CN104246608A

CN104246608A - Photosensitive resin composition, process for producing cured film, cured film, organic el display device, and liquid-crystal display device

Info

Publication number: CN104246608A
Application number: CN201380019967.8A
Authority: CN
Inventors: 山田悟; 柏木大助; 佐竹亮
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2012-04-16
Filing date: 2013-04-10
Publication date: 2014-12-24
Also published as: KR20140147847A; TW201348865A; JPWO2013157459A1; WO2013157459A1

Abstract

Provided is a photosensitive resin composition which is excellent in terms of all of sensitivity, adhesion, and high-temperature transparency. The photosensitive resin composition comprises (A) a polymer component which comprises one or more polymers satisfying the following (1) and/or (2), (B) a photo-acid generator, (C) a compound represented by general formula (I), and (D) a solvent: (1) a polymer having (a1) structural units having a residue formed by protecting an acid group with an acid-decomposable group and (a2) structural units having a crosslinkable group; and (2) a polymer having (a1) structural units having a residue formed by protecting an acid group with an acid-decomposable group and a polymer having (a2) structural units having a crosslinkable group.

Description

The manufacture method of photosensitive polymer combination, cured film, cured film, organic EL display and liquid crystal indicator

Technical field

The present invention relates to a kind of photosensitive polymer combination.Particularly relate to a kind of chemical amplification positive photosensitive polymer combination.In addition, the present invention relates to a kind of manufacture method of cured film of use sense photosensitive resin composition, the cured film that this photosensitive composite is hardened, use the various image display devices of this cured film.

More specifically; the present invention relates to one be suitable for being formed the positive type photosensitive organic compound of the planarization film of the electronic component such as liquid crystal indicator, organic electroluminescent (Electroluminescence, EL) display device, integrated circuit component, solid photographic element, diaphragm or interlayer dielectric and use its manufacture method of cured film.

Background technology

With regard to promoting brightness, reducing the viewpoints such as power consumption, in organic EL display or liquid crystal indicator etc., be provided with interlayer dielectric.Few and can obtain with regard to sufficient flatness etc. with regard to the number of steps in order to obtain required pattern form, in the formation of this interlayer dielectric, widely use photosensitive polymer combination.

Herein, requiring to use photosensitive polymer combination as above and forming figuratum interlayer dielectric is the effect film that after development and after heat hardening, the reliabilities such as contiguity is excellent, heat resistant transparent is excellent are high.In addition, in recent years in order to productivity manufactures organic EL display or liquid crystal indicator well, and the ISO of photosensitive polymer combination is required.

In the past, as the photosensitive polymer combination of ISO, there will be a known the patent documentation 1 etc. such as using and there is the bonding agent of ethylidene ether structure or ketal structure.Although just inferring that silane coupling agent is as contiguity modifying agent, these compositions cannot reach gratifying adhesion.In addition, considering the interaction with substrate, having by using amine to promote this idea of adhesion, but there is light sensitivity and correspond to the increase of addition and this shortcoming that declines, cannot reach light sensitivity and adhesion and deposit.In addition, the usual storage stability of bonding agent with ethylidene ether structure is not too high, therefore expects the contiguity modifying agent finding a kind of harmless stability.

[prior art document]

[patent documentation]

[patent documentation 1] Japanese Patent Laid-Open 2011-221494 publication

Summary of the invention

The problem that invention will solve

The present application is by the invention solved for the purpose of above-mentioned problem, and its object is to provides a kind of light sensitivity and adhesion, the equal excellent photosensitive polymer combination of heat resistant transparent.

The technological means of dealing with problems

The present inventor carries out making great efforts the result of research in order to solve above-mentioned problem, find that the compound by adding in photosensitive polymer combination represented by following general formula (I) is (following, also referred to as " specific sulfocompound "), above-mentioned problem can be solved.That is, find by the decomposition of the S-S key of specific sulfocompound and produce free radical, and attack causes dysgenic compound, result to make the liftings such as the transparency to the transparency.

Specifically, by following means <1>, solve above-mentioned problem preferably by means <2> ~ means <15>.

<1> photosensitive polymer combination, it comprises: (A) containing the component of polymer of the polymkeric substance of at least one meeting following (1) and following (2),

(1) there is the Component units of the residue that (a1) is protected by sour decomposability base containing acidic group and the polymkeric substance of (a2) Component units containing bridging property base,

(2) there is the polymkeric substance of the Component units of the residue that (a1) is protected by sour decomposability base containing acidic group and there is the polymkeric substance of (a2) Component units containing bridging property base;

(B) light acid producing agent;

(C) compound represented by following general formula (I); And

(D) solvent,

General formula (I)

[changing 1]

(in general formula (I), R ¹¹and R ¹²represent the base of at least 1 containing aliphatic alkyl, aromatic hydrocarbyl and heterocyclic radical respectively, n represents the integer of 2 ~ 4).

The photosensitive polymer combination of <2> as described in <1>, in its formula of (I), R ¹¹and R ¹²be respectively aliphatic alkyl or aromatic hydrocarbyl.

The photosensitive polymer combination of <3> as described in <1>, in its formula of (I), R ¹¹and R ¹²be respectively the alkyl of carbon number 1 ~ 10 or the aryl of carbon number 6 ~ 11.

The photosensitive polymer combination of <4> as described in <1>, wherein (C) compound represented by general formula (I) is represented by following general formula (II)

[changing 2]

R ²¹-L ¹¹-L ¹-S-S-L ²-L ¹²-R ²² (II)

(in general formula (II), R ²¹and R ²²represent hydrogen atom, alkyl or aryl respectively, L ¹and L ²represent alkylidene or arlydene respectively, L ¹¹and L ²²represent respectively *-O-C (=O)-or *-NH-C (=O)-; At * side and L ¹or L ²carry out bond).

The photosensitive polymer combination of <5> according to any one of <1> to <4>, the wherein Component units of residue of above-mentioned Component units (a1) for there is carboxyl being protected by the form of acetal.

The photosensitive polymer combination of <6> according to any one of <1> to <4>, wherein above-mentioned Component units (a1) is the Component units represented by following formula (A2 ')

Formula (A2 ')

[changing 3]

(in formula, R ¹and R ²represent hydrogen atom, alkyl or aryl respectively, at least R ¹and R ²any one be alkyl or aryl, R ³represent alkyl or aryl, R ¹or R ²with R ³can link and form cyclic ether, R ⁴represent hydrogen atom or methyl, X represents singly-bound or arlydene).

The photosensitive polymer combination of <7> according to any one of <1> to <6>, wherein above-mentioned bridging property base is for being selected from epoxy radicals, oxetanyl ,-NH-CH ₂at least a kind in-OR, R is the alkyl of carbon number 1 ~ 20.

The photosensitive polymer combination of <8> according to any one of <1> to <7>, wherein above-mentioned photosensitive polymer combination is chemical amplification positive photosensitive polymer combination.

The photosensitive polymer combination of <9> according to any one of <1> to <8>, wherein (B) light acid producing agent is oxime sulfonate compounds or salt compound.

The manufacture method of a <10> cured film, is characterized in that comprising:

(1) photosensitive polymer combination such as according to any one of <1> to <9> is applied to the step on substrate;

(2) in the photosensitive polymer combination applied, remove the step of solvent;

(3) active radioactive ray are utilized to carry out the step exposed;

(4) aqueous developer solution is utilized to carry out the step of developing; And

(5) the rear baking procedure of thermmohardening is carried out.

The manufacture method of the cured film of <11> as described in <10>, comprising after above-mentioned development step, before rear baking procedure, carries out the step of blanket exposure.

The manufacture method of the cured film of <12> as described in <10> or <11>, wherein aforesaid substrate is metal substrate.

<13> cured film, it makes the photosensitive polymer combination according to any one of <1> to <9> harden and be formed.

The cured film of <14> as described in <13>, it is interlayer dielectric.

<15> liquid crystal indicator or organic EL display, it comprises the cured film as described in <13> or <14>.

The effect of invention

According to the present invention, the photosensitive polymer combination that a kind of adhesion, heat resistant transparent are all excellent can be provided.

Accompanying drawing explanation

Fig. 1 represents the formation concept map of an example of organic EL display.Represent the constructed profile of the substrate in the organic EL display of bottom emission type, and there is planarization film 4.

Fig. 2 represents the formation concept map of an example of liquid crystal indicator.Represent the constructed profile of the active-matrix substrate in liquid crystal indicator, and there is the cured film 17 as interlayer dielectric.

Embodiment

Below, content of the present invention is described in detail.The explanation of constitutive requirements described is below carried out based on representative embodiment of the present invention sometimes, but the present invention is not limited thereto kind of an embodiment.Moreover in present specification, " ~ " to comprise before and after it described numerical value to use as the implication of lower limit and higher limit.

[photosensitive polymer combination]

The feature of photosensitive polymer combination of the present invention is to comprise: (A) is containing meeting compound represented by following general formula (I) of the component of polymer of the polymkeric substance of at least one of following (1) and following (2), (B) light acid producing agent, (C) and (D) solvent.

(2) there is the polymkeric substance of the Component units of the residue that (a1) is protected by sour decomposability base containing acidic group and there is the polymkeric substance of (a2) Component units containing bridging property base,

General formula (I)

[changing 4]

(in general formula (I), R ¹¹and R ¹²represent the base of at least 1 containing aliphatic alkyl, aromatic hydrocarbyl and heterocyclic radical respectively, n represents the integer of 2 ~ 4.)

Photosensitive polymer combination of the present invention is positive type photosensitive organic compound.In addition, photosensitive polymer combination of the present invention is preferably the positive type photosensitive organic compound (chemically amplified positive photosensitive polymer combination) of chemical amplification type.

Below, for photosensitive polymer combination of the present invention, the preferred form of each composition is described successively.

< (A) composition >

Photosensitive polymer combination of the present invention contains (A) and meets the component of polymer of at least one of following (1) and following (2) as (A) composition.

(2) there is the polymkeric substance of the Component units of the residue that (a1) is protected by sour decomposability base containing acidic group and there is the polymkeric substance of (a2) Component units containing bridging property base.

Herein; the form of above-mentioned (1) is for comprising at least a kind of polymkeric substance, and this polymkeric substance has the Component units of the residue that (a1) is protected by sour decomposability base containing acidic group and the form of (a2) Component units containing bridging property base.This polymkeric substance also and then can contain other repetitives.In addition, Component units (a1) or Component units (a2) can contain two or more respectively.

The form of above-mentioned (2) is for comprising at least 2 kinds of polymkeric substance, and at least 1 of this polymkeric substance kind has Component units (a1), and other at least 1 kinds of above-mentioned polymkeric substance have the form of Component units (a2).

And then in the form of (2), the polymkeric substance containing Component units (a1) also and then can contain Component units (a2) or other Component units.Similarly, the polymkeric substance containing Component units (a2) also can contain Component units (a1) or other Component units.In such cases, become satisfied (1) and (2) both forms.In this instructions, be called that the situation of " composition A " is the meaning comprising any one component of polymer above-mentioned without special instruction in advance.

Preferred first example of the present invention is for comprising polymkeric substance of more than two kinds as (A) composition; and at least 1 of this polymkeric substance kind is the polymkeric substance of the Component units at least with the residue protected by sour decomposability base containing acidic group, other at least 1 kinds of above-mentioned polymkeric substance is the polymkeric substance of the Component units at least had containing bridging property base.With regard to the viewpoint of the degree of freedom of MOLECULE DESIGN; be more preferably the above-mentioned polymkeric substance at least with the Component units of the residue protected by sour decomposability base containing acidic group and do not contain Component units (a2) in fact, and the polymkeric substance at least with the Component units containing bridging property base does not contain Component units (a1) in fact.Herein, what is called does not contain in fact, refers to be such as less than 3 % by mole relative to the ratio of total Component units, and then is less than 1 % by mole.

As preferred second example of the present invention, with regard to the viewpoint of compatibility, the polymkeric substance can enumerated containing above-mentioned Component units (a1) contains the form of above-mentioned Component units (a2).

And then, as the 3rd form, also can consider the polymkeric substance of above-mentioned first example and the polymkeric substance of the second example and to deposit and as the form of component of polymer (A).

(A) composition is preferably the resin of addition polymerization type, is more preferably the polymkeric substance containing the Component units being derived from (methyl) acrylic acid and/or its ester.Moreover, also can have the Component units beyond the Component units being derived from (methyl) acrylic acid and/or its ester, such as, be derived from cinnamic Component units or be derived from the Component units etc. of vinyl compound.

Above-mentioned (A) composition is preferably relative to the total Component units in polymkeric substance, containing the Component units being derived from (methyl) acrylic acid and/or its ester of more than 50 % by mole, be more preferably the Component units being derived from (methyl) acrylic acid and/or its ester containing more than 90 % by mole, be particularly preferably the polymkeric substance only comprising the Component units being derived from (methyl) acrylic acid and/or its ester.

Moreover, also " being derived from the Component units of (methyl) acrylic acid and/or its ester " is called " acrylic acid series Component units ".In addition, " (methyl) acrylic acid " refers to " methacrylic acid and/or acrylic acid ".

(A) composition is preferably alkali-insoluble, and is preferably the resin becoming alkali-soluble when the sour decomposability base had at Component units (a1) decomposes.Herein, so-called sour decomposability base, refers to decomposable functional group in the presence of acid.Namely; the Component units of the protection carboxyl protected by sour decomposability base containing carboxyl is decomposed by Protecting gene acid; thus can carboxyl be generated; in addition; the Component units of the protection phenolic hydroxyl group protected by sour decomposability base containing phenolic hydroxyl group is decomposed by Protecting gene acid, thus can generate phenolic hydroxyl group.Herein, in the present invention, so-called " alkali-soluble ", refer to by the solution of this compound (resin) is coated on substrate, and the film (thickness is 3 μm) of this compound (resin) heating 2 minutes at 90 DEG C and formed is more than 0.01 μm/second for the dissolution velocity of 0.4% tetramethyl ammonium hydroxide aqueous solution at 23 DEG C, so-called " alkali-insoluble ", refer to by the solution of this compound (resin) is coated on substrate, and the film (thickness is 3 μm) of this compound (resin) heating 2 minutes at 90 DEG C and formed for the dissolution velocity of 0.4% tetramethyl ammonium hydroxide aqueous solution at 23 DEG C less than 0.01 μm/second.

