solution containing an alicyclic hydrocarbon-containing monomer unit (a1) and a carboxyl group-containing monomer unit (a2) was prepared. The weight average molecular weight (Mw) was 13,000.

(알칼리 가용성 수지(A2-1) 용액)(Alkali soluble resin (A2-1) solution)

세퍼러블 4구 플라스크에 온도계, 냉각관, 질소 가스 도입관, 적하관 및 교반 장치를 부착한 반응 용기에 시클로헥산온 196부를 투입하고, 80℃로 승온하고, 반응 용기 내를 질소 치환한 후, 적하관으로부터, n-부틸메타크릴레이트 37.2부, 2-히드록시에틸메타크릴레이트 12.9부, 메타크릴산 12.0부, 파라쿠밀페놀에틸렌옥사이드 변성 아크릴레이트(TOAGOSEI CO., LTD. 제조 「Aronix M110」) 20.7부, 2,2'-아조비스이소부티로니트릴 1.1부의 혼합물을 2시간 걸쳐 적하했다. 적하 종료 후, 추가로 3시간 반응을 계속하여, 아크릴 수지의 용액을 얻었다. 실온까지 냉각한 후, 수지 용액 약 2부를 샘플링하여 180℃, 20분간 가열 건조하여 불휘발분을 측정하고, 먼저 합성한 수지 용액에 불휘발분이 20질량％가 되도록 PGMAc를 첨가하여, 비감광성의 알칼리 가용성 수지(A2-1) 용액을 조제했다. 중량 평균 분자량(Mw)은 26,000이었다.196 parts of cyclohexanone was added to a reaction vessel equipped with a thermometer, cooling pipe, nitrogen gas introduction pipe, dropping pipe, and stirring device in a separable four-necked flask, the temperature was raised to 80°C, and the inside of the reaction vessel was purged with nitrogen. From the dropping tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenolethylene oxide modified acrylate (“Aronix M110” manufactured by TOAGOSEI CO., LTD. ) A mixture of 20.7 parts and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for an additional 3 hours to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried at 180°C for 20 minutes to measure the non-volatile content. PGMAc was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass, and a non-photosensitive alkali was added to the resin solution. A soluble resin (A2-1) solution was prepared. The weight average molecular weight (Mw) was 26,000.

(알칼리 가용성 수지(A2-2) 용액)(Alkali soluble resin (A2-2) solution)

세퍼러블 4구 플라스크에 온도계, 냉각관, 질소 가스 도입관, 적하관 및 교반 장치를 부착한 반응 용기에 시클로헥산온 207부를 투입하고, 80℃로 승온하고, 반응 용기 내를 질소 치환한 후, 적하관으로부터, 메타크릴산 20부, 벤질메타크릴레이트 20부, 파라쿠밀페놀에틸렌옥사이드 변성 아크릴레이트(TOAGOSEI CO., LTD. 제조 M110) 20부, 메타크릴산메틸 25부, 2-히드록시에틸메타크릴레이트 8.5부, 및 2,2'-아조비스이소부티로니트릴 1.33부의 혼합물을 2시간 걸쳐 적하했다. 적하 종료 후, 추가로 3시간 반응을 계속하여, 공중합체 수지 용액을 얻었다. 다음으로 얻어진 공중합체 용액 전량에 대하여, 질소 가스를 정지하고 건조 공기를 1시간 주입하면서 교반한 후에, 실온까지 냉각한 후, 2-메타크릴로일옥시에틸이소시아네이트(Showa Denko K.K. 제조 Karenz MOI) 6.5부, 라우린산디부틸주석 0.08부, 시클로헥산온 26부의 혼합물을 70℃에서 3시간 걸쳐 적하했다. 적하 종료 후, 추가로 1시간 반응을 계속하고, 수지의 용액을 얻은 불휘발분이 20질량％가 되도록 시클로헥산온을 첨가하여, 감광성의 알칼리 가용성 수지(A2-2) 용액을 조제했다. 중량 평균 분자량(Mw)은 18,000이며, 불휘발분 산가가 130㎎KOH／g이었다.207 parts of cyclohexanone was added to a reaction vessel equipped with a thermometer, cooling pipe, nitrogen gas introduction pipe, dropping pipe, and stirring device in a separable four-necked flask, the temperature was raised to 80°C, and the inside of the reaction vessel was purged with nitrogen. From the dropping tube, 20 parts of methacrylic acid, 20 parts of benzyl methacrylate, 20 parts of paracumylphenolethylene oxide modified acrylate (M110 manufactured by TOAGOSEI CO., LTD.), 25 parts of methyl methacrylate, and 2-hydroxyethyl. A mixture of 8.5 parts of methacrylate and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for an additional 3 hours to obtain a copolymer resin solution. Next, the entire amount of the obtained copolymer solution was stirred while stopping nitrogen gas and injecting dry air for 1 hour, then cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz MOI, manufactured by Showa Denko K.K.) 6.5 A mixture of 1 part, 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70°C over 3 hours. After completion of the dropwise addition, the reaction was continued for an additional hour, cyclohexanone was added so that the non-volatile content of the resin solution was 20% by mass, and a photosensitive alkali-soluble resin (A2-2) solution was prepared. The weight average molecular weight (Mw) was 18,000, and the non-volatile acid value was 130 mgKOH/g.