Above-mentioned (A) multipolymer also can have other Component units etc. containing carboxyl described later, the structure being derived from carboxylic acid anhydrides and/or phenolic hydroxyl group.But, when importing acidic groups, be preferably above-mentioned (A) multipolymer entirety to be remained alkali-insoluble scope in importing.

The Component units >> of the residue that << (a1) is protected by sour decomposability base containing acidic group

(A) composition at least has the Component units of the residue that (a1) is protected by sour decomposability base containing acidic group.By (A) composition, there is Component units (a1), can be made into the photosensitive polymer combination that light sensitivity is high.

Component units (a1) in the present invention preferably comprises the Component units containing the protection carboxyl protected by sour decomposability base or the Component units containing the protection phenolic hydroxyl group protected by sour decomposability base.

Below, successively the Component units (a1-1) containing the protection carboxyl protected by sour decomposability base and the Component units (a1-2) containing the protection phenolic hydroxyl group protected by sour decomposability base are described respectively.

The Component units >>> of <<< (a1-1) containing the protection carboxyl protected by sour decomposability base

The Component units (a1-1) of the above-mentioned protection carboxyl containing being protected by sour decomposability base be the carboxyl of the Component units containing carboxyl have following by describe in detail by the Component units of the protection carboxyl of sour decomposability base protection.

As the above-mentioned Component units containing carboxyl that can be used for the above-mentioned Component units (a1-1) containing the protection carboxyl by sour decomposability base protection, known Component units can be used with no particular limitation.Include, for example: be derived from the Component units (a1-1-1) in unsaturated monocarboxylic acid, unsaturated dicarboxylic, unsaturated tricarboxylic acids equimolecular with the unsaturated carboxylic acid of at least 1 carboxyl etc., or there is ethene unsaturated group and the Component units (a1-1-2) of structure being derived from acid anhydrides simultaneously.

Below, be derived from molecule the Component units of the unsaturated carboxylic acid with at least 1 carboxyl etc. and (a1-1-2) to (a1-1-1) that can be used as the above-mentioned Component units containing carboxyl successively there is ethene unsaturated group to be simultaneously described respectively with the Component units of the structure being derived from acid anhydrides.

<<<< (a1-1-1) is derived from molecule the Component units >>>GreatT.Grea T.GT of the unsaturated carboxylic acid with at least 1 carboxyl etc.

As the above-mentioned Component units (a1-1-1) being derived from molecule the unsaturated carboxylic acid with at least 1 carboxyl etc., the unsaturated carboxylic acid lifted as listed below can be used as the unsaturated carboxylic acid used in the present invention.That is, as unsaturated monocarboxylic acid, include, for example: acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid etc.In addition, as unsaturated dicarboxylic, include, for example: maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc.In addition, the unsaturated polybasic carboxylic acid for obtaining the Component units containing carboxyl also can be its acid anhydrides.Specifically, maleic anhydride, itaconic anhydride, citraconic anhydride etc. can be enumerated.In addition, unsaturated polybasic carboxylic acid also can be list (2-methacryloxyalkyl) ester of polybasic carboxylic acid, include, for example: succinic acid list (2-acryloyl-oxyethyl) ester, succinic acid list (2-methacryloxyethyl) ester, phthalic acid list (2-acryloyl-oxyethyl) ester, phthalic acid list (2-methacryloxyethyl) ester etc.And then unsaturated polybasic carboxylic acid also can be list (methyl) acrylate of its two ends dicarboxyl polymkeric substance, include, for example ω-carboxy-polycaprolactone mono acrylic ester, ω-carboxy-polycaprolactone monomethacrylates etc.In addition, as unsaturated carboxylic acid, acrylic acid-2-carboxyethyl, methacrylic acid-2-carboxyethyl, maleic acid mono alkyl ester, fumaric acid mono alkyl ester, 4-carboxyl styrene etc. also can be used.

Wherein, with regard to the viewpoint of developability, in order to form the above-mentioned Component units (a1-1-1) being derived from molecule the unsaturated carboxylic acid with at least 1 carboxyl etc., preferably use the acid anhydride etc. of acrylic acid, methacrylic acid or unsaturated polybasic carboxylic acid, be more preferably and use acrylic or methacrylic acid.

The above-mentioned Component units (a1-1-1) being derived from molecule the unsaturated carboxylic acid with at least 1 carboxyl etc. can comprise separately a kind, also can comprise two or more.

<<<< (a1-1-2) has ethene unsaturated group and the Component units >>>GreatT.Grea T.GT of structure being derived from acid anhydrides simultaneously

There is the unit that ethene unsaturated group and the Component units (a1-1-2) of structure being derived from acid anhydrides are preferably derived from the monomer that the hydroxyl existing for making in the Component units containing ethene unsaturated group and acid anhydrides carry out reacting and obtain simultaneously.

As above-mentioned acid anhydrides, known acid anhydrides can be used, specifically, can enumerate: the dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; The acid anhydrides such as trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic anhydride, biphenyltetracarboxyacid acid acid anhydride.Among these acid anhydrides, with regard to the viewpoint of developability, be preferably phthalic anhydride, tetrabydrophthalic anhydride or succinic anhydride.

With regard to the viewpoint of developability, above-mentioned acid anhydrides is preferably 10 % by mole ~ 100 % by mole for the reaction rate of hydroxyl, is more preferably 30 % by mole ~ 100 % by mole.

<<<< can be used for the sour decomposability base >>>GreatT.Grea T.GT of Component units (a1-1)

As the above-mentioned sour decomposability base of Component units (a1-1) that can be used for the above-mentioned protection carboxyl containing being protected by sour decomposability base, sour decomposability base and known can be used as, be not particularly limited.In the past, as sour decomposability base, there will be a known than base acetal system functional groups such as () such as THP trtrahydropyranyl being easier to decompose because of acid or compare the base (such as the tributyl system functional group such as tributyl base, carbonic acid tributyl base) being difficult to decompose because of sour.

Among these sour decomposability bases, with regard to the viewpoint of the basic physical properties of photosensitive polymer combination, particularly light sensitivity or pattern form, the formative of contact hole, the storage stability of photosensitive polymer combination, be preferably acetal system functional group.And then, among the protection carboxyl protected by sour decomposability base, with regard to the viewpoint of light sensitivity, be more preferably carboxyl by the protection carboxyl protected with the form of the acetal represented by following general formula (a1-1).Moreover when carboxyl is by the protection carboxyl protected with the form of the acetal represented by following general formula (a1-1), the entirety of protection carboxyl becomes-(C=O)-O-CR ¹⁰¹r ¹⁰²(OR ¹⁰³) structure.

General formula (a1-1)

[changing 5]

(in formula (a1-1), R ¹⁰¹and R ¹⁰²separately represent hydrogen atom or alkyl, wherein, get rid of R ¹⁰¹with R ¹⁰²be the situation of hydrogen atom.R ¹⁰³represent alkyl.R ¹⁰¹or R ¹⁰²with R ¹⁰³can link and form cyclic ether.)

In above-mentioned general formula (a1-1), R ¹⁰¹~ R ¹⁰³separately represent hydrogen atom or alkyl, this alkyl can be straight-chain, branched, ring-type any one.Herein, there is not R ¹⁰¹and R ¹⁰²all represent the situation of hydrogen atom, R ¹⁰¹and R ¹⁰²at least one represent alkyl.

In above-mentioned general formula (a1-1), work as R ¹⁰¹, R ¹⁰²and R ¹⁰³when representing alkyl, this alkyl can be any one of straight-chain, branched or ring-type.

As the alkyl of above-mentioned straight-chain or branched, be preferably carbon number 1 ~ 12, be more preferably carbon number 1 ~ 6, and then be more preferably carbon number 1 ~ 4.Specifically, can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, the second butyl, tributyl, n-pentyl, neopentyl, n-hexyl, 2,3-dimethyl-2-butyl (thexyl), n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, positive decyl etc.

As above-mentioned cyclic alkyl, be preferably carbon number 3 ~ 12, be more preferably carbon number 4 ~ 8, and then be more preferably carbon number 4 ~ 6.As above-mentioned cyclic alkyl, include, for example: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, norborny, isobornyl etc.

Abovementioned alkyl also can have substituting group, alternatively base, can illustrate halogen atom, aryl, alkoxy.When have halogen atom alternatively base time, R ¹⁰¹, R ¹⁰², R ¹⁰³become haloalkyl, when have aryl alternatively base time, R ¹⁰¹, R ¹⁰², R ¹⁰³become aralkyl.

As above-mentioned halogen atom, fluorine atom, chlorine atom, bromine atoms, atomic iodine can be illustrated, among these halogen atoms, be preferably fluorine atom or chlorine atom.

In addition, as above-mentioned aryl, be preferably the aryl of carbon number 6 ~ 20, be more preferably the aryl of carbon number 6 ~ 12, specifically, phenyl, Alpha-Methyl phenyl, naphthyl etc. can be illustrated, overall as the alkyl replaced by aryl, i.e. aralkyl, can illustrate benzyl, α-methylbenzyl, phenethyl, naphthyl methyl etc.

As above-mentioned alkoxy, be preferably the alkoxy of carbon number 1 ~ 6, be more preferably the alkoxy of carbon number 1 ~ 4, and then be more preferably methoxy or ethoxy.

In addition, when abovementioned alkyl is naphthenic base, this naphthenic base can have the straight-chain of carbon number 1 ~ 10 or the alkyl alternatively base of branched, when alkyl is the alkyl of straight-chain or branched, can have the naphthenic base alternatively base of carbon number 3 ~ 12.

These substituting groups also can be replaced by above-mentioned substituting group further.

In above-mentioned general formula (a1-1), work as R ¹⁰¹, R ¹⁰²and R ¹⁰³when representing aryl, this aryl is preferably carbon number 6 ~ 12, is more preferably carbon number 6 ~ 10.This aryl can have substituting group, as this substituting group, preferably can illustrate the alkyl of carbon number 1 ~ 6.As aryl, such as, can illustrate phenyl, tolyl, silylation, cumenyl, 1-naphthyl etc.

In addition, R ¹⁰¹, R ¹⁰²and R ¹⁰³can bond mutually, and together form ring with the carbon atom of these bonds.As R ¹⁰¹with R ¹⁰², R ¹⁰¹with R ¹⁰³or R ¹⁰²with R ¹⁰³ring structure during bond, include, for example: cyclobutyl, cyclopentyl, cyclohexyl, suberyl, tetrahydrofuran base, adamantyl and THP trtrahydropyranyl etc.

Moreover, in above-mentioned general formula (a1-1), be preferably R ¹⁰¹and R ¹⁰²any one be hydrogen atom or methyl.

The preferred form of the Component units (a1-1) of the above-mentioned protection carboxyl containing being protected by sour decomposability base is the Component units represented by formula (A2 ').

Formula (A2 ')

[changing 6]

(in formula, R ¹and R ²represent hydrogen atom, alkyl or aryl respectively, at least R ¹and R ²any one be alkyl or aryl, R ³represent alkyl or aryl, R ¹or R ²with R ³can link and form cyclic ether, R ⁴represent hydrogen atom or methyl, X represents singly-bound or arlydene.)

Work as R ¹and R ²during for alkyl, be preferably the alkyl of carbon number 1 ~ 10.Work as R ¹and R ²during for aryl, be preferably phenyl.R ¹and R ²be preferably the alkyl of hydrogen atom or carbon number 1 ~ 4 respectively.

R ³represent alkyl or aryl, be preferably the alkyl of carbon number 1 ~ 10, be more preferably the alkyl of 1 ~ 6.

X represents singly-bound or arlydene, is preferably singly-bound.

Free radical polymerization monomer for the formation of the Component units containing the protection carboxyl represented by above-mentioned general formula (a1-1) can use commercially available free radical polymerization monomer, also can use the free radical polymerization monomer utilized synthesized by known method.

As the preferred concrete example of the Component units (a1-1) of the above-mentioned protection carboxyl containing being protected by sour decomposability base, following Component units can be illustrated.Moreover R represents hydrogen atom or methyl.

[changing 7]

The Component units >>> of <<< (a1-2) containing the protection phenolic hydroxyl group protected by sour decomposability base

The Component units (a1-2) of the above-mentioned protection phenolic hydroxyl group containing being protected by sour decomposability base has the Component units of the Component units containing phenolic hydroxyl group by the following protection phenolic hydroxyl group protected by the sour decomposability base described in detail.

The Component units >>>GreatT.Grea T.GT of <<<< (a1-2-1) containing phenolic hydroxyl group

As the above-mentioned Component units containing phenolic hydroxyl group, the Component units in the resin of hydroxy styrenes system Component units or novolaks system can be enumerated, among these Component units, with regard to the viewpoint of the transparency, be preferably derived from the Component units of hydroxy styrenes or Alpha-Methyl hydroxy styrenes.Among the Component units of phenolic hydroxyl group, with regard to the viewpoint of the transparency, light sensitivity, be preferably the Component units represented by following general formula (a1-2).

General formula (a1-2)

[changing 8]

(in general formula (a1-2), R ²²⁰represent hydrogen atom or methyl, R ²²¹represent the concatenating group of singly-bound or divalence, R ²²²represent the alkyl of the straight or branched of halogen atom or carbon number 1 ~ 5, a represents the integer of 1 ~ 5, and b represents the integer of 0 ~ 4, and a+b is less than 5.Moreover, as the R of existence more than 2 ²²²time, these R ²²²mutually can be different, also can be identical.)

In above-mentioned general formula (a1-2), R ²²⁰represent hydrogen atom or methyl, be preferably methyl.

In addition, R ²²¹represent the concatenating group of singly-bound or divalence.Work as R ²²¹during for singly-bound, can promotion feeling luminosity, and then the transparency of cured film can be promoted, therefore preferably.As R ²²¹the concatenating group of divalence, can alkylidene be illustrated, as R ²²¹for the concrete example of alkylidene, can enumerate: methylene, ethylidene, propylidene, isopropylidene, sub-normal-butyl, isobutylidene, sub-tributyl, pentylidene, isoamylidene, sub-neopentyl, hexylidene etc.Wherein, R ²²¹be preferably singly-bound, methylene, ethylidene.In addition, the concatenating group of above-mentioned divalence can have substituting group, and alternatively base can enumerate halogen atom, hydroxyl, alkoxy etc.In addition, a represents the integer of 1 ~ 5, but with regard to effect of the present invention viewpoint or easily manufacture with regard to this viewpoint, being preferably a is 1 or 2, and being more preferably a is 1.

In addition, when will with R ²²¹when the carbon atom carrying out bond is as benchmark (1), the binding site of the hydroxyl in phenyl ring is preferably binding on 4.

R ²²²for the alkyl of the straight or branched of halogen atom or carbon number 1 ~ 5.

Specifically, can enumerate: fluorine atom, chlorine atom, bromine atoms, methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl, tributyl, amyl group, isopentyl, neopentyl etc.Wherein, just easily manufacture with regard to this viewpoint, be preferably chlorine atom, bromine atoms, methyl or ethyl.

In addition, b represents the integer of 0 or 1 ~ 4.

<<<< can be used for the sour decomposability base >>>GreatT.Grea T.GT of Component units (a1-2)

As the above-mentioned sour decomposability base that can be used for the above-mentioned Component units (a1-2) containing the protection phenolic hydroxyl group by sour decomposability base protection; in the same manner as can be used for the above-mentioned sour decomposability base of the above-mentioned Component units (a1-1) of protection carboxyl containing being protected by sour decomposability base; known sour decomposability base can be used, be not particularly limited.Among acid decomposability base; with regard to the basic physical properties of resist; the particularly viewpoint of light sensitivity or pattern form, the storage stability of photosensitive polymer combination, the formative of contact hole, is preferably the Component units containing the protection phenolic hydroxyl group protected by the form of acetal.

And then, among sour decomposability base, with regard to the viewpoint of light sensitivity, be more preferably phenolic hydroxyl group by the protection phenolic hydroxyl group protected with the form of the acetal represented by above-mentioned general formula (a1-1).Moreover when phenolic hydroxyl group is by the protection phenolic hydroxyl group protected with the form of the acetal represented by above-mentioned general formula (a1-1), the entirety of protection phenolic hydroxyl group becomes-Ar-O-CR ¹⁰¹r ¹⁰²(OR ¹⁰³) structure.Moreover Ar represents arlydene.

The preference of the acetal ester structure of phenolic hydroxyl group can illustrate R ¹⁰¹=R ¹⁰²=R ¹⁰³=methyl or R ¹⁰¹=R ¹⁰²=methyl and R ¹⁰³the combination of=benzyl.

In addition; as the free radical polymerization monomer of the Component units for the formation of the protection phenolic hydroxyl group protected by the form of acetal containing phenolic hydroxyl group, include, for example free radical polymerization monomer etc. described in the paragraph 0042 of Japanese Patent Laid-Open 2011-215590 publication.

Among these free radical polymerization monomers, with regard to the viewpoint of the transparency, be preferably the 1-alkoxyalkyl protective of methacrylic acid 4-hydroxylphenyl ester, the THP trtrahydropyranyl protective of methacrylic acid 4-hydroxylphenyl ester.

As the concrete example of the acetal protecting group of phenolic hydroxyl group; 1-alkoxyalkyl can be enumerated; include, for example 1-ethoxyethyl group, 1-methoxy ethyl, 1-n-butoxyethyl, 1-isobutoxyethy, 1-(2-chloroethoxy) ethyl, 1-(2-ethyl hexyl oxy) ethyl, 1-positive propoxy ethyl, 1-cyclohexyloxy ethyl, 1-(2-cyclohexylethoxy radical) ethyl, 1-Benzyloxyethyl etc., these bases can be used alone or two or more combinationally used.

Free radical polymerization monomer for the formation of the Component units (a1-2) of the above-mentioned protection phenolic hydroxyl group containing being protected by sour decomposability base can use commercially available free radical polymerization monomer, also can use the free radical polymerization monomer utilized synthesized by known method.Such as, by making the compound containing phenolic hydroxyl group and vinyl ether carry out reacting synthesizing in the presence of acid catalyst.Above-mentioned synthesis also can make the monomer containing phenolic hydroxyl group and other monomers carry out copolymerization in advance, then reacts with vinyl ether in the presence of acid catalyst.

As the preferred concrete example of the Component units (a1-2) of the above-mentioned protection phenolic hydroxyl group containing being protected by sour decomposability base, following Component units can be illustrated, but the present invention is not limited to these Component units.

[changing 9]

[changing 10]

[changing 11]

The preferred form >>> of <<< Component units (a1)

When the polymkeric substance containing above-mentioned Component units (a1) is not in fact containing Component units (a2), in the polymkeric substance containing this Component units (a1), Component units (a1) is preferably 5 % by mole ~ 90 % by mole, is more preferably 20 % by mole ~ 80 % by mole.

When the polymkeric substance containing above-mentioned Component units (a1) contains above-mentioned Component units (a2), with regard to the viewpoint of light sensitivity, in the polymkeric substance containing this Component units (a1) and Component units (a2), single Component units (a1) is preferably 3 % by mole ~ 70 % by mole, is more preferably 10 % by mole ~ 60 % by mole.In addition, especially when the above-mentioned sour decomposability base that can be used for above-mentioned Component units (a1) is the Component units of the protection carboxyl protected by the form of acetal containing carboxyl, and then 10 % by mole ~ 40 % by mole are more preferably.

And then, in the present invention, no matter which kind of form, at (A) total in the Component units of composition, be preferably the Component units (a1) containing 3 % by mole ~ 70 % by mole, be more preferably the Component units (a1) containing 10 % by mole ~ 60 % by mole.

Compared with the Component units (a1-2) of the above-mentioned protection phenolic hydroxyl group containing being protected by sour decomposability base, the Component units (a1-1) of the above-mentioned protection carboxyl containing being protected by sour decomposability base has development this feature fast.Therefore, when for rapid development, be preferably the Component units (a1-1) containing the protection carboxyl protected by sour decomposability base.On the contrary, when making development slack-off, be preferably the Component units (a1-2) used containing the protection phenolic hydroxyl group protected by sour decomposability base.

The Component units >> of << (a2) containing crosslinking group

(A) composition has the Component units (a2) containing crosslinking group.As long as above-mentioned crosslinking group produces the base of sclerous reaction by heating, be then not particularly limited.As the form of the preferred Component units containing crosslinking group, can enumerate containing being selected from by oxirane base (oxiranyl group), oxetanyl ,-NH-CH ₂the Component units of at least 1 in the group that-OR (R is the alkyl of carbon number 1 ~ 20) and ethene unsaturated group form.

Wherein, photosensitive polymer combination of the present invention is more preferably above-mentioned (A) composition and comprises Component units containing at least 1 in oxirane base and oxetanyl, is particularly preferably above-mentioned (A) composition and comprises Component units containing oxetanyl.More specifically, can enumerate following.

<<< (a2-1) has the Component units >>> of oxirane base and/or oxetanyl

Above-mentioned (A) multipolymer is preferably containing the Component units (Component units (a2-1)) with oxirane base and/or oxetanyl.The cyclic ether group of above-mentioned 3 rings is also referred to as oxirane base, and the cyclic ether group of 4 rings is also referred to as oxetanyl.As the above-mentioned Component units (a2-1) with oxirane base and/or oxetanyl, preferably there is the Component units of alicyclic ring oxirane base and/or oxetanyl, be more preferably the Component units with oxetanyl.

Above-mentioned have the Component units (a2-1) of oxirane base and/or oxetanyl as long as have at least 1 oxirane base or oxetanyl in 1 Component units, the oxirane base of more than 1 and the oxetanyl of more than 1 can be had, the oxirane base of more than 2, or more than 2 oxetanyls, be not particularly limited, but preferably there is the oxirane base and/or oxetanyl that add up to 1 ~ 3, be more preferably the oxirane base and/or oxetanyl that have and add up to 1 or 2, and then be more preferably there is 1 oxirane base or oxetanyl.

As for the formation of the concrete example of free radical polymerization monomer of Component units with oxirane base, include, for example glycidyl acrylate, glycidyl methacrylate, α-ethylacrylate ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-n-butyl acryloyloxy ethyl acid glycidyl ester, acrylic acid-3, 4-epoxy radicals butyl ester, methacrylic acid-3, 4-epoxy radicals butyl ester, acrylic acid-3, 4-epoxycyclohexanecarboxylate, methacrylic acid-3, 4-epoxycyclohexanecarboxylate, α-ethylacrylate-3, 4-epoxycyclohexanecarboxylate, adjacent vinylbenzyl glycidyl ether, between vinylbenzyl glycidyl ether, to vinylbenzyl glycidyl ether, the compound etc. containing ester ring type epoxy radicals skeleton described in the paragraph 0031 ~ paragraph 0035 of Jap.P. No. 4168443 publication.

As for the formation of the concrete example of free radical polymerization monomer of Component units with oxetanyl, include, for example (methyl) acrylate etc. with oxetanyl described in the paragraph 0011 ~ paragraph 0016 of Japanese Patent Laid-Open 2001-330953 publication.

As for the formation of the above-mentioned concrete example with the free radical polymerization monomer of the Component units (a2-1) of oxirane base and/or oxetanyl, be preferably containing the monomer of metacrylic acid ester structure, the monomer containing acrylate structural.

Among these monomers, preferred monomer is (methyl) acrylate with oxetanyl contained described in the compound of ester ring type epoxy radicals skeleton and the paragraph 0011 ~ paragraph 0016 of Japanese Patent Laid-Open 2001-330953 publication described in the paragraph 0034 ~ paragraph 0035 of Jap.P. No. 4168443 publication, and particularly preferred monomer is (methyl) acrylate with oxetanyl described in the paragraph 0011 ~ paragraph 0016 of Japanese Patent Laid-Open 2001-330953 publication.Among these, be preferably glycidyl methacrylate, acrylic acid 3,4-epoxycyclohexanecarboxylate, methacrylic acid 3,4-epoxycyclohexanecarboxylate, acrylic acid (3-Ethyloxetane-3-base) methyl esters and methacrylic acid (3-Ethyloxetane-3-base) methyl esters, most preferably be acrylic acid (3-Ethyloxetane-3-base) methyl esters and methacrylic acid (3-Ethyloxetane-3-base) methyl esters.These Component units can be used alone a kind or two or more combinationally used.

As the above-mentioned Component units (a2-1) with oxirane base and/or oxetanyl, can with reference to the record of the paragraph 0053 ~ paragraph 0055 of Japanese Patent Laid-Open 2011-215590 publication.

As the above-mentioned preferred concrete example with the Component units (a2-1) of oxirane base and/or oxetanyl, following Component units can be illustrated.Moreover R represents hydrogen atom or methyl.

[changing 12]

In the present invention, with regard to the viewpoint of light sensitivity, be preferably oxetanyl.In addition, with regard to the viewpoint of transmitance (transparency), be preferably alicyclic ring oxirane base and oxetanyl.According to the above, in the present invention, as oxirane base and/or oxetanyl, be preferably alicyclic ring oxirane base and oxetanyl, be particularly preferably oxetanyl.

<<< (a2-2) has the Component units >>> of ethene unsaturated group

As a kind of the above-mentioned Component units (a2) containing crosslinking group, the Component units (a2-2) (hereinafter also referred to as " Component units (a2-2) ") with ethene unsaturated group can be enumerated.As the above-mentioned Component units (a2-2) with ethene unsaturated group, be preferably Component units side chain with ethene unsaturated group, be more preferably end and there is ethene unsaturated group and the Component units with the side chain of carbon number 3 ~ 16, and then be more preferably the Component units of the side chain had represented by following general formula (a2-2-1).

General formula (a2-2-1)

[changing 13]

(in general formula (a2-2-1), R ³⁰¹represent the concatenating group of the divalence of carbon number 1 ~ 13, R ³⁰²represent hydrogen atom or methyl, * represents and the position that the main chain of the Component units (a2) containing crosslinking group links.)

R ³⁰¹for the concatenating group of the divalence of carbon number 1 ~ 13, the base comprising thiazolinyl, cycloalkenyl group, arlydene or these combined, also can contain the keys such as ester bond, ehter bond, amido link, amino-formate bond.In addition, the concatenating group of divalence can have the substituting group such as hydroxyl, carboxyl on arbitrary position.As R ³⁰¹concrete example, the concatenating group of following divalence can be enumerated.

[changing 14]

Among side chain represented by above-mentioned general formula (a2-2-1), preferably comprise by above-mentioned R ³⁰¹the aliphatic side chain of the concatenating group of represented divalence.

There is about other (a2-2) Component units of ethene unsaturated group, can with reference to the record of the paragraph 0077 ~ paragraph 0090 of Japanese Patent Laid-Open 2011-215580 publication.

<<< (a2-3) has by-NH-CH ₂the Component units >>> of the part-structure represented by-O-R (R is the alkyl of carbon number 1 ~ 20)

The multipolymer used in the present invention is for having by-NH-CH ₂the Component units (a2-3) of the part-structure represented by-O-R (R is the alkyl of carbon number 1 ~ 20) is also preferred.By containing Component units (a2-3), the heating of mitigation can be utilized to produce sclerous reaction, and the cured film of various excellent can be obtained.Herein, R is preferably the alkyl of carbon number 1 ~ 9, is more preferably the alkyl of carbon number 1 ~ 4.In addition, alkyl can be any one of alkyl of straight chain, branch or ring-type, but is preferably the alkyl of straight chain or branch.Component units (a2) is more preferably the Component units of the base had represented by following general formula (1).

General formula (1)

[changing 15]

(in above-mentioned formula, R ¹represent hydrogen atom or methyl, R ²represent the alkyl of carbon number 1 ~ 20.)

R ²be preferably the alkyl of carbon number 1 ~ 9, be more preferably the alkyl of carbon number 1 ~ 4.In addition, alkyl can be any one of alkyl of straight chain, branch or ring-type, but is preferably the alkyl of straight chain or branch.

As R ²concrete example, can enumerate: methyl, ethyl, normal-butyl, isobutyl, cyclohexyl and n-hexyl.Wherein, isobutyl, normal-butyl, methyl is preferably.

The preferred form >>> of <<< Component units (a2)

When the polymkeric substance containing above-mentioned Component units (a2) is not in fact containing Component units (a1), in the polymkeric substance containing this Component units (a1), Component units (a1) is preferably 5 % by mole ~ 90 % by mole, is more preferably 20 % by mole ~ 80 % by mole.