<분산 수지(G)의 제조><Manufacture of dispersion resin (G)>

(분산 수지(G-1) 용액)(Dispersion Resin (G-1) Solution)

가스 도입관, 온도, 콘덴서, 교반기를 구비한 반응 용기에, 메타크릴산 10부, 메틸메타크릴레이트 100부, i-부틸메타크릴레이트 70부, 벤질메타크릴레이트 20부, PGMAc 50부를 투입하고, 질소 가스로 치환했다. 반응 용기 내를 50℃로 가열 교반하고, 3-메르캅토-1,2-프로판디올 12부를 첨가했다. 90℃로 승온하고, 2,2'-아조비스이소부티로니트릴 0.1부를 PGMAc 90부에 더한 용액을 첨가하면서 7시간 반응했다. 불휘발분 측정에 의해 95％가 반응한 것을 확인했다. 피로멜리트산무수물 19부, PGMAc 50부, 시클로헥산온 50부, 촉매로서 1,8-디아자비시클로-[5.4.0]-7-운데센 0.4부를 추가하고, 100℃에서 7시간 반응시켰다. 산가의 측정으로 98％ 이상의 산무수물이 하프 에스테르화하고 있는 것을 확인하여 반응을 종료하고, 불휘발분 측정으로 불휘발분 30％가 되도록 PGMAc를 더하여 희석하고, 산가 70㎎KOH／g, 중량 평균 분자량 8,500의 분산 수지(G-1) 용액을 얻었다.Into a reaction vessel equipped with a gas introduction tube, temperature, condenser, and stirrer, 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc were added. , was replaced with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50°C, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and reaction was conducted for 7 hours while adding a solution of 0.1 part of 2,2'-azobisisobutyronitrile to 90 parts of PGMAc. It was confirmed that 95% had reacted by measuring non-volatile matter. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and reacted at 100°C for 7 hours. By measuring the acid value, it was confirmed that more than 98% of the acid anhydride was half-esterified, and the reaction was terminated. By measuring the non-volatile content, it was diluted by adding PGMAc to a non-volatile content of 30%. The acid value was 70 mg KOH/g, and the weight average molecular weight was 8,500. A dispersion resin (G-1) solution was obtained.

(분산 수지(G-2) 용액)(Dispersion Resin (G-2) Solution)

가스 도입관, 온도계, 콘덴서, 교반기를 구비한 반응 용기에, 1-티오글리세롤 108부, 피로멜리트산무수물 174부, PGMAc 650부, 촉매로서 모노부틸주석옥사이드 0.2부를 투입하고, 질소 가스로 치환한 후, 120℃에서 5시간 반응시켰다(제1 공정). 산가의 측정으로 95％ 이상의 산무수물이 하프 에스테르화하고 있는 것을 확인했다. 다음으로, 제1 공정에서 얻어진 화합물을 불휘발분 환산으로 160부, 2-히드록시프로필메타크릴레이트 200부, 에틸아크릴레이트 200부, t-부틸아크릴레이트 150부, 2-메톡시에틸아크릴레이트 200부, 메틸아크릴레이트 200부, 메타크릴산 50부, PGMAc 663부를 투입하고, 반응 용기 내를 80℃로 가열하여, 2,2'-아조비스(2,4-디메틸발레로니트릴) 1.2부를 첨가하고, 12시간 반응했다(제2 공정). 불휘발분 측정에 의해 95％가 반응한 것을 확인했다. 마지막으로, 제2 공정에서 얻어진 화합물의 불휘발분 50％의 PGMAc 희석 용액을 500부, 2-메타크릴로일옥시에틸이소시아네이트(MOi) 27.0부, 히드로퀴논 0.1부를 투입하고, IR로 이소시아네이트기에 기초하는 2270㎝-1의 피크의 소실을 확인할 때까지 반응을 행했다(제3 공정). 피크 소실의 확인 후, 반응 용액을 냉각하여, PGMAc로 불휘발분을 조정함으로써 불휘발분 30％의 분산 수지(G-2) 용액을 얻었다. 얻어진 분산 수지(G-2)의 산가는 68㎎KOH／g, 불포화 이중 결합 당량은 1,593, 중량 평균 분자량은 13,000이었다.Into a reaction vessel equipped with a gas introduction tube, thermometer, condenser, and stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyl tin oxide as a catalyst were added, and the reaction mixture was replaced with nitrogen gas. Afterwards, reaction was performed at 120°C for 5 hours (first step). By measuring the acid value, it was confirmed that more than 95% of the acid anhydride was half-esterified. Next, the compound obtained in the first step was divided into 160 parts in terms of non-volatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, and 200 parts of 2-methoxyethyl acrylate. 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc were added, the inside of the reaction vessel was heated to 80°C, and 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) was added. and reacted for 12 hours (second process). It was confirmed that 95% had reacted by measuring non-volatile matter. Finally, 500 parts of a diluted solution of PGMAc containing 50% of the non-volatile content of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOi), and 0.1 part of hydroquinone were added, and 2270 based on the isocyanate group was added by IR. The reaction was performed until disappearance of the peak at cm -1 was confirmed (third process). After confirmation of disappearance of the peak, the reaction solution was cooled and the non-volatile content was adjusted with PGMAc to obtain a dispersion resin (G-2) solution with a non-volatile content of 30%. The acid value of the obtained dispersion resin (G-2) was 68 mgKOH/g, the unsaturated double bond equivalent was 1,593, and the weight average molecular weight was 13,000.

(분산 수지(G-3) 용액)(Dispersion Resin (G-3) Solution)

가스 도입관, 콘덴서, 교반 날개, 및 온도계를 구비한 반응 장치에, 메틸메타크릴레이트 30부, n-부틸메타크릴레이트 30부, 히드록시에틸메타크릴레이트 20부, 테트라메틸에틸렌디아민 13.2부를 투입하고, 질소를 흘리면서 50℃에서 1시간교반하고, 계(系) 내를 질소 치환했다. 다음으로, 브로모이소부티르산에틸 9.3부, 염화제1구리 5.6부, PGMAc 133부를 투입하고, 질소 기류 하에서, 110℃까지 승온하여 제1 블록(B 블록)의 중합을 개시했다. 4시간 중합 후, 중합 용액을 샘플링하여 불휘발분 측정을 행하고, 불휘발분으로부터 환산하여 중합 전화율이 98％ 이상인 것을 확인했다.Into a reaction device equipped with a gas introduction tube, condenser, stirring blade, and thermometer, 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine were added. Then, the mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were added, and the temperature was raised to 110°C under a nitrogen stream to initiate polymerization of the first block (B block). After polymerization for 4 hours, the polymerization solution was sampled, the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more by converting it from the non-volatile content.