When the polymkeric substance containing above-mentioned Component units (a2) contains above-mentioned Component units (a1), with regard to the viewpoint of light sensitivity, in the polymkeric substance containing this Component units (a1) and Component units (a2), single Component units (a1) is preferably 3 % by mole ~ 70 % by mole, is more preferably 10 % by mole ~ 60 % by mole.

And then, in the present invention, no matter which kind of form, in all Component units of (A) composition, be preferably the Component units (a2) containing 3 % by mole ~ 70 % by mole, be more preferably the Component units (a2) containing 10 % by mole ~ 60 % by mole.

If in the scope of above-mentioned numerical value, then the transparency of the cured film obtained by photosensitive polymer combination and tin indium oxide (Indium Tin Oxide, ITO) sputter tolerance become good.

<< (a3) other Component units >>

In the present invention, (A) composition, except above-mentioned Component units (a1) and Component units (a2), also can have other Component units (a3).As the monomer becoming other Component units (a3), there is no particular restriction.Include, for example: phenylethylene, (methyl) alkyl acrylate, (methyl) acrylic acid cyclic alkyl ester, (methyl) benzyl acrylate, unsaturated dicarboxylic diester, dicyclo unsaturated compound class, maleimide compounds class, unsaturated aromatics, conjugated diolefine based compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic, unsaturated dicarboxylic acid anhydride, other unsaturated compounds.

Specifically, the Component units formed by following compound can be enumerated: styrene, 3rd butyl phenyl ether ethene, methyl styrene, hydroxy styrenes, α-methyl styrene, acetoxy-styrene, methoxy styrene, ethoxystyrene, chlorostyrene, vinylbenzoate, vinyl benzoic acid ethyl ester, 4-HBA (3-methacryloxypropyl) ester, (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) acrylic acid tributyl, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) benzyl acrylate, (methyl) isobornyl acrylate, vinyl cyanide, ethylene glycol single acetyl acetic acid esters list (methyl) acrylate etc.In addition, compound described in the paragraph 0021 ~ paragraph 0024 of Japanese Patent Laid-Open 2004-264623 publication can be enumerated.

Wherein, with regard to the viewpoint of film strength, preferably have and heated by (finally) and carry out other Component units (a3) of the base reacted with Component units (a2) or the other crosslinking chemical added.

Specifically, preferably there is the base of alcohol hydroxyl group, be particularly preferably 2-hydroxyethyl methacrylate.Above-mentioned have to be heated by (finally) and to be preferably 1 % by mole ~ 50 % by mole with other Component units (a3) that Component units (a2) or the crosslinking chemical that adds in addition carry out the base reacted relative to the ratio of whole (A) composition, be more preferably 5 % by mole ~ 40 % by mole, be particularly preferably 10 % by mole ~ 30 % by mole.

In addition; with regard to the viewpoint of light sensitivity; above-mentioned (A) composition is preferably relative to whole (A) composition; comprise the Component units containing the carboxyl not obtaining protection of 1 % by mole ~ 50 % by mole or contain the Component units not obtaining the phenolic hydroxyl group protected; be more preferably the above-mentioned Component units comprising 3 % by mole ~ 40 % by mole, be particularly preferably the above-mentioned Component units comprising 5 % by mole ~ 20 % by mole.As the above-mentioned Component units containing not obtaining carboxyl or the phenolic hydroxyl group protected, the monomer containing known acidic groups can be enumerated, wherein, being preferably hydroxy styrenes class or (methyl) acrylic acid, being more preferably methacrylic acid.

The above-mentioned monomer becoming other Component units (a3) can be used alone or two or more be combinationally used.

In addition, as other Component units (a3), with regard to the viewpoint of electrical characteristics, be preferably phenylethylene, there is the base of aliphatics ring type skeleton.Specifically, can enumerate: styrene, the 3rd butyl phenyl ether ethene, methyl styrene, hydroxy styrenes, α-methyl styrene, (methyl) acrylic acid two ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate etc.

In addition, as other Component units (a3), with regard to the viewpoint of adhesion, be preferably (methyl) alkyl acrylate.Specifically, (methyl 1) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate etc. can be enumerated.

About (A) composition, in any one form above-mentioned, all can have Component units (a3) composition, also can and with multiple.

In the present invention, preferably comprise the Component units containing carboxyl or the phenolic hydroxyl group protected by the form of acetal and the Component units containing the carboxyl or phenolic hydroxyl group that do not obtain protection simultaneously.

In photosensitive polymer combination of the present invention, (A) component of polymer preferably accounts for more than the 70wt% (percentage by weight) of the composition beyond desolventizing, and is more preferably and accounts for more than 90wt%.

The molecular weight >> of << (A) multipolymer

(A) molecular weight of multipolymer is with polystyrene conversion weight average molecular weight, is preferably 1,000 ~ 200,000, is more preferably 2,000 ~ 50, the scope of 000.If in the scope of above-mentioned numerical value, then light sensitivity and ITO adaptability good.

The ratio (dispersion degree) of number average molecular weight and weight average molecular weight is preferably 1.0 ~ 5.0, is more preferably 1.5 ~ 3.5.

The manufacture method >> of << (A) multipolymer

In addition, about the synthetic method of (A) composition, also there will be a known various method, if enumerate an example, then by utilizing radical polymerization initiator, make at least to carry out being polymerized in organic solvent synthesizing containing the free radical polymerization monomer potpourri for the formation of the free radical polymerization monomer of the Component units represented by above-mentioned (a1) and above-mentioned (a2).In addition, also synthesize by so-called high molecular weight reactive.

As the concrete example of multipolymer (A), as the example meeting (1), can enumerate:

Methacrylic acid 1-ethoxy ethyl ester/methacrylic acid/methacrylic acid (3-Ethyloxetane-3-base) methyl esters/2-hydroxyethyl methacrylate multipolymer (45/8/35/12),

Methacrylic acid 1-ethoxy ethyl ester/methacrylic acid/glycidyl methacrylate/allyl methacrylate/methacrylic acid two ring pentyl ester/styrol copolymer (35/10/30/5/15/15),

Methacrylic acid 1-cyclohexyloxy ethyl ester/methacrylic acid/glycidyl methacrylate/2-hydroxyethyl methacrylate/styrol copolymer (40/8/35/12/5),

Methacrylic acid tetrahydrofuran-2-base ester/methacrylic acid/methacrylic acid (3-Ethyloxetane-3-base) methyl esters/glycidyl methacrylate/2-hydroxyethyl methacrylate/styrol copolymer (35/10/15/15/15/10),

Methacrylic acid 1-ethoxy ethyl ester/methacrylic acid/methacrylic acid (3-Ethyloxetane-3-base) methyl esters/N-methoxy acrylamide/2-hydroxyethyl methacrylate multipolymer (40/5/40/5/10),

Methacrylic acid oxinane-2-base ester/methacrylic acid/methacrylic acid (3-Ethyloxetane-3-base) methyl esters/2-hydroxyethyl methacrylate/methacrylic acid two ring pentyl ester multipolymer (42/11/25/18/4),

As the example meeting (2), can enumerate:

The combination of methacrylic acid 1-ethoxy ethyl ester/methacrylic acid/2-hydroxyethyl methacrylate/benzylmethacrylate copolymers (60/10/10/20) and methacrylic acid (3-Ethyloxetane-3-base) methyl esters/methacrylic acid/2-hydroxyethyl methacrylate/benzylmethacrylate copolymers (60/10/10/20),

The combination etc. of methacrylic acid oxinane-2-base ester/methacrylic acid/2-hydroxyethyl methacrylate/methacrylic acid two ring pentyl ester multipolymer (65/5/10/20) and glycidyl methacrylate/N-methoxy acrylamide/methacrylic acid/methacrylic acid two ring pentyl ester/styrol copolymer (50/15/5/15/15).

< (B) light acid producing agent >

As the light acid producing agent used in the present invention, being preferably induction wavelength is more than 300nm, is preferably actinic ray and acidic compound that wavelength is 300nm ~ 450nm, but does not limit by its chemical constitution.In addition, be the photoactinic smooth acid producing agent of more than 300nm about directly not responding to wavelength, if by being used for responding to sensitizer the actinic ray and acidic compound that wavelength is more than 300nm, then preferably use after also can combining with sensitizer.As the light acid producing agent used in the present invention, be preferably and produce the light acid producing agent that pKa is the acid of less than 4, be more preferably and produce the light acid producing agent that pKa is the acid of less than 3.

With regard to the viewpoint of light sensitivity, (B) composition is preferably salt compound or oxime sulfonate compounds.Among these, with regard to the viewpoint of electrical characteristics, be more preferably oxime sulfonates.When oxime sulfonate compounds is used as acid producing agent, the compound that imines carries out dimerization is by-product as painted accessory substance.Although be infer all the time, think the compound represented by general formula (C) S-S decomposition and the free radical that produces can attack this coloring material, suppress painted thus.

As the example of light acid producing agent, can enumerate: trichloromethyl-s-triazine, sulfonium salt Huo Iodonium salt, quarternary ammonium salt class, diazomethane compound, acid imide sulfonate compound and oxime sulfonate compounds etc.Among these light acid producing agents, with regard to the viewpoint of insulativity, preferably use oxime sulfonate compounds.These light acid producing agents can be used alone a kind or two or more combinationally used.As the concrete example of trichloromethyl-s-triazine, two fragrant base Iodonium salts, triaryl matte salt, quarternary ammonium salt class and diazomethane derivative, compound described in the paragraph 0077 ~ paragraph 0078 of Japanese Patent Laid-Open 2011-221494 publication can be illustrated.

As oxime sulfonate compounds, namely there is the compound of oxime sulfonates structure, preferably can illustrate the compound containing the oxime sulfonates structure represented by following general formula (B1).

General formula (B1)

[changing 16]

(in general formula (B1), R ²¹represent alkyl, aryl, fluorinated alkyl, fluorinated alkyl.Wave-like line represents the bond with other bases.)

Any base all can be substituted, R ²¹in alkyl can be straight-chain, also can be branch-like, also can be ring-type.The substituting group of allowing below is described.

As R ²¹alkyl, be preferably the straight-chain alkyl of carbon number 1 ~ 10 or branch-like alkyl.R ²¹alkyl can be replaced by the alkoxy of the aryl of carbon number 6 ~ 11, carbon number 1 ~ 10 or naphthenic base (comprise the endocyclic alicyclic groups such as 7,7-dimethyl-2-oxo norborny, be preferably bicyclic alkyl etc.).

As R ²¹aryl, be preferably the aryl of carbon number 6 ~ 11, be more preferably phenyl or naphthyl.R ²¹aryl can by low alkyl group, alkoxy or halogen atom replace.

Above-claimed cpd containing oxime sulfonates structure represented by above-mentioned general formula (B1) for the oxime sulfonate compounds represented by following general formula (B2) also preferred.

[changing 17]

(in formula (B2), R ⁴²represent alkyl, aryl, fluorinated alkyl, fluorinated alkyl, X represents alkyl, alkoxy or halogen atom, and m4 represents the integer of 0 ~ 3, and when m4 is 2 or 3, multiple X can be identical, also can be different.)

Alkyl as X is preferably straight-chain alkyl or the branch-like alkyl of carbon number 1 ~ 4.

Alkoxy as X is preferably straight-chain alkoxy or the branch-like alkoxy of carbon number 1 ~ 4.

Halogen atom as X is preferably chlorine atom or fluorine atom.

M4 is preferably 0 or 1.

In above-mentioned general formula (B2), to be particularly preferably m4 be 1, X is methyl, and the position of substitution of X is ortho position, R ⁴²for straight-chain alkyl, 7,7-dimethyl-2-oxo norborny methyl or the compounds to toluyl groups of carbon number 1 ~ 10.

Compound containing oxime sulfonates structure represented by above-mentioned general formula (B1) for the oxime sulfonate compounds represented by following general formula (B3) also more preferably.

[changing 18]

(in formula (B3), R ⁴³implication and formula (B2) in R ⁴²identical, X ¹represent the alkoxy of the alkyl of halogen atom, hydroxyl, carbon number 1 ~ 4, carbon number 1 ~ 4, cyano group or nitro, n4 represents the integer of 0 ~ 5.)

As the R in above-mentioned general formula (B3) ⁴³, be preferably methyl, ethyl, n-pro-pyl, normal-butyl, n-octyl, trifluoromethyl, pentafluoroethyl group, perfluor-n-pro-pyl, perfluor-normal-butyl, p-methylphenyl, 4-chlorphenyl or pentafluorophenyl group, be particularly preferably n-octyl.

X ¹be preferably the alkoxy of carbon number 1 ~ 5, be more preferably methoxyl.

N4 is preferably 0 ~ 2, is particularly preferably 0 ~ 1.

As the concrete example of the compound represented by above-mentioned general formula (B3), can enumerate: α-(sulfonyloxy methyl oxygen base imido grpup) benzyl cyanide, α-(ethylsulfonyloxy imido grpup) benzyl cyanide, α-(n-pro-pyl sulfonyloxy imido grpup) benzyl cyanide, α-(normal-butyl sulfonyloxy imido grpup) benzyl cyanide, α-(4-tosyloxy imido grpup) benzyl cyanide, α-[(sulfonyloxy methyl oxygen base imido grpup)-4-methoxyphenyl] acetonitrile, α-[(ethylsulfonyloxy imido grpup)-4-methoxyphenyl] acetonitrile, α-[(n-pro-pyl sulfonyloxy imido grpup)-4-methoxyphenyl] acetonitrile, α-[(normal-butyl sulfonyloxy imido grpup)-4-methoxyphenyl] acetonitrile, α-[(4-tosyloxy imido grpup)-4-methoxyphenyl] acetonitrile.

As the concrete example of preferred oxime sulfonate compounds, can enumerate following compound (i) ~ compound (viii) etc., these compounds can be used alone a kind, or and use two or more.Compound (i) ~ compound (viii) can be used as commercially available product and obtains.In addition, also can combinationally use with (B) light acid producing agent of other kinds.

[changing 19]

As the compound containing the oxime sulfonates structure represented by above-mentioned general formula (B1), the compound represented by following general formula (OS-1) is also preferred.

[changing 20]

In above-mentioned general formula (OS-1), R ¹⁰¹represent hydrogen atom, alkyl, thiazolinyl, alkoxy, alkoxy carbonyl, acyl group, carbamyl, sulfamoyl, sulfo group, cyano group, aryl or heteroaryl.R ¹⁰²represent alkyl or aryl.

X ¹⁰¹represent-O-,-S-,-NH-,-NR ¹⁰⁵-,-CH ₂-,-CR ¹⁰⁶h-or-CR ¹⁰⁵r ¹⁰⁷-, R ¹⁰⁵~ R ¹⁰⁷represent alkyl or aryl.

R ¹²¹~ R ¹²⁴separately represent hydrogen atom, halogen atom, alkyl, thiazolinyl, alkoxy, amino, alkoxy carbonyl, alkyl-carbonyl, aryl carbonyl, amide group, sulfo group, cyano group or aryl.R ¹²¹~ R ¹²⁴in 2 can mutual bond and form ring respectively.

As R ¹²¹~ R ¹²⁴, be preferably hydrogen atom, halogen atom and alkyl, in addition, also preferably can enumerate R ¹²¹~ R ¹²⁴in at least 2 mutual bonds and form the form of aryl.Wherein, with regard to the viewpoint of light sensitivity, be preferably R ¹²¹~ R ¹²⁴be the form of hydrogen atom.

Already described functional group all can have substituting group further.

As the preference of the compound represented by above-mentioned general formula (OS-1), general formula described in the paragraph 0194 ~ paragraph 0202 of Japanese Patent Laid-Open 2011-221496 publication and exemplary compounds thereof can be enumerated.

In the present invention, as the compound containing the oxime sulfonates structure represented by above-mentioned general formula (B1), be preferably the oxime sulfonate compounds represented by following general formula (OS-3), following general formula (OS-4) or following general formula (OS-5).

[changing 21]

(in general formula (OS-3) ~ general formula (OS-5), R ²², R ²⁵and R ²⁸separately represent alkyl, aryl or heteroaryl, R ²³, R ²⁶and R ²⁹separately represent hydrogen atom, alkyl, aryl or halogen atom, R ²⁴, R ²⁷and R ³⁰separately represent halogen atom, alkyl, alkoxy, sulfonic group, amino-sulfonyl or alkyloxysulfonyl, X ¹~ X ³separately represent oxygen atom or sulphur atom, n ¹~ n ³separately represent 1 or 2, m ¹~ m ³separately represent the integer of 0 ~ 6.)

In above-mentioned general formula (OS-3) ~ general formula (OS-5), R ²², R ²⁵and R ²⁸in alkyl, aryl or heteroaryl can have substituting group.

In above-mentioned formula (OS-3) ~ general formula (OS-5), as R ²², R ²⁵and R ²⁸in alkyl, preferably can have the alkyl of substituent total carbon number 1 ~ 30.

In addition, in above-mentioned general formula (OS-3) ~ general formula (OS-5), as R ²², R ²⁵and R ²⁸in aryl, preferably can have the aryl of substituent total carbon number 6 ~ 30.

In addition, in above-mentioned general formula (OS-3) ~ general formula (OS-5), as R ¹in heteroaryl, preferably can have the heteroaryl of substituent total carbon number 4 ~ 30.

In above-mentioned general formula (OS-3) ~ general formula (OS-5), R ²², R ²⁵and R ²⁸as long as in heteroaryl at least 1 ring be assorted aromatic rings, such as mix aromatic rings and phenyl ring also can carry out contracting ring.

In above-mentioned general formula (OS-3) ~ general formula (OS-5), R ²³, R ²⁶and R ²⁹be preferably hydrogen atom, alkyl or aryl, be more preferably hydrogen atom or alkyl.

In above-mentioned general formula (OS-3) ~ general formula (OS-5), be preferably the R of existence more than 2 in compound ²³, R ²⁶and R ²⁹in 1 or 2 be alkyl, aryl or halogen atom, be more preferably 1 for alkyl, aryl or halogen atom, be particularly preferably 1 for alkyl and remaining as hydrogen atom.

In above-mentioned general formula (OS-3) ~ general formula (OS-5), R ²³, R ²⁶and R ²⁹in alkyl or aryl can have substituting group.Herein, as R ²³, R ²⁶and R ²⁹in the alkyl or aryl substituting group that can have, can illustrate and above-mentioned R ²², R ²⁵and R ²⁸in the identical base of the alkyl or aryl substituting group that can have.

As R ²³, R ²⁶and R ²⁹in alkyl, preferably can have the alkyl of substituent total carbon number 1 ~ 12, be more preferably the alkyl can with substituent total carbon number 1 ~ 6.

As R ²³, R ²⁶and R ²⁹in aryl, preferably can have the aryl of substituent total carbon number 6 ~ 30.

As R ²³, R ²⁶and R ²⁹in halogen atom, fluorine atom, chlorine atom, bromine atoms, atomic iodine can be enumerated.

Among these, be preferably chlorine atom, bromine atoms.

In above-mentioned general formula (OS-3) ~ general formula (OS-5), X ¹~ X ³separately represent O or S, be preferably O.

In above-mentioned general formula (OS-3) ~ general formula (OS-5), containing X ¹~ X ³ring as ring element is 5 rings or 6 rings.

In above-mentioned general formula (OS-3) ~ general formula (OS-5), n ¹~ n ³separately represent 1 or 2, work as X ¹~ X ³during for O, be preferably n ¹~ n ³be independently 1, in addition, work as X ¹~ X ³during for S, be preferably n ¹~ n ³be independently 2.

In above-mentioned general formula (OS-3) ~ general formula (OS-5), R ²⁴, R ²⁷and R ³⁰separately represent halogen atom, alkyl, alkoxy, sulfonic group, amino-sulfonyl or alkyloxysulfonyl.Wherein, R is preferably ²⁴, R ²⁷and R ³⁰be independently alkyl or alkoxy.

R ²⁴, R ²⁷and R ³⁰in alkyl, alkoxy, sulfonic group, amino-sulfonyl and alkyloxysulfonyl can have substituting group.

In above-mentioned general formula (OS-3) ~ general formula (OS-5), as R ²⁴, R ²⁷and R ³⁰in alkyl, preferably can have the alkyl of substituent total carbon number 1 ~ 30.

In above-mentioned general formula (OS-3) ~ general formula (OS-5), as R ²⁴, R ²⁷and R ³⁰in alkoxy, preferably can have the alkoxy of substituent total carbon number 1 ~ 30.

In addition, about preferred scope or the exemplary compounds of general formula (OS-3) ~ general formula (OS-5), can with reference to the record of the paragraph 0171 ~ paragraph 0200 of Japanese Patent Laid-Open 2011-227449 publication.

In photosensitive polymer combination of the present invention, (solid constituent is preferably relative to all resinous principles in photosensitive polymer combination, be more preferably above-mentioned (A) multipolymer) 100 mass parts, (B) light acid producing agent is preferably use 0.1 mass parts ~ 10 mass parts, is more preferably use 0.5 mass parts ~ 10 mass parts.Also can and use two or more.

Photosensitive polymer combination of the present invention also can containing 1,2-quinone di-azido compound as the photoactinic smooth acid producing agent of induction.1, although 2-quinone di-azido compound generates carboxyl by progressively type photochemical reaction, its quantum yield must be less than 1.

Compound (specific sulfocompound) > of < (C) represented by general formula (I)

Photoresist of the present invention is tieed up into thing and is contained (C) compound represented by following general formula (I).By adopting specific sulfocompound, adhesion can be reached and promote, and can promotion feeling luminosity, obtain the hardening thing that heat resistant transparent is high.

General formula (I)

[changing 22]

R ¹¹and R ¹²represent the base of at least 1 containing aliphatic alkyl, aromatic hydrocarbyl and heterocyclic radical respectively, be preferably aliphatic alkyl or aromatic hydrocarbyl, be preferably alkyl or aryl.Aliphatic alkyl and aromatic hydrocarbyl can have substituting group.

Aliphatic alkyl is preferably alkyl.Alkyl can have substituting group, in addition, also can be the alkyl of any one of straight chain, branch and ring-type.Under not containing substituent state, the carbon number of alkyl is preferably carbon number 1 ~ 10, is preferably 1 ~ 6, and then is more preferably 1 ~ 3.As the substituting group that alkyl can have, only otherwise depart from purport of the present invention, then and not specially provided for, but-OH ,-C (=O)-OR (R is hydrogen atom or substituting group) ,-NHCOR (R is hydrogen atom or substituting group), halogen atom, cyano group, thioether group and aryl can be illustrated.As R, be preferably hydrogen atom or alkyl, be preferably the alkyl of hydrogen atom or carbon number 1 ~ 10, be more preferably hydrogen atom or methyl, and then be more preferably methyl.

Aromatic hydrocarbyl is preferably aryl.Aryl can have substituting group, can be monocycle, also can be condensed ring.The carbon number of aryl is preferably carbon number 6 ~ 11, is more preferably carbon number 6.Aryl is preferably phenyl or naphthyl, is more preferably phenyl.As the substituting group that aryl can have, can illustrate :-OH ,-C (=O)-OR (R is hydrogen atom or substituting group) ,-NHCOR (R is hydrogen atom or substituting group), alkyl, halogen atom, cyano group, thioether group and aryl.As R, be preferably hydrogen atom or alkyl, be preferably the alkyl of hydrogen atom or carbon number 1 ~ 10, be more preferably hydrogen atom or methyl, and then be more preferably methyl.

Preferably comprise hydrogen atom as the base containing heterocyclic radical.Heterocycle can be heteroaromatic, also can be aliphatic heterocycle, in addition, is preferably 5 rings or 6 rings.In addition, can be monocycle, also can be condensed ring.

N is preferably 2 or 3, is more preferably 2.

(C) compound represented by general formula (I) is preferably represented by following general formula (II).

[changing 23]

R ²¹-L ¹¹-L ¹-S-S-L ²-L ¹²-R ²² (II)

(in general formula (II), R ²¹and R ²²represent hydrogen atom, alkyl or aryl respectively, L ¹and L ²represent alkylidene or arlydene respectively, L ¹¹and L ²²represent respectively *-O-C (=O)-or *-NH-C (=O)-.At * side and L ¹or L ²carry out bond.)

R ²¹and R ²²be preferably hydrogen atom or alkyl, be more preferably alkyl, and then be more preferably the alkyl of carbon number 1 ~ 10.

L ¹and L ²represent alkylidene or arlydene respectively, be preferably alkylidene.The carbon number of alkylidene is preferably 1 ~ 10, is more preferably 2 ~ 4, is particularly preferably 2.In addition, this alkylidene can by replacements such as alkyl, hydroxyl, alkoxy, halogen atom, cyano group, thioether group, carbonyls.But, be preferably alkylidene by-(CH ₂) _m-represent, m by more than 2 integer representation.Being more preferably m is 2 ~ 4.

The carbon number of arlydene is preferably 6 ~ 12, is more preferably 6.Arlydene can by replacements such as the alkyl be unsubstituted, hydroxyl, alkoxy, halogen atom, cyano group, thioether group, carbonyls.Arlydene is preferably phenylene.

L ¹¹and L ²²represent respectively *-O-C (=O)-or *-NH-C (=O)-, be more preferably *-O-C (=O)-.

It is 100 ~ 1000 that the specific sulfocompound used in the present invention is preferably molecular weight, and being more preferably molecular weight is 200 ~ 800, and then to be more preferably molecular weight be 200 ~ 600.By molecular weight is set to this kind of scope, can be non-volatile and promote contiguity, and promotion feeling luminosity under baking condition.

In photosensitive polymer combination of the present invention, relative to solid constituent 100 mass parts in photosensitive polymer combination, (C) specific sulfocompound is preferably use 0.1 mass parts ~ 10 mass parts, be more preferably use 0.5 mass parts ~ 5 mass parts, most preferably be use 1.0 mass parts ~ 4.0 mass parts.Also can and use two or more.In situation of more than two kinds, total amount becomes above-mentioned scope.

Below, the preference of (C) used in the present invention specific sulfocompound is represented.The present invention is not limited to these examples certainly.

[changing 24]

[changing 25]

< (D) solvent >

Photosensitive polymer combination of the present invention contains (D) solvent.Photosensitive polymer combination of the present invention is preferably prepared as following solution: make above-mentioned (A) composition ~ (D) composition as required composition, (E) described later composition ~ (I) composition as preferred composition and the solution of arbitrary component dissolves described later in (D) solvent.

As (D) solvent used in photosensitive polymer combination of the present invention, known solvent can be used, can illustrate: ethylene glycol monoalkyl ether class, glycol dialkyl ether class, ethylene glycol monoalkyl ether acetate class, propylene-glycol monoalky lether class, propylene glycol dialkyl ether, propylene-glycol monoalky lether acetate esters, diethylene glycol dialkyl ether class, diethylene glycol monoalkyl ether acetate class, dipropylene glycol monoalkylether class, dipropylene glycol dialkyl ether, dipropylene glycol monoalkylether acetate esters, ester class, ketone, amide-type, lactone etc.

As (D) solvent used in photosensitive polymer combination of the present invention, such as can with reference to the record of the paragraph 0166 ~ paragraph 0169 of Japanese Patent Laid-Open 2011-215580 publication.

These solvents can be used alone a kind or two or more is used in combination.Solvent used in the present invention be preferably used alone a kind or and with 2 kinds, be more preferably and use 2 kinds, and then be more preferably and use propylene-glycol monoalky lether acetate esters or dialkyl ether, diacetate esters class and diethylene glycol dialkyl ether class, or ester class and butylene glycol alkylether acetates class, most preferably be and use propylene glycol methyl ether acetate and diethylene glycol ethyl methyl ether.

In addition, as components D, be preferably that boiling point is more than 130 DEG C, solvent less than 160 DEG C, boiling point is the solvent of more than 160 DEG C, or these potpourri, be more preferably that boiling point is more than 130 DEG C, solvent less than 160 DEG C, boiling point is the solvent of more than 160 DEG C, less than 200 DEG C, or these potpourri, and then be more preferably boiling point and be more than 130 DEG C, be the potpourri of the solvent of more than 160 DEG C, less than 200 DEG C less than the solvents of 160 DEG C and boiling point.

As boiling point be more than 130 DEG C, solvent less than 160 DEG C, can illustrate: propylene glycol methyl ether acetate (boiling point is 146 DEG C), propylene glycol monoethyl ether acetate (boiling point is 158 DEG C), propylene glycol methyl-n-butyl ether (boiling point is 155 DEG C), propylene glycol methyl-positive propyl ether (boiling point is 131 DEG C).