다음으로, 이 반응 장치에, PGMAc 61부, 제2 블록(A 블록) 모노머로서 1,2,2,6,6-펜타메틸피페리딜메타크릴레이트 20부(Hitachi Chemical Company, Ltd. 제조, FANCRYL FA-711MM)를 투입하고, 110℃에서 질소 분위기 하를 유지한 채로 교반하고, 반응을 계속했다. 1,2,2,6,6-펜타메틸피페리딜메타크릴레이트 투입으로부터 2시간 후, 중합 용액을 샘플링하여 불휘발분 측정을 행하고, 불휘발분으로부터 환산하여 제2 블록(A 블록)의 중합 전화율이 98％ 이상인 것을 확인하고, 반응 용액을 실온까지 냉각하여 중합을 정지했다. 불휘발분 측정으로 불휘발분 30％가 되도록 PGMAc를 더하여 희석하고, 불휘발분당의 아민가가 57㎎KOH／g, 수평균 분자량 4,500(Mn)인 분산 수지(G-3) 용액을 얻었다.Next, to this reaction apparatus, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (manufactured by Hitachi Chemical Company, Ltd.) as second block (A block) monomers were added. FANCRYL FA-711MM) was added, stirred while maintaining a nitrogen atmosphere at 110°C, and the reaction was continued. 2 hours after adding 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled to measure the non-volatile content, and converted from the non-volatile content to obtain the polymerization conversion rate of the second block (A block). After confirming that this was 98% or more, the reaction solution was cooled to room temperature and polymerization was stopped. By measuring the non-volatile content, PGMAc was added and diluted so that the non-volatile content was 30%, and a dispersion resin (G-3) solution with an amine value per non-volatile content of 57 mg KOH/g and a number average molecular weight of 4,500 (Mn) was obtained.

(분산 수지(G-4) 용액)(Dispersion Resin (G-4) Solution)

냉각관, 첨가용 로트, 질소용 인렛, 기계적 교반기, 디지털 온도계를 구비한 500mL 환저(丸底) 4구 세퍼러블 플라스크에, 테트라히드로퓨란(THF) 250질량부 및 개시제의 디메틸케텐메틸트리메틸실릴아세탈 5.81질량부를, 첨가용 로트를 통해 더하고, 충분히 질소 치환을 행했다. 촉매의 테트라부틸암모늄m-클로로벤조에이트의 1몰／L 아세토니트릴 용액 0.5질량부를, 시린지를 이용하여 주입하고, 친용제성을 갖는 블록용 모노머의 메타크릴산2-히드록시에틸 19.7질량부, 메타크릴산2-에틸헥실 7.5질량부, 메타크릴산n-부틸 12.9질량부, 메타크릴산벤질 10.7질량부, 메타크릴산메틸 30.9질량부를, 첨가용 로트를 이용하여 60분 걸쳐 적하했다. 반응 플라스크를 빙욕(氷浴)에서 냉각함으로써, 온도를 40℃ 미만으로 유지했다. 1시간 후, 색재 흡착 기능 블록용 모노머인 디메틸아미노프로필메타크릴아미드 18.3질량부를 20분 걸쳐 적하했다. 1시간 반응시킨 후, 메탄올 1질량부를 더하여 반응을 정지시켰다. 얻어진 블록 공중합체 THF 용액은 헥산 중에서 재침전시키고, 여과, 진공 건조에 의해 정제를 행했다.In a 500 mL round bottom four-neck separable flask equipped with a cooling tube, an addition lot, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, 250 parts by mass of tetrahydrofuran (THF) and dimethylketenemethyltrimethylsilyl acetal as an initiator. 5.81 parts by mass was added through an addition lot, and nitrogen substitution was sufficiently performed. 0.5 parts by mass of a 1 mol/L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst was injected using a syringe, and 19.7 parts by mass of 2-hydroxyethyl methacrylate as a solvent-philic blocking monomer and meta 7.5 parts by mass of 2-ethylhexyl acrylate, 12.9 parts by mass of n-butyl methacrylate, 10.7 parts by mass of benzyl methacrylate, and 30.9 parts by mass of methyl methacrylate were added dropwise over 60 minutes using an addition lot. The temperature was maintained below 40°C by cooling the reaction flask in an ice bath. After 1 hour, 18.3 parts by mass of dimethylaminopropyl methacrylamide, which is a monomer for the color material adsorption functional block, was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to stop the reaction. The obtained block copolymer THF solution was reprecipitated in hexane and purified by filtration and vacuum drying.

계속해서, 100mL 환저 플라스크 중에서 PGMAc 35질량부에, 얻어진 블록 공중합체 15.0질량부를 용해시켜, 염 형성 성분인 페닐포스핀산 1.1질량부(디메틸아미노프로필메타크릴아미드에 대해, 0.5몰 등량) 더하고, 반응 온도 30℃에서 20시간 교반하고, PGMAc를 첨가하여 조정하고, 불휘발분 30％의 분산 수지(G-4) 용액을 얻었다.Subsequently, 15.0 parts by mass of the obtained block copolymer were dissolved in 35 parts by mass of PGMAc in a 100 mL round bottom flask, 1.1 parts by mass of phenylphosphinic acid (relative to dimethylaminopropyl methacrylamide, 0.5 molar equivalent) as a salt forming component was added, and reaction was carried out. The mixture was stirred at a temperature of 30°C for 20 hours, adjusted by adding PGMAc, and a dispersion resin (G-4) solution with a non-volatile content of 30% was obtained.