As the solvent that boiling point is more than 160 DEG C, can illustrate: 3-ethoxyl ethyl propionate (boiling point is 170 DEG C), diethylene glycol methyl ethyl ether (boiling point is 176 DEG C), propylene glycol monomethyl ether propionate (boiling point is 160 DEG C), dipropylene glycol methyl ether acetic acid esters (boiling point is 213 DEG C), 3-methoxyl butyl ether acetic acid esters (boiling point is 171 DEG C), diethylene glycol diethyl ether (boiling point is 189 DEG C), diethylene glycol dimethyl ether (boiling point is 162 DEG C), propylene-glycol diacetate (boiling point is 190 DEG C), diethylene glycol monoethyl ether acetic acid esters (boiling point is 220 DEG C), dimethyl ether (boiling point is 175 DEG C), 1, 3-butylene glycol diacetate esters (boiling point is 232 DEG C).

(solid constituent is preferably relative to all resinous principles in photosensitive polymer combination, be more preferably above-mentioned (A) multipolymer) 100 mass parts, the content of (D) solvent in photosensitive polymer combination of the present invention is preferably 50 mass parts ~ 3,000 mass parts, be more preferably 100 mass parts ~ 2,000 mass parts, and then be more preferably 150 mass parts ~ 1,500 mass parts.

Other compositions of < >

In positive type photosensitive organic compound of the present invention, except (A) composition, (B) composition, (C) composition and (D) composition, optionally preferably can add (E) sensitizer, (F) crosslinking chemical, (G) touch modifying agent, (H) alkali compounds, (I) surfactant.And then, in positive type photosensitive organic compound of the present invention, plasticiser can be added, hot radical produces agent, antioxidant, thermal acid generator, ultraviolet light absorber, tackifier, development accelerant and organic or inorganic the known adjuvant such as antisettling agent.

(E) sensitizer

Photosensitive polymer combination of the present invention be preferably with the combination of (B) light acid producing agent in containing sensitizer, to promote the decomposition of light acid producing agent.Sensitizer absorbs actinic ray or radioactive ray and becomes electron excitation state.The sensitizer becoming electron excitation state contacts with light acid producing agent, and produces the effects such as electronics moves, energy moves, heating.Thus, light acid producing agent produces chemical change and decomposes, and generates acid.As the example of preferred sensitizer, can enumerate belong to following compounds and the wave band of 350nm ~ 450nm any one in there is the compound of absorbing wavelength.

The polynuclear aromatic same clan (such as pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxy anthracene, 9,10-diethoxy anthracene, 3,7-dimethoxy anthracene, 9,10-dipropoxy anthracene), xanthene (xanthene) class (such as fluorescein, eosin, erythrosine (erythrosine), rhodamine B, rose bengal), xanthone (such as xanthone, thioxanthone, dimethyl thioxanthone, diethyl thioxanthone), cyanine class (such as thia-carbonyl cyanine, oxa-carbocyanine), merocyanine class (such as merocyanine, carbonyl merocyanine), if red cyanines class, oxonols class, thiazide (such as thionine, methylenum careuleum, toluidine blue), acridine (such as acridine orange, chloroflavin, acriflavine), acridine ketone (such as acridone, 10-butyl-2-chloro-acridine ketone), Anthraquinones (such as anthraquinone), salt (such as the sour inner salt in side) in side's acid, styrene base class, basicity styrene base class (such as 2-[2-[4-(dimethylamino) phenyl] vinyl] benzoxazole), Coumarins (such as 7-diethylin 4-methylcoumarin, 7-hydroxyl 4-methylcoumarin, 2,3,6,7-tetrahydrochysene-9-methyl isophthalic acid H, 5H, 11H [1] chromene is [6,7,8-ij] quinolizine-11-ketone also).

Among these sensitizers, be preferably the polynuclear aromatic same clan, acridine ketone, styrene base class, basicity styrene base class, Coumarins, be more preferably the polynuclear aromatic same clan.Among the polynuclear aromatic same clan, most preferably be anthracene derivant.

Relative to light acid producing agent 100 weight portion of photosensitive polymer combination, the addition of the sensitizer in photosensitive polymer combination of the present invention is preferably 0 weight portion ~ 1000 weight portion, be more preferably 10 weight portion ~ 500 weight portions, and then be more preferably 50 weight portion ~ 200 weight portions.

Also can and use two or more.

(F) crosslinking chemical

Optionally, photosensitive polymer combination of the present invention is preferably containing crosslinking chemical.By adding crosslinking chemical, the cured film obtained by photosensitive polymer combination of the present invention can be made to become more firmly film.

As crosslinking chemical, as long as Yin Re and produce cross-linking reaction, then and unrestricted.(except A composition).Such as, there is in the molecule that can add the following stated the epoxy radicals of more than 2 or the compound of oxetanyl, the crosslinking chemical containing alkoxy methyl or there is the compound of at least 1 ethene unsaturated double-bond.

Among these crosslinking chemicals, be preferably in molecule and there is the epoxy radicals of more than 2 or the compound of oxetanyl, be particularly preferably epoxy resin.

Relative to total solid composition 100 weight portion of photosensitive polymer combination, the addition of the crosslinking chemical in photosensitive polymer combination of the present invention is preferably 0.01 weight portion ~ 50 weight portion, be more preferably 0.5 weight portion ~ 30 weight portion, and then be more preferably 2 weight portion ~ 10 weight portions.By adding within the scope of this, the cured film of physical strength and excellent solvent resistance can be obtained.Crosslinking chemical also can and with multiple, in the case, all crosslinking chemicals added up to and are calculated content.

There is in < molecule the epoxy radicals of more than 2 or the compound > of oxetanyl

As the concrete example of compound of epoxy radicals in molecule with more than 2, can enumerate: bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, aliphatic epoxy resin etc.

These compounds can be used as commercially available product and obtain.Include, for example commercially available product etc. described in the paragraph 0189 of Japanese Patent Laid-Open 2011-221494 publication.

In addition, also can enumerate: Ai Dike resin (ADEKA RESIN) EP-4000S, Ai Dike resin (ADEKA RESIN) EP-4003S, Ai Dike resin (ADEKA RESIN) EP-4010S, Ai Dike resin (ADEKA RESIN) EP-4011S (more than, Ai Dike (ADEKA) (share) manufactures), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (more than, Ai Dike (share) manufactures), Dai Nake (Denacol) EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (more than, length is rapids changes into manufacture), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (more than, Nippon Steel's chemistry manufactures) etc.

These compounds can be used alone a kind or two or more combinationally used.

Among these compounds, can more preferably enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin and aliphatic epoxy, aliphatic epoxy resin, particularly preferably can enumerate bisphenol A type epoxy resin.

As the concrete example of compound of oxetanyl in molecule with more than 2, can use sub-imperial oxetanes (ARON OXETANE) OXT-121, OXT-221, OX-SQ, PNOX (more than, East Asia synthesis (share) manufacture).

In addition, as other crosslinking chemicals, described containing the crosslinking chemical of alkoxy methyl and there is the compound etc. of at least 1 ethene unsaturated double-bond in the paragraph 0107 ~ paragraph 0108 of Japanese Patent Laid-Open 2012-8223 publication also preferably can be used.

(G) modifying agent is touched

Photosensitive polymer combination of the present invention also can touch modifying agent containing (G).(G) of photosensitive polymer combination used in the present invention touches the compound that modifying agent is the adhesion promoting inorganics silicon compounds such as (, the metals such as gold, copper, aluminium) such as silicon, monox, silicon nitrides and the dielectric film becoming base material.Specifically, silane coupling agent, mercaptan based compound etc. can be enumerated.The silane coupling agent touching modifying agent as (G) that use in the present invention is modified as target with surface, is not particularly limited, can uses known silane coupling agent.

As preferred silane coupling agent, include, for example: gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-glycidyloxypropyl silane, γ-glycidoxypropyl alkyl-dialkoxysilanes, γ-methacryloxypropyl trialkoxy silane, γ-methacryloxypropyl alkyl-dialkoxysilanes, γ-chloropropyl trialkoxy silane, γ-mercaptopropyi trialkoxy silane, β-(3,4-epoxycyclohexyl) ethyltrialkoxysilanes, vinyl trialkyl oxysilane.Among these, be more preferably γ-glycidyloxypropyl silane or γ-methacryloxypropyl trialkoxy silane, and then be preferably γ-glycidyloxypropyl silane, and then be more preferably 3-glycidoxypropyltrimewasxysilane.These silane coupling agents can be used alone a kind or two or more combinationally used.These silane coupling agents are effective for the lifting of the adhesion with substrate, and also effective for the adjustment of the cone angle with substrate.

Relative to total solid composition 100 mass parts in photosensitive polymer combination, the content that (G) in photosensitive polymer combination of the present invention touches modifying agent is preferably 0.1 mass parts ~ 30 mass parts, is more preferably 0.5 mass parts ~ 10 mass parts.

(H) alkali compounds

Photosensitive polymer combination of the present invention also can contain (H) alkali compounds.As (H) alkali compounds, at random select in the alkali compounds that can use in Chemical amplification resist to use.Include, for example: the quarternary ammonium salt etc. of fatty amine, aromatic amine, hetero ring type amine, hydroxide level Four ammonium, carboxylic acid.As these concrete example, compound described in the paragraph 0204 ~ paragraph 0207 of Japanese Patent Laid-Open 2011-221494 publication can be enumerated.

Alkali compounds used in the present invention can be used alone a kind, also can and with two or more, be preferably and with two or more, be more preferably and use 2 kinds, and then be more preferably and use 2 kinds of hetero ring type amine.

Relative to total solid composition 100 mass parts in photosensitive polymer combination, the content of (H) alkali compounds in photosensitive polymer combination of the present invention is preferably 0.001 mass parts ~ 1 mass parts, is more preferably 0.005 mass parts ~ 0.2 mass parts.

(I) surfactant

Photosensitive polymer combination of the present invention also can contain (I) surfactant.As (I) surfactant, can use negative ion system, kation system, nonionic system or both sexes any one, but preferred surfactant is nonionic system surfactant.

As the example of nonionic system surfactant, can enumerate: the higher aliphatic acid diesters class of polyoxyethylene higher alkyl ether, polyoxyethylene higher alkyl benzene ethers, polyoxyethylene glycol, silicone-based, fluorine system surfactant.In addition, following trade name can be enumerated: KP (SHIN-ETSU HANTOTAI's chemical industry (share) manufacture), Po Lifuluo (Polyflow) (common prosperity society chemistry (share) manufacture), Ai Futuo (Eftop) (Mitsubishi Materials electronics changes into (JEMCO) company and manufactures), Mei Jiafa (Megafac) (Di Aisheng (DIC) (share) manufactures), Fu Luode (Fluorad) (Sumitomo 3M (share) manufacture), A Sajia (Asahi Guard), Sha Fulong (Surflon) (Asahi Glass (share) manufacture), Pohle Floex (PolyFox) (manufacture of Ou Nuofa (OMNOVA) company), each series such as SH-8400 (eastern beautiful DOW CORNING silicone (Dow Coming Toray Silicone)).

In addition, as surfactant, compound described in the paragraph 0185 ~ paragraph 0188 of Japanese Patent Laid-Open 2011-215580 publication also can be adopted.

These surfactants can be used alone a kind or two or more is used in combination.

Relative to total solid composition 100 mass parts in photosensitive polymer combination, the addition of (I) surfactant in photosensitive polymer combination of the present invention is preferably below 10 mass parts, be more preferably 0.001 mass parts ~ 10 mass parts, and then be preferably 0.01 mass parts ~ 10 mass parts, and then be more preferably 0.01 mass parts ~ 3 mass parts, be particularly preferably 0.01 mass parts ~ 1 mass parts.

Antioxidant

Photosensitive polymer combination of the present invention also can contain antioxidant.Can containing known antioxidant as antioxidant.By adding antioxidant, there is following advantage: can prevent cured film painted, maybe the thickness that can reduce caused by decomposing reduce, in addition, heat resistant transparent is excellent.

As this kind of antioxidant, as this kind of antioxidant, such as, with reference to the record of the paragraph 0104 of Japanese Patent Laid-Open 2012-073609 publication, its content can be enrolled in present specification.

Relative to the total solid composition of photosensitive polymer combination, the content of antioxidant is preferably 0.1 quality % ~ 10 quality %, is more preferably 0.2 quality % ~ 5 quality %, is particularly preferably 0.5 quality % ~ 4 quality %.By being set within the scope of this, the film formed can obtain the sufficient transparency and pattern formed time light sensitivity also become good.

In addition, also using various ultraviolet light absorber described in " new development (Nikkan Kogyo Shimbun (share)) of polymeric additive " or metal passivator etc. as the adjuvant beyond antioxidant, can be added in photosensitive polymer combination of the present invention.

In addition, in the present invention, use and can not produce acid because of the irradiation exposing light in fact, and it is also preferred to carry out acidic sulphonic acid ester by heat.

Acid can not be produced by according to the infrared ray (Infrared before and after the exposure of compound in fact because exposing the irradiation of light, IR) spectrum or nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) spectroscopic assay, spectrum is unchanged to be judged.

The molecular weight of sulphonic acid ester is preferably 230 ~ 1, and 000, be more preferably 230 ~ 800.

Sulphonic acid ester used in the present invention can use commercially available sulphonic acid ester, also can use the sulphonic acid ester utilized synthesized by known method.Sulphonic acid ester such as by the basic conditions, makes sulfonic acid chloride or sulphonic acid anhydride and corresponding polyvalent alcohol carry out reacting to synthesize.

When the total content of (A) composition is set to 100 weight portion, the content of thermal acid generator in photosensitive polymer combination is preferably 0.5 weight portion ~ 20 weight portion, is more preferably 1 weight portion ~ 15 weight portion.

[acid proliferation generator]

In order to promotion feeling luminosity, photosensitive polymer combination of the present invention can use acid proliferation generator.

Acid proliferation generator used in the present invention produces acid further by acid catalyst reaction and make the compound that the acid concentration in reactive system rises, and the compound for stably existing under the state that there is not acid.This kind of compound increases the acid of more than a kind by 1 secondary response, therefore with the progress of reaction, reaction is carried out post, but the acid produced itself can bring out selfdecomposition, therefore the intensity of the acid of this place generation is in acid ionization constant, pKa, is preferably less than 3, is particularly preferably less than 2.