<중합성 화합물(B)의 제조><Preparation of polymerizable compound (B)>

(우레탄 결합을 갖는 중합성 화합물(B3-1) 용액) (Polymerizable compound (B3-1) solution having a urethane bond)

교반기, 환류 냉각관, 질소 도입관, 온도계, 적하관을 구비한 5구 플라스크에, 디펜타에리트리톨펜타아크릴레이트 400부, PGMAc 100부, N,N-디메틸벤질아민 0.5부를 투입하고, 70℃로 승온하고, 적하관으로부터 톨루엔디이소시아네이트 66부와 PGMAc 66부의 혼합물을 2시간 걸쳐 적하했다. 적하 후, 50 ∼ 70℃의 온도에서 8시간 반응시키고, IR에 의해 2180㎝-1의 이소시아네이트의 흡수의 소실을 확인했다. 그 다음에, 메르캅토아세트산 35부, 4-메톡시페놀 0.6부를 투입하고, 50 ∼ 60℃의 온도에서 6시간 반응시켰다. 불휘발분이 50질량％가 되도록 조정하고, 우레탄 결합을 갖는 중합성 화합물(B3-1) 용액을 얻었다.400 parts of dipentaerythritolpentaacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine were added to a five-necked flask equipped with a stirrer, reflux condenser, nitrogen introduction tube, thermometer, and dropping tube, and incubated at 70°C. The temperature was raised to , and a mixture of 66 parts of toluene diisocyanate and 66 parts of PGMAc was added dropwise from a dropping tube over 2 hours. After dropwise addition, reaction was performed at a temperature of 50 to 70°C for 8 hours, and loss of absorption of isocyanate at 2180 cm -1 was confirmed by IR. Next, 35 parts of mercaptoacetic acid and 0.6 parts of 4-methoxyphenol were added, and reaction was performed at a temperature of 50 to 60°C for 6 hours. The non-volatile content was adjusted to 50% by mass, and a solution of the polymerizable compound (B3-1) having a urethane bond was obtained.

<분산체의 제조><Preparation of dispersion>

(분산체 1)(Dispersion 1)

하기의 원료를 균일해지도록 교반 혼합한 후, 직경 0.5㎜의 지르코니아 비드를 이용하여, EIGER MILL(Eiger Japan co., ltd. 제조 「미니 모델 M-250MKII」)로 3시간 분산한 후, 공경(孔徑) 1.0㎛의 필터로 여과하여, 분산체 1을 제작했다. 유기 용제(P-1)는, PGMAc이다.After stirring and mixing the following raw materials to uniformity, dispersing them for 3 hours using EIGER MILL (“Mini Model M-250MKII” manufactured by Eiger Japan co., Ltd.) using zirconia beads with a diameter of 0.5 mm, and then dispersing them using zirconia beads with a diameter of 0.5 mm ( Confucius) Dispersion 1 was produced by filtering with a 1.0 ㎛ filter. The organic solvent (P-1) is PGMAc.

미세화한 청색 안료(E-3): 9.05질량부Micronized blue pigment (E-3): 9.05 parts by mass

미세화한 자색 안료(E-4): 0.31질량부Micronized purple pigment (E-4): 0.31 parts by mass

염료(E-11): 4.16질량부Dye (E-11): 4.16 parts by mass

색소 유도체(F-1): 1.04질량부Pigment derivative (F-1): 1.04 parts by mass

분산 수지(G-1) 용액: 3.47질량부Dispersion resin (G-1) solution: 3.47 parts by mass

알칼리 가용성 수지(A2-1) 용액: 2.00질량부Alkali-soluble resin (A2-1) solution: 2.00 parts by mass

유기 용제(P-1): 79.97질량부Organic solvent (P-1): 79.97 parts by mass

색소 유도체(F-1): 하기 구조Pigment derivative (F-1): Structure below

[화 13][Tuesday 13]

pc는, 프탈로시아닌 골격을 나타낸다.pc represents the phthalocyanine skeleton.

표 1에 기재한 원료, 양을 바꾼 것 이외는, 분산체 1과 마찬가지로 분산체 2 ∼ 9를 작성했다.Dispersions 2 to 9 were prepared in the same manner as dispersion 1, except that the raw materials and amounts listed in Table 1 were changed.

[표 1][Table 1]

표 1의 색소 유도체(F-2): 하기 구조Pigment derivative (F-2) in Table 1: Structure below

[화 14][Tuesday 14]

표 1의 색소 유도체(F-3): 하기 구조Pigment derivative (F-3) in Table 1: Structure below

[화 15][Tuesday 15]

<감광성 조성물의 제조><Preparation of photosensitive composition>

[실시예 1][Example 1]

(감광성 조성물 1)(Photosensitive composition 1)

이하의 원료를 혼합, 교반하고, 공경 1.0㎛의 필터로 여과하여 감광성 착색 조성물 1을 얻었다.The following raw materials were mixed, stirred, and filtered through a filter with a pore diameter of 1.0 μm to obtain photosensitive coloring composition 1.

분산체 1: 28.85질량부Dispersion 1: 28.85 parts by mass

알칼리 가용성 수지(A1-1) 용액: 10.00질량부Alkali-soluble resin (A1-1) solution: 10.00 parts by mass

중합성 화합물(B1-1): 3.00질량부Polymerizable compound (B1-1): 3.00 parts by mass

중합성 화합물(B2-1): 3.00질량부Polymerizable compound (B2-1): 3.00 parts by mass

중합성 화합물(B3-1) 용액: 2.00질량부Polymerizable compound (B3-1) solution: 2.00 parts by mass

옥심계 광중합개시제(C1-1): 0.50질량부Oxime-based photopolymerization initiator (C1-1): 0.50 parts by mass

옥심계 광중합개시제(C2-6): 0.50질량부Oxime-based photopolymerization initiator (C2-6): 0.50 parts by mass

티올계 연쇄 이동제(D): 0.35질량부Thiol-based chain transfer agent (D): 0.35 parts by mass

열경화성 화합물(I): 0.50질량부 Thermosetting compound (I): 0.50 parts by mass

중합 금지제(J): 0.01질량부Polymerization inhibitor (J): 0.01 parts by mass

레벨링제(M): 1.00질량부Leveling agent (M): 1.00 parts by mass

유기 용제(P): 50.29질량부Organic solvent (P): 50.29 parts by mass

[실시예 2 ∼ 35, 비교예 1 ∼ 3][Examples 2 to 35, Comparative Examples 1 to 3]

(감광성 조성물 2 ∼ 38)(Photosensitive compositions 2 to 38)

실시예 1의 감광성 조성물 1을, 표 2-1 ∼ 표 2-4에 기재한 원료, 양으로 바꾼 것 이외는, 실시예 1과 마찬가지로 하여 감광성 조성물 2 ∼ 38을 제작했다.Photosensitive compositions 2 to 38 were produced in the same manner as in Example 1, except that photosensitive composition 1 of Example 1 was replaced with the raw materials and amounts shown in Tables 2-1 to 2-4.

[표 2-1][Table 2-1]

[표 2-2][Table 2-2]

[표 2-3][Table 2-3]

[표 2-4][Table 2-4]

표 2-1 ∼ 표 2-4에 기재한 각각의 원료에 대해서는, 이하와 같다.Each raw material listed in Tables 2-1 to 2-4 is as follows.

[중합성 화합물(B)][Polymerizable compound (B)]

(락톤 변성된 중합성 화합물(B1))(Lactone-modified polymerizable compound (B1))

B1-1: KAYARAD DPCA-30(Nippon Kayaku Co., Ltd. 제조)B1-1: KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)

(산기를 갖는 중합성 화합물(B2))(Polymerizable compound having an acid group (B2))

B2-1: Aronix M-520(TOAGOSEI CO., LTD. 제조)B2-1: Aronix M-520 (manufactured by TOAGOSEI CO., LTD.)

(그 외 중합성 화합물(B4))(Other polymerizable compounds (B4))

B4-1: Aronix M-420(TOAGOSEI CO., LTD. 제조)B4-1: Aronix M-420 (manufactured by TOAGOSEI CO., LTD.)

[광중합개시제(C)][Light polymerization initiator (C)]

(옥심계 광중합개시제(C1))(Oxime-based photopolymerization initiator (C1))

C1-1: 상술한 화학식(2)의 화합물 C1-1: Compound of formula (2) described above

C1-2: 상술한 화학식(3)의 화합물 C1-2: Compound of formula (3) described above

C1-3: 상술한 화학식(4)의 화합물 C1-3: Compound of formula (4) described above

C1-4: 상술한 화학식(5)의 화합물 C1-4: Compound of formula (5) described above

C1-5: 상술한 화학식(6)의 화합물 C1-5: Compound of formula (6) described above

C1-6: 상술한 화학식(7)의 화합물 C1-6: Compound of formula (7) described above

(옥심계 광중합개시제(C2))(Oxime-based photopolymerization initiator (C2))

C2-1: 상술한 화학식(8)의 화합물 C2-1: Compound of formula (8) described above

C2-2: 상술한 화학식(9)의 화합물 C2-2: Compound of formula (9) described above

C2-3: 상술한 화학식(10)의 화합물 C2-3: Compound of formula (10) described above

C2-4: 상술한 화학식(11)의 화합물 C2-4: Compound of formula (11) described above

C2-5: 상술한 화학식(12)의 화합물 C2-5: Compound of formula (12) described above

C2-6: 상술한 화학식(13)의 화합물 C2-6: Compound of formula (13) described above

C2-7: 상술한 화학식(14)의 화합물 C2-7: Compound of formula (14) described above

C2-8: 상술한 화학식(15)의 화합물 C2-8: Compound of formula (15) described above

C2-9: 상술한 화학식(16)의 화합물 C2-9: Compound of formula (16) described above

(그 외 광중합개시제(C3))(Other photopolymerization initiators (C3))

C3-1: Omnirad 907(IGM Resins Inc. 제조, 아세토페논계 광중합개시제)C3-1: Omnirad 907 (manufactured by IGM Resins Inc., acetophenone-based photopolymerization initiator)

[티올계 연쇄 이동제(D)][Thiol-based chain transfer agent (D)]

D-1: 트리메틸올프로판트리스(3-메르캅토부틸레이트)D-1: Trimethylolpropane tris (3-mercaptobutyrate)

D-2: 펜타에리트리톨테트라키스(3-메르캅토프로피오네이트)D-2: Pentaerythritol tetrakis (3-mercaptopropionate)

이상, (D-1) 및 (D-2)를 각각 동량(同量)으로 혼합하고, 티올계 연쇄 이동제(D)로 했다.Above, (D-1) and (D-2) were mixed in equal amounts to obtain a thiol-based chain transfer agent (D).

[증감제(H)][Sensitizer (H)]

H-1: KAYACURE DETX-S(Nippon Kayaku Co., Ltd. 제조, 티오크산톤계 화합물)H-1: KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd., thioxanthone-based compound)

H-2: CHEMARK DEABP(Chemark Chemical사 제조, 벤조페논계 화합물)H-2: CHEMARK DEABP (manufactured by Chemark Chemical, benzophenone-based compound)

이상, (H-1) 및 (H-2)를 각각 동량으로 혼합하고, 증감제(H)로 했다.Above, (H-1) and (H-2) were mixed in equal amounts to prepare the sensitizer (H).

[열경화성 화합물(I)][Thermosetting compound (I)]

(에폭시 화합물(I1))(Epoxy compound (I1))

I1-1: EHPE-3150(Daicel Corporation 제조)I1-1: EHPE-3150 (manufactured by Daicel Corporation)

I1-2: DENACOL EX611(Nagase Chemtex Corporation 제조)I1-2: DENACOL EX611 (manufactured by Nagase Chemtex Corporation)

I1-3: 이소시아누르산트리글리시딜I1-3: Triglycidyl isocyanurate

이상, (I1-1) ∼ (I1-3)을 각각 동량 혼합하고, 열경화성 화합물(I)로 했다.Above, equal amounts of (I1-1) to (I1-3) were mixed to obtain thermosetting compound (I).