As the concrete example of acid proliferation generator, can enumerate: compound described in page the 2nd row of the paragraph 0203 ~ paragraph 0223 of Japanese Patent Laid-Open 10-1508 publication, the paragraph 0016 ~ paragraph 0055 of Japanese Patent Laid-Open 10-282642 publication and Jap.P. JP-A 9-512498 publication the 39th page of the 12nd row ~ 47.

Specifically, following compound etc. can be enumerated.

[changing 26]

As acid proliferation generator used in the present invention, the acid because producing from acid producing agent can be enumerated and decompose, and producing the compound that the pKa such as dichloroacetic acid, trichloroacetic acid, methane-sulforic acid, benzene sulfonic acid, trifluoromethanesulfonic acid, phenyl-phosphonic acid are the acid of less than 3.

With regard to the viewpoint of the dissolving contrast in exposure portion and unexposed portion, relative to light acid producing agent 100 weight portion, the content of acid proliferation generator in photosensitive polymer combination is preferably set to 10 weight portion ~ 1,000 weight portion, is more preferably and is set to 20 weight portion ~ 500 weight portions.

[development accelerant]

Photosensitive polymer combination of the present invention can contain development accelerant.

As development accelerant, the arbitrary compound with development accelaration effect can be used, but the compound of at least one structure during preferably there is the group being selected from carboxyl, phenolic hydroxyl group and alkylene oxide group, be more preferably the compound with carboxyl or phenolic hydroxyl group, most preferably be the compound with phenolic hydroxyl group.

In addition, as the molecular weight of (M) development accelerant, be preferably 100 ~ 2000, be more preferably 100 ~ 1000, most suitable is 100 ~ 800.

As the example of development accelerant, with reference to the record of the paragraph 0217 ~ paragraph 0217 of Japanese Patent Laid-Open 2011-221496 publication, its content can be enrolled in present specification.

Development accelerant can be used alone a kind, also can and use two or more.

With regard to the viewpoint of light sensitivity and residual film ratio, when (A) is become to be divided into 100 mass parts, the addition of the development accelerant in photosensitive polymer combination of the present invention is preferably 0 mass parts ~ 30 mass parts, be more preferably 0.1 mass parts ~ 20 mass parts, most preferably be 0.5 mass parts ~ 10 mass parts.

In addition, hot radical generation agent described in the paragraph 0120 ~ paragraph 0121 of Japanese Patent Laid-Open 2012-8223 publication and thermal acid generator also can be used as other adjuvants.

[manufacture method of cured film]

Secondly, the manufacture method of cured film of the present invention is described.

The manufacture method of cured film of the present invention preferably comprises the step of following (1) ~ (5).

(1) positive type photosensitive organic compound of the present invention is applied to the step on substrate;

(2) in the positive type photosensitive organic compound applied, remove the step of solvent;

(3) actinic ray is utilized to carry out the step exposed;

(4) aqueous developer solution is utilized to carry out the step of developing;

(5) the rear baking procedure of thermmohardening is carried out.

Next coming in order are described each step.

In the applying step of (1), be preferably the moistening film being applied to by positive type photosensitive organic compound of the present invention and substrate making containing solvent.

In the solvent removal step of (2), in the above-mentioned film applied, remove solvent by decompression (vacuum) and/or heating, thus form dry coating on substrate.

In the step of exposure of (3), be the actinic ray of more than 300nm, below 450nm to obtained film illumination wavelength.In this step, (B) light acid producing agent decomposes and produces acid.(A) catalyst action of the acid that contained in multipolymer sour decomposability gene produces and being hydrolyzed, thus generate carboxyl or phenolic hydroxyl group.

Having in the region of acid catalyst in generation, in order to accelerate said hydrolyzed reaction, and carrying out exposing rear heating: postexposure bake (Post Exposure Bake) (hereinafter also referred to as " PEB ").By PEB, can promote from the sour carboxyl of decomposability base or the generation of phenolic hydroxyl group.Temperature when carrying out PEB is preferably more than 30 DEG C, less than 130 DEG C, is more preferably more than 40 DEG C, less than 110 DEG C, is particularly preferably more than 50 DEG C, less than 100 DEG C.

The energy of activation that sour decomposability base in the Component units represented by formula (a1-1) in the present invention decomposes due to acid is low, easy reason exposes the acid being derived from acid producing agent that produces and decomposes, and produce carboxyl or phenolic hydroxyl group, therefore not PEB must be carried out, also erect image (positive image) is formed by development, but in the manufacture method of cured film of the present invention, the photosensitive polymer combination of the application of the invention carries out the rear baking procedure of (5), and the cured film obtained can reduce heat flow.Therefore, the cured film obtained by the manufacture method of cured film of the present invention when such as resist for substrate, even if heat cured film of the present invention together with substrate, the analyticity of pattern also worsens hardly.Moreover, in this manual, so-called " heat flow ", refers to that the section shape of the pattern cured film formed by exposure and development step is heating (preferably more than 180 DEG C to this cured film, be more preferably 200 DEG C ~ 240 DEG C) time distortion, the deterioration such as size, cone angle.

In the development step of (4), alkaline-based developer is used to develop to the multipolymer with free carboxyl or phenolic hydroxyl group.Removing comprising the region, exposure portion with the resin combination being easily dissolved in carboxyl in alkaline-based developer or phenolic hydroxyl group, forming erect image thus.

In the rear baking procedure of (5), by heating obtained erect image, the sour decomposability base in Component units (a1) can be made to carry out thermal decomposition and generate carboxyl or phenolic hydroxyl group, and be cross-linked with the crosslinking group, crosslinking chemical etc. of Component units (a2), can cured film be formed thus.This heating is preferably heated to the high temperature of more than 150 DEG C, is more preferably and is heated to 180 DEG C ~ 250 DEG C, is particularly preferably and is heated to 200 DEG C ~ 240 DEG C.Heat time can the suitable setting according to heating-up temperature etc., but is preferably set in the scope of 10 minutes ~ 120 minutes.

If added before rear baking procedure and irradiate actinic ray to developing pattern comprehensively, be preferably ultraviolet step, then the acid produced by irradiation actinic ray can be utilized to promote cross-linking reaction.

And then the cured film obtained by photosensitive polymer combination of the present invention also can be used as dry etching resist (dry etching resist).

When the cured film obtained utilizing the rear baking procedure of (5) to carry out thermmohardening is used as dry etching resist, the dry etching process such as ashing, plasma etching, ozone etching can be carried out as etch processes.

Secondly, the formation method of the cured film using photosensitive polymer combination of the present invention is specifically described.

The preparation method > of < photosensitive polymer combination

With arbitrary method, the required composition of (A) ~ (D) to be mixed with the ratio of regulation, then carry out stirring and dissolving to prepare photosensitive polymer combination.Such as, also can be dissolved in (D) solvent after making solution respectively making in advance (A) composition ~ (C) composition, these are prepared resin combination with the mixing of the ratio of regulation.The composition solution be prepared from as described above also can use aperture be after the filtrator etc. of 0.2 μm filters, in.

< applying step and solvent removal step >

Photosensitive polymer combination is applied on the substrate of regulation, removes solvent by reducing pressure and/or heating (prebake conditions), desired dry coating can be formed thus.As aforesaid substrate, such as, in the manufacture of liquid crystal display cells, can illustrate and Polarizer is set, and then black-matrix layer, color filter layers are optionally set, and then the glass plate etc. of transparent conductive circuit layer is set.There is no particular restriction for the method being applied to by photosensitive polymer combination on substrate, wherein, is preferably towards photosensitive resin coating composition on substrate in the present invention.Be not particularly limited towards the coating process on substrate, such as, can use the methods such as slot coated method, spray-on process, rolling method, method of spin coating.Wherein, be just suitable for regard to this viewpoint of large substrate, be preferably slot coated method.If manufacture with large substrate, then productivity is high and preferred.So-called large substrate herein, refers to that each limit is the substrate of size of more than 1m, below 5m.

In addition, (2) in the Component units (a1) of the heating condition of solvent removal step in unexposed portion in (A) composition, acid decomposability base decomposes, and do not make (A) composition be dissolvable in water scope in alkaline-based developer, also according to the kind of each composition or allotment than and different, but to be preferably at 80 DEG C ~ 130 DEG C heating 30 seconds ~ about 120 seconds.

< step of exposure and development step (pattern formation method) >

In step of exposure, across having the mask of pattern of regulation, actinic ray is irradiated to the substrate being provided with film.After step of exposure, optionally carry out heating (PEB), then in development step, use alkaline-based developer removed in region, exposure portion and form picture pattern.

Utilizing in photoactinic exposure, Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, chemical lamp, light emitting diode (Light Emitting Diode can be used, LED) light source, excimer laser generation device etc., can preferably use g ray (436nm), i ray (365nm), h ray (405nm) etc. to have the actinic ray of wavelength of more than wavelength 300nm, below 450nm.In addition, optionally also irradiation light is adjusted by point optical filter as long wavelength cutoff wave filter, short wavelength's cut-off filter, bandpass filter.

Containing alkali compounds in the developer solution preferably used in development step.As alkali compounds, such as, can use: the alkali metal hydroxides such as lithium hydroxide, NaOH, potassium hydroxide; The alkali carbonate such as sodium carbonate, sal tartari class; The alkaline metal bicarbonate such as sodium bicarbonate, potassium bicarbonate class; The ammonium hydroxide classes such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, bursine; The aqueous solution of sodium silicate, sodium metasilicate etc.In addition, also the aqueous solution of adding the water-miscible organic solvents such as appropriate methyl alcohol or ethanol or surfactant in the aqueous solution to above-mentioned bases can be used as developer solution.

The pH of developer solution is preferably 10.0 ~ 14.0.

Development time is preferably 30 seconds ~ 180 seconds, and in addition, the method for development can be covers any one method such as liquid formula (puddle) development method, infusion process etc.After development, the flowing water cleaning of 30 seconds ~ 90 seconds can be carried out, and the pattern desired by being formed.

After development, also rinsing step can be carried out.In rinsing step, utilize the substrate after the cleaning developments such as pure water, thus accompanying developer solution is removed, and the residue that will develop is removed.ELUTION METHOD can use known method.Include, for example spray drip washing or dipping drip washing etc.

Baking procedure (cross-linking step) > after <

Use the heating arrangement such as heating plate or baking oven; in the temperature of regulation; such as, at 180 DEG C ~ 250 DEG C; with official hour; if such as heating plate is then 5 minutes ~ 90 minutes, if baking oven is then 30 minutes ~ 120 minutes, the pattern corresponding with the unexposed area obtained by developing is heated; make cross-linking reaction carry out thus, the excellent diaphragm such as thermotolerance, hardness or interlayer dielectric can be formed thus.In addition, when heating, also can carry out in a nitrogen environment, promoting the transparency thus.

Also can before rear baking, toast with lower temperature after carry out after baking (middle baking procedure add).When carrying out centre baking, being preferably and heating after 1 minute ~ 60 minutes at 90 DEG C ~ 150 DEG C, toasting after carrying out under the high temperature more than 200 DEG C.In addition, also centre can be toasted, rear baking is divided into the multistage in more than 3 stages and heats.By the design of baking, rear baking in the middle of this kind, the cone angle of adjustable pattern.These heating can use the known heating means such as heating plate, baking oven, infrared heater.

Moreover, be preferably before heating, after utilizing actinic ray to expose again the figuratum substrate of formation, carry out rear baking (expose again/toast afterwards), produce acid from (B) composition be present in unexposed portion thus, and make it as promoting that the catalyzer of cross-linking step plays function.

That is, the formation method of cured film of the present invention is preferably between development step and rear baking procedure, comprises the step of exposure again utilizing actinic ray to expose again.As long as the exposure again in step of exposure utilizes the method identical with above-mentioned step of exposure to carry out, but in above-mentioned step of exposure again, be preferably the side the utilizing photosensitive polymer combination of the present invention of substrate being formed with to film and carry out blanket exposure.

The preferred exposure of step of exposure is 100mJ/cm again ²~ 1,000mJ/cm ².

[cured film]

Cured film of the present invention is cured film photosensitive polymer combination sclerosis of the present invention obtained.

Cured film of the present invention can be used as interlayer dielectric aptly.In addition, the cured film that obtains preferably by the formation method of cured film of the present invention of cured film of the present invention.

According to photosensitive polymer combination of the present invention, insulativity excellence can be obtained, also there is when at high temperature toasting the interlayer dielectric of high transparent.The interlayer dielectric of photosensitive polymer combination of the present invention is used to have high transparent, and cured film physical properties excellent, the purposes therefore for organic EL display or liquid crystal indicator is useful.

[organic EL display, liquid crystal indicator]

The feature of organic EL display of the present invention and liquid crystal indicator is to possess cured film of the present invention.

As organic EL display of the present invention or liquid crystal indicator, except have use the photosensitive polymer combination of the invention described above to be formed planarization film or interlayer dielectric except, there is no particular restriction, can enumerate the known various organic EL display or liquid crystal indicator that adopt various structure.

In addition, photosensitive polymer combination of the present invention and cured film of the present invention are not limited to such use, can be used for various uses.Such as; except planarization film or interlayer dielectric, also can be suitably used for colored filter diaphragm or in order to the thickness of the liquid crystal layer in liquid crystal indicator to be remained in fixing sept or solid photographic element the lenticule etc. be arranged on colored filter.

Glass substrate 6 is formed the TFT 1 of bottom gate polar form, and formation comprises Si under the state covering this TFT 1 ₃n ₄dielectric film 3.Formed on the insulating film 3 after explanations are omitted hering illustrated contact hole, form via this contact hole the distribution 2 (being highly 1.0 μm) being connected to TFT 1 on the insulating film 3.Distribution 2 is the lines in order to will be connected with TFT 1 between TFT 1 or by the organic EL formed in step thereafter.

And then, in order to make to form produced concavo-convex planarization by distribution 2, imbedding under the concavo-convex state produced by distribution 2, forming planarization layer 4 on the insulating film 3.

Planarization film 4 is formed the organic EL of bottom emission type.That is, the first electrode 5 comprising ITO is made to be connected to distribution 2 via contact hole 7 and to be formed on planarization film 4.In addition, the first electrode 5 is equivalent to the anode of organic EL.