[중합 금지제(J)][Polymerization inhibitor (J)]

J-1: 4-메틸카테콜J-1: 4-methylcatechol

J-2: 메틸히드로퀴논J-2: Methylhydroquinone

J-3: t-부틸히드로퀴논J-3: t-butylhydroquinone

이상, (J-1) ∼ (J-3)을 각각 동량으로 혼합하고, 중합 금지제(J)로 했다.Above, (J-1) to (J-3) were mixed in equal amounts to prepare the polymerization inhibitor (J).

[레벨링제(M)][Leveling Agent (M)]

M-1: BYK-330(BYK-Chemie Inc. 제조)M-1: BYK-330 (manufactured by BYK-Chemie Inc.)

M-2: MEGAFACE F-551(DIC Corporation 제조)M-2: MEGAFACE F-551 (manufactured by DIC Corporation)

이상, (M-1) 및 (M-2)를 각각 1부 혼합하고, PGMAc 98부에 용해시킨 혼합 용액을 레벨링제(M)로 했다.As mentioned above, 1 part each of (M-1) and (M-2) were mixed, and the mixed solution dissolved in 98 parts of PGMAc was used as the leveling agent (M).

[유기 용제(P)][Organic solvent (P)]

P-1: 프로필렌글리콜모노메틸에테르아세테이트 30부P-1: 30 parts of propylene glycol monomethyl ether acetate

P-2: 시클로헥산온 30부P-2: 30 parts of cyclohexanone

P-3: 3-에톡시프로피온산에틸 10부P-3: 10 parts of ethyl 3-ethoxypropionate

P-4: 프로필렌글리콜모노메틸에테르 10부P-4: 10 parts of propylene glycol monomethyl ether

P-5: 시클로헥산올아세테이트 10부P-5: 10 parts of cyclohexanol acetate

P-6: 디프로필렌글리콜메틸에테르아세테이트 10부P-6: 10 parts of dipropylene glycol methyl ether acetate

이상, (P-1) ∼ (P-6)을 각각 상기 질량부로 혼합하고, 유기 용제(P)로 했다.Above, (P-1) to (P-6) were each mixed in the above mass parts to obtain an organic solvent (P).

<감광성 조성물의 평가><Evaluation of photosensitive composition>

얻어진 감광성 조성물 1 ∼ 38(실시예 1 ∼ 35, 비교예 1 ∼ 3)에 대해서, 물 얼룩, 패턴 형성성(밀착성, 직선성), 및 잔막률의 평가를 하기의 방법으로 행했다. 평가 결과를 표 3에 나타낸다.The obtained photosensitive compositions 1 to 38 (Examples 1 to 35, Comparative Examples 1 to 3) were evaluated for water staining, pattern formation (adhesion, linearity), and residual film rate by the following methods. The evaluation results are shown in Table 3.

[물 얼룩 평가][Water stain evaluation]

얻어진 감광성 조성물에 대해서, 종 100㎜ × 횡 100㎜, 0.7㎜의 유리 기판(Corning Inc. 제조 EAGLE 2000) 상에, 건조 후의 막두께가 3.0㎛가 되도록 도공하고, 70℃에서 1분간 핫플레이트로 건조했다. 그 다음에, 100㎛ 폭의 스트라이프 패턴을 갖는 마스크를 통해 고압 수은등을 이용하여 조도 30mW／㎠, 40mJ／㎠의 조건 하에서 자외선 노광을 행했다. 그 후, 비이온계 계면활성제 0.12％와 수산화칼륨 0.04％를 포함하는 수계 현상액에, 23℃에서 40초간 침지하여 현상하고, 순수로 세정했다. 얻어진 패턴을 Nikon사 제조 ECLIPSE LV100POL Model 광학 현미경을 이용하여, 패턴의 표면을 관찰하고, 변색되어 있는 부분의 정도를 평가했다. 평가 기준은, 이하와 같으며, 3 이상을 실용 가능으로 한다.The obtained photosensitive composition was coated on a glass substrate (EAGLE 2000 manufactured by Corning Inc.) measuring 100 mm long x 100 mm wide x 0.7 mm so that the film thickness after drying was 3.0 μm, and heated on a hot plate at 70°C for 1 minute. It was dry. Next, ultraviolet ray exposure was performed under conditions of illuminance of 30 mW/cm2 and 40 mJ/cm2 using a high-pressure mercury lamp through a mask with a stripe pattern of 100 μm width. After that, it was developed by immersing it in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 23°C for 40 seconds, and washed with pure water. The surface of the obtained pattern was observed using an ECLIPSE LV100POL Model optical microscope manufactured by Nikon, and the degree of discolored portion was evaluated. The evaluation criteria are as follows, and a score of 3 or higher is considered practical.

5: 물 얼룩이 없었다.5: There were no water stains.

4: 물 얼룩이 전체의 10％ 미만이었다.4: Water stains were less than 10% of the total.

3: 물 얼룩이 전체의 10％ 이상 ∼ 20％ 미만이었다.3: Water stains were 10% to 20% of the total.

2: 물 얼룩이 전체의 20％ 이상 ∼ 30％ 미만이었다.2: Water stains were 20% or more to less than 30% of the total.

1: 물 얼룩이 전체의 30％ 이상이었다.1: Water stains accounted for more than 30% of the total.

<패턴 형성성 평가용 기판의 제작><Production of substrate for pattern formation evaluation>

얻어진 감광성 조성물을, 스핀 코팅법에 의해 종 100㎜ × 횡 100㎜, 0.7㎜ 두께의 유리 기판(Corning Inc. 제조 EAGLE 2000)에, 건조 후의 막두께가 3.0㎛가 되도록 도공하고, 70℃에서 1분간 핫플레이트로 건조했다. 그 다음에, 이 기판을 실온으로 냉각 후, 고압 수은등 램프를 이용하여 5㎛ 폭 간격의 스트라이프 패턴의 포토마스크를 개재하여 조도 30mW／㎠, 40mJ／㎠로 노광했다. 그 후, 이 기판을 23℃의 비이온계 계면활성제 0.12질량％와 수산화칼륨 0.04질량％를 포함하는 수계 현상액을 이용하여 스프레이 현상한 후, 이온 교환수로 세정, 풍건(風乾)하고, 클린 오븐 중 230℃에서 30분간 가열하여 패턴 형성성 평가용 기판을 얻었다. 스프레이 현상은, 각각의 감광성 조성물에서의 피막에 대해서, 현상 남김없이 패턴 형성 가능한 최단 시간에 행했다.The obtained photosensitive composition was coated on a glass substrate (EAGLE 2000 manufactured by Corning Inc.) measuring 100 mm long x 100 mm wide and 0.7 mm thick by spin coating so that the film thickness after drying was 3.0 ㎛, and 1 ℃ at 70°C. It was dried on a hot plate for one minute. Next, this substrate was cooled to room temperature, and then exposed using a high-pressure mercury lamp at an illumination intensity of 30 mW/cm2 and 40 mJ/cm2 through a photomask with a stripe pattern at 5-μm-width intervals. Thereafter, this substrate was spray developed at 23°C using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide, then washed with ion-exchanged water, air dried, and placed in a clean oven. A substrate for evaluating pattern formation was obtained by heating at 230°C for 30 minutes. Spray development was performed on the film of each photosensitive composition in the shortest time possible to form a pattern without leaving behind development.

[패턴 형성성 평가(1): 밀착성][Pattern formation evaluation (1): Adhesion]

상기 방법으로 작성된 패턴 형성성 평가용 기판 중 폭 5, 10, 15, 20, 및 25㎛의 패턴에 대해서, 광학 현미경으로 관찰하고, 잔존한 패턴의 최소 선폭을 확인했다. 평가 기준은, 이하와 같으며, 3 이상을 실용 가능으로 한다.Patterns with widths of 5, 10, 15, 20, and 25 μm among the substrates for pattern formation evaluation prepared by the above method were observed with an optical microscope to confirm the minimum line width of the remaining pattern. The evaluation criteria are as follows, and a score of 3 or higher is considered practical.

5: 10㎛ 이하의 가는 선이 잔존해 있다.5: A thin line of 10 μm or less remains.

4: 15㎛ 이하의 가는 선이 잔존해 있다.4: A thin line of 15 μm or less remains.

3: 20㎛ 이하의 가는 선이 잔존해 있다.3: A thin line of 20 μm or less remains.

2: 25㎛ 이하의 가는 선이 잔존해 있다.2: A thin line of 25 μm or less remains.

1: 가는 선이 잔존해 있지 않다.1: No thin lines remain.

[패턴 형성성 평가(2): 직선성][Pattern formation evaluation (2): linearity]

패턴 형성성 평가(1)에서 작성한 기판을, Nikon사 제조 ECLIPSE LV100POL Model 광학 현미경을 이용하여, 10개소의 스트라이프 패턴의 선폭의 최대와 최소 부분을 측정하고 그 평균을 구함으로써 평가를 행했다. 평가 기준은, 이하와 같으며, 3 이상을 실용 가능으로 한다.The substrate prepared in pattern formability evaluation (1) was evaluated by measuring the maximum and minimum line widths of the stripe pattern at 10 locations using an ECLIPSE LV100POL Model optical microscope manufactured by Nikon and calculating the average. The evaluation criteria are as follows, and a score of 3 or higher is considered practical.

5: 선폭의 최대치와 최소치의 차가 0.5㎛ 미만5: The difference between the maximum and minimum line width is less than 0.5㎛

4: 선폭의 최대치와 최소치의 차가 0.5㎛ 이상 1.0㎛ 미만4: The difference between the maximum and minimum line width is 0.5㎛ or more and less than 1.0㎛

3: 선폭의 최대치와 최소치의 차가 1.0㎛ 이상 1.5㎛ 미만3: The difference between the maximum and minimum line width is 1.0㎛ or more and less than 1.5㎛

2: 선폭의 최대치와 최소치의 차가 1.5㎛ 이상 2.0㎛ 미만2: The difference between the maximum and minimum line width is 1.5㎛ or more and less than 2.0㎛

1: 선폭의 최대치와 최소치의 차가 2.0㎛ 이상1: The difference between the maximum and minimum line width is 2.0㎛ or more.

[잔막률 평가][Evaluation of residual film rate]

상기 패턴 형성성 평가용 기판의 작성 시에 있어서, 스프레이 현상을 행하고, 이온 교환수로 세정하고 풍건 후의 도막의 막두께를 측정했다. 이 막두께를 현상 후 막두께로 한다. 그 후, 클린 오븐 중 230℃에서 30분간 가열하고, 현상 후 막두께를 측정한 같은 장소의 막두께를 측정했다. 이 막두께를 베이크 후 막두께로 한다. 2개의 막두께로부터 하기 수식에 의해 잔막률을 산출했다. 평가 기준은, 이하와 같으며, 3 이상을 실용 가능으로 한다. 또, 막두께는, Dektak 3030(ULVAC Japan, Ltd. 제조)을 이용하여 행했다.When preparing the substrate for evaluating pattern formation, spray development was performed, and the film thickness of the coating film after washing with ion-exchanged water and air drying was measured. This film thickness is referred to as the film thickness after development. Afterwards, it was heated at 230°C for 30 minutes in a clean oven, and the film thickness was measured at the same location where the film thickness was measured after development. This film thickness is referred to as the film thickness after baking. The remaining film rate was calculated from the two film thicknesses using the following formula. The evaluation criteria are as follows, and a score of 3 or higher is considered practical. In addition, the film thickness was measured using Dektak 3030 (manufactured by ULVAC Japan, Ltd.).

수식: 잔막률(％) ＝ 베이크 후 막두께 ÷ 현상 후 막두께 × 100Formula: Residual film rate (%) = film thickness after baking ÷ film thickness after development × 100

5: 잔막률 85％ 이상5: Remaining film rate of 85% or more

4: 잔막률 80％ 이상 85％ 미만4: Residual film rate 80% or more but less than 85%

3: 잔막률 75％ 이상 80％ 미만3: Residual film rate 75% or more but less than 80%

2: 잔막률 70％ 이상 75％ 미만2: Residual film rate 70% or more but less than 75%

1: 잔막률 70％ 미만1: Remaining film rate less than 70%

[표 3][Table 3]

Claims (9)

알칼리 가용성 수지(A), 중합성 화합물(B), 및 광중합개시제(C)를 포함하는 감광성 조성물로서,
상기 광중합개시제(C)는, 하기 일반식(1)으로 표시되는 옥심계 광중합개시제(C1), 및 옥심계 광중합개시제(C1) 이외의 옥심계 광중합개시제(C2)를 포함하는, 감광성 조성물.
[화 1]
일반식(1)

(일반식(1) 중, R1은, 수소 원자, 탄소 원자수 1 ∼ 20의 알킬기, 탄소 원자수 6 ∼ 30의 아릴기, 탄소 원자수 7 ∼ 30의 아릴알킬기, 또는 탄소 원자수 2 ∼ 20의 복소환기를 나타낸다.
R2은, 탄소 원자수 3 ∼ 20의 알킬기, 탄소 원자수 6 ∼ 30의 아릴기, 탄소 원자수 7 ∼ 30의 아릴알킬기, 또는 탄소 원자수 2 ∼ 20의 복소환기를 나타낸다.
R3은, 탄소 원자수 3 ∼ 20의 알킬기, 탄소 원자수 6 ∼ 30의 아릴기, 탄소 원자수 7 ∼ 30의 아릴알킬기, 또는 탄소 원자수 2 ∼ 20의 복소환기를 나타낸다.
R4은, 치환기를 가져도 되는 벤조일기를 나타내고, n은, 1을 나타낸다.)A photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), and a photopolymerization initiator (C),
The photopolymerization initiator (C) includes an oxime-based photopolymerization initiator (C1) represented by the following general formula (1), and an oxime-based photopolymerization initiator (C2) other than the oxime-based photopolymerization initiator (C1). A photosensitive composition.
[Tuesday 1]
General formula (1)

(In General Formula (1), R 1 is a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or 2 to 2 carbon atoms. It represents the heterocycle of 20.
R 2 represents an alkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.
R 3 represents an alkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.
R 4 represents a benzoyl group which may have a substituent, and n represents 1.) 제1항에 있어서,
상기 옥심계 광중합개시제(C1)와 상기 옥심계 광중합개시제(C1) 이외의 옥심계 광중합개시제(C2)의 질량비는, 90:10 ∼ 10:90인, 감광성 조성물.According to paragraph 1,
A photosensitive composition wherein the mass ratio of the oxime-based photopolymerization initiator (C1) and the oxime-based photopolymerization initiator (C2) other than the oxime-based photopolymerization initiator (C1) is 90:10 to 10:90. 제1항에 있어서,
상기 옥심계 광중합개시제(C1)와 상기 옥심계 광중합개시제(C1) 이외의 옥심계 광중합개시제(C2)의 합계 함유량은, 상기 광중합개시제(C) 100질량％ 중, 50질량％ 이상인, 감광성 조성물.According to paragraph 1,
The total content of the oxime-based photopolymerization initiator (C1) and the oxime-based photopolymerization initiator (C2) other than the oxime-based photopolymerization initiator (C1) is 50% by mass or more in 100% by mass of the photopolymerization initiator (C). A photosensitive composition. 제1항에 있어서,
상기 알칼리 가용성 수지(A)는, 지환식 탄화수소 함유 단량체 단위(a1), 및 카르복시기 함유 단량체 단위(a2)를 함유하는 알칼리 가용성 수지(A1)를 포함하는, 감광성 조성물.According to paragraph 1,
The alkali-soluble resin (A) is a photosensitive composition comprising an alicyclic hydrocarbon-containing monomer unit (a1) and an alkali-soluble resin (A1) containing a carboxyl group-containing monomer unit (a2). 제4항에 있어서,
상기 알칼리 가용성 수지(A1)는, 상기 지환식 탄화수소 함유 단량체 단위(a1)를, 상기 알칼리 가용성 수지(A1)의 전체 구성 단위 중, 5 ∼ 60몰％ 포함하는, 감광성 조성물.According to paragraph 4,
The photosensitive composition wherein the alkali-soluble resin (A1) contains the alicyclic hydrocarbon-containing monomer unit (a1) in an amount of 5 to 60 mol% based on the total structural units of the alkali-soluble resin (A1). 제1항에 있어서,
티올계 연쇄 이동제(D)를 더 포함하는, 감광성 조성물.According to paragraph 1,
A photosensitive composition further comprising a thiol-based chain transfer agent (D). 기판, 및 제1항 내지 제5항 중 어느 한 항에 기재된 감광성 조성물로 형성되어 이루어지는 필터 세그먼트를 갖는, 광학 필터.An optical filter comprising a substrate and a filter segment formed from the photosensitive composition according to any one of claims 1 to 5. 제7항에 기재된 광학 필터를 갖는, 화상 표시 장치.An image display device comprising the optical filter according to claim 7. 제7항에 기재된 광학 필터를 갖는, 고체 촬상 소자.
A solid-state imaging device comprising the optical filter according to claim 7.
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