Forming the dielectric film 8 of the shape of the periphery of covering first electrode 5, by arranging this dielectric film 8, the short circuit between the second electrode of being formed in the first electrode 5 and step thereafter can be prevented.

And then, although not shown in Fig. 1, but carry out evaporation successively via desired pattern mask to arrange hole transmission layer, organic luminous layer, electron transfer layer, then, whole of surface is formed the second electrode comprising A1, then by using glass for sealing plate and ultraviolet ray hardening type epoxy resin to carry out fitting sealing, and the organic EL display connecting the active array type in order to the TFT1 driven it on each organic EL is obtained.

Fig. 2 is the concept sectional view of an example of the liquid crystal indicator 10 representing active matrix mode.This color liquid crystal display arrangement 10 has the liquid crystal panel of back light unit 12 for the back side, and liquid crystal panel is configured with the element of the TFT16 corresponding with being configured in the 2 sheet glass substrates 14, all pixels between glass substrate 15 that are pasted with light polarizing film.Be formed in each element on glass substrate, by being formed at contact hole 18 in cured film 17 and the ito transparent electrode 19 of the tangible pixel electrode of distribution.The layer that ito transparent electrode 19 is provided with liquid crystal 20 and the RGB colored filter 22 being configured with black matrix".

Embodiment

Below, embodiment is enumerated to further illustrate the present invention.Only otherwise depart from purport of the present invention, then following the material shown in embodiment, use amount, ratio, contents processing, handling procedure etc. can be suitable for changing.Therefore, scope of the present invention is not limited to concrete example shown below.Moreover as long as in advance without special instruction, then " part ", " % " are quality criteria.

(A) component of polymer

In following synthesis example, following symbol represents following compound respectively.

V-65:2,2 '-azo two (2,4-methyl pentane nitrile) (manufacturing with the pure pharmaceutical worker's industry of light)

V-601: dimethyl-2,2 '-azo two (propionic acid 2-methyl esters) (manufacturing with the pure pharmaceutical worker's industry of light)

MATHF: methacrylic acid tetrahydrochysene-2H-furans-2-base ester (composite)

MAEVE: methacrylic acid 1-ethoxy ethyl ester (composite)

MATHP: methacrylic acid tetrahydrochysene-2H-pyrans-2-base ester (Xin Zhong village chemical industry)

StOEVE:4-(1-ethoxy ethoxy) styrene (composite)

GMA: glycidyl methacrylate (manufacturing with the pure pharmaceutical worker's industry of light)

OXE-30: methacrylic acid (3-Ethyloxetane-3-base) methyl esters (Osaka Organic Chemical Industry (share) manufacture)

NBMA: n-butoxy methyl acrylamide (the beautiful sun of Mitsubishi (share) manufacture)

HEMA: 2-hydroxyethyl methacrylate (manufacturing with the pure pharmaceutical worker's industry of light)

St: styrene (manufacturing with the pure pharmaceutical worker's industry of light)

DCPM: methacrylic acid two ring pentyl ester (Hitachi changes into industry)

MMA: methyl methacrylate (manufacturing with the pure pharmaceutical worker's industry of light)

PGMEA: acetic acid methoxyl propyl ester (manufacture of Showa electrician company)

HS-EDM: Ha Yisuo (Hisolve) EDM (manufacture of Dong Bang chemical industrial company)

The synthesis > of <MATHF

First methacrylic acid (86g, 1mol) is cooled to 15 DEG C, then adds camphorsulfonic acid (4.6g, 0.02mol).2-dihydrofuran (71g, 1mol, 1.0 equivalents) is dripped in this solution.Stir after 1 hour, add saturated sodium bicarbonate (500mL), and utilize ethyl acetate (500mL) to extract, after utilizing magnesium sulfate to carry out drying, insolubles is filtered, then below 40 DEG C, reduced pressure concentration is carried out, decompression distillation is carried out to the yellow oil of residue, and obtains methacrylic acid tetrahydrochysene-2H-furans-2-base ester (MATHF) 125g (productive rate is 80%) as boiling point (bp.) 54 DEG C ~ 56 DEG C/3.5mmHg cut of colorless oil.

The synthesis > of <MAEVE

To ethyl vinyl ether (144.2 parts, 2 molar equivalents) middle interpolation phenothiazine (phenothiazine) (0.5 part), in reactive system, one side is cooled to less than 10 DEG C one sides and drips methacrylic acid (86.1 parts, 1 molar equivalent) after, stir 4 hours under room temperature (25 DEG C).After adding p-toluenesulfonic acid pyridine (5.0 parts), at room temperature stir 2 hours, then at room temperature place a night.Sodium bicarbonate 5 parts and sodium sulphate (5 parts) is added in reactant liquor, at room temperature stir 1 hour, below 40 DEG C, reduced pressure concentration is carried out after being filtered by insolubles, decompression distillation is carried out to the yellow oil of residue, and obtains the methacrylic acid 1-ethoxy ethyl ester (MAEVE) (134.0 parts) as boiling point (bp.) 43 DEG C ~ 45 DEG C/7mmHg cut of colorless oil.

The synthesis > of < multipolymer (A) A-1

Under stream of nitrogen gas, HS-EDM (82 parts) heating is stirred to 90 DEG C.Last 2 hours and drip MATHF (43 parts (45.5 % by mole of equivalents)), OXE-30 (48 parts (37.5 % by mole of equivalents)), MAA (6 parts (9.5 % by mole of equivalents)), HEMA (11 parts (12.5 % by mole of equivalents)), radical polymerization initiator V-601 (trade name, with the pure pharmaceutical worker's industry of light (, share) manufacture, 4.3 parts) and the mixed solution of PGMEA (82 parts), and then react 2 hours at 90 DEG C, obtain the PGMEA solution (solid component concentration: 40%) of polymer A-1 thus.

The weight average molecular weight measured by gel permeation chromatography (Gel Permeation Chromatography, GPC) of the polymer A-1 obtained is 15,000.

The synthesis > of other polymkeric substance of <

Except described in used each monomer and use amount thereof being altered in following table, synthesize each multipolymer respectively in the mode identical with the synthesis of polymer A-1.

In above-mentioned table, the numerical value of the not additional especially unit in table using mol% as unit.The numerical value of polymerization initiator is mol% when monomer component being set to 100mol%.Solid component concentration represents as monomer weight/(monomer weight+weight of solvent) × 100 (unit weight %).When using V-601 as polymerization initiator, temperature of reaction being set to 90 DEG C, when using V-65 as polymerization initiator, temperature of reaction being set to 70 DEG C.

(B) light acid producing agent

B-1: gorgeous good solid (Irgacure) PAG-103 (manufacture of BASF (BASF) company)

B-2:PAI-101 (trade name, greening is learned (Midori Kagaku) company and manufactured)

B-3: the structure (thereafter synthesis example being described) shown in following

B-4: the structure shown in following, TPS-1000 (greening company manufactures)

B-1

[changing 27]

B-2

[changing 28]

B-3

[changing 29]

B-4

[changing 30]

Ts represents tosyl (p-toluenesulfonyl).

The synthesis > of <B-3

In the suspension solution of beta naphthal (10g), chlorobenzene (30mL), add aluminum chloride (10.6g), 2-chlorpromazine chloride (10.1g), react 2 hours after mixed liquor being heated to 40 DEG C.Under ice cooling, 4, in reactant liquor, drip the HCl aqueous solution (60mL) of 4N, then add ethyl acetate (50mL) and carry out separatory.Sal tartari (19.2g) is added in organic layer, react at 40 DEG C after 1 hour, add the HCl aqueous solution (60mL) of 2N and carry out separatory, after organic layer is concentrated, utilize diisopropyl ether (10mL) by crystallization more slurried (reslurry), then carry out filtering, dry and obtain ketonic compound (6.5g).

In the suspension solution of obtained ketonic compound (3.0g), methyl alcohol (30mL), add acetic acid (7.3g), 50 quality % aqueous hydroxylamine solutions (8.0g), and carry out heating backflow.After placing cooling, add water (50mL), separated out crystallization is filtered, after utilizing cold methanol to clean, in addition dry and obtain oxime compound (2.4g).

Obtained oxime compound (1.8g) is dissolved in acetone (20mL), adds triethylamine (1.5g), paratoluensulfonyl chloride (2.4g) under ice cooling, 4, react 1 hour after being warming up to room temperature.In reactant liquor, add water (50mL), after filtering separated out crystallization, utilize methyl alcohol (20mL) slurried again, then carry out filtering, dry and obtain B-6 (said structure) 2.3g.

Moreover, B-6's ¹h-NMR spectrum (300MHz, CDCl ₃) be δ=8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q, 1H), 2.4 (s, 3H), 1.7 (d, 3H).

(C) specific sulfocompound (compound by represented by general formula (I))

C-2: dibutyl disulfide, Ai Erdixi (Aldrich) company manufactures

C-5: diisoamyl disulfide, Tokyo changes into (share), and company manufactures

C-10: dithio dipropyl dimethyl phthalate, and light pure pharmaceutical worker's industry (share) company manufactures

C-11: dithiodipropionic acid, Tokyo changes into (share), and company manufactures

C-16: diphenyl disulfide, Ai Erdixi company manufactures

C-20: two (2-benzamide phenyl) disulfide, Tokyo changes into (share), and company manufactures

C-31: dipropyl trisulfide, composite

C-32: diphenyl trisulfide, composite

C-33: diphenyl tetrasulfide, composite

C-31 utilizes method described in " american chemical magazine (J.Am.Chem.Soc.) " 1952,74,3982 to synthesize, C-32 utilizes method described in " organic chemistry periodical (J.Org.Chem.) " 1980,45,5155 to synthesize, and C-33 utilizes method described in " organic chemistry periodical (J.Org.Chem.) " 2003,68,2489 to synthesize.

(D) solvent

Chemistry incorporated company of HS-EDM (diethylene glycol ethyl methyl ether) eastern nation manufactures

(E) sensitizer

E-1:DBA (dibutoxy anthracene) Kawasaki changes into industry (share) company and manufactures

(F) crosslinking chemical

F-1:JER157S65 (japan epoxy resin (Japan Epoxy Resins) (share) manufactures for trade name, phenol novolak type epoxy resin)

F-2: Buddhist nun's Clarke (Nikalac) MW-100LM (three manufacture with chemistry (Sanwa Chemical) (share))

F-3: trimethylolpropane triacrylate (East Asia synthesis manufactures)

(G) adhesion modifying agent

G-1:KBM-403 (trade name, 3-glycidoxypropyltrimewasxysilane, the structure shown in following, SHIN-ETSU HANTOTAI's chemical industry (share) manufactures)

[changing 31]

(H) alkali compounds

H-1:1,5-diazabicyclo [4.3.0]-5-nonene

H-2: triphenylimidazolyl

(1) surfactant

I-1: polyoxyethylene sorbitan fatty acid ester type surfactant (Suo Lugen (Sorgen) 90, first industrial pharmaceutical manufacture)

I-2: silicone-based surfactant SH-8400 (eastern beautiful DOW CORNING silicone)

(R) compare and use compound

In a comparative example, use following compound as the replacement composition of (C) compound represented by general formula (I).

R-1: dibutyl thiourea, and light pure pharmaceutical worker's industry company manufactures

R-2: two adjacent phenylthioureas, and light pure pharmaceutical worker's industry company manufactures

R-3: methyl-3-mercaptopropionic acid ester, SC organic chemistry (share) company manufactures, trade name MPM

R-4: thio-2 acid dimethyl ester, SC organic chemistry (share) company manufactures, TDM

R-5: diphenyl sulfide, and the pure pharmaceutical worker's industry (company) of light manufactures

R-6: dibutyl sulfide compound, and the pure pharmaceutical worker's industry (company) of light manufactures

R-7: thio-2 acid, and the pure pharmaceutical worker's industry (company) of light manufactures

[embodiment 1]

In the mode becoming the composition of table, each component dissolves is mixed, utilize bore to be that the teflon filtrator of 0.2 μm filters, and obtain the photosensitive polymer combination of embodiment 1.

[other embodiments and comparative example]

Except each compound used in embodiment 1 being altered to compound described in following table, carrying out dissolving with the addition identical with embodiment 1 and mix, and prepare the photosensitive polymer combination of following embodiment and comparative example.

The evaluation > of < light sensitivity

1 minute surface-treated glass substrate (healthy and free from worry (Corning) 1737 is being carried out with hexamethyldisilazane steam, 0.7mm thick (manufacture of healthy and free from worry (Corning) company)) on, after each photosensitive polymer combination of slot coated, carried out prebake conditions with 85 DEG C/150 seconds on hot plate and solvent is volatilized, thus forming the photosensitive polymer combination layer that thickness is 4.0 μm.

Then, utilize the PLA-501F exposure machine (extra-high-pressure mercury vapour lamp) that Canon (Canon) (share) manufactures, the mask across 9 μm of sectional hole patterns exposes obtained photosensitive polymer combination layer.Then, utilize alkaline-based developer (the tetramethyl ammonium hydroxide aqueous solution of 0.4 quality %), after the photosensitive composition layer after exposure being developed with 24 DEG C/60 seconds, utilize ultrapure water drip washing 20 seconds.

Optimum exposure (Eopt) when being formed the sectional hole patterns of 9 μm by these operations is set to light sensitivity.Moreover metewand is as described below.Value is more large better, and usage range is 6 ~ 4.

6: less than 30mJ/cm ²

5:30mJ/cm ²above, less than 60mJ/cm ²

4:60mJ/cm ²above, less than 90mJ/cm ²

3:90mJ/cm ²above, less than 120mJ/cm ²

2:120mJ/cm ²above, less than 150mJ/cm ²

1:150mJ/cm ²above

The < transparency evaluates >

At the film that glass substrate (healthy and free from worry (Corning) 1737,0.7mm thick (Corning Incorporated's manufacture)) upper formation thickness is 3.0 μm.Then, use i ray stepper (Canon's (share) FPA-3000i5+ processed), the mask across regulation exposes.After utilizing alkaline-based developer (2.38wt% tetramethyl ammonium hydroxide aqueous solution) to carry out within 65 seconds, covering the development of liquid formula at 23 DEG C, ultrapure water is utilized to carry out drip washing in 1 minute.Use extra-high-pressure mercury vapour lamp, under wavelength 365nm, 300mJ/cm is irradiated to the film after development ²light after, in an oven with 220 DEG C heating 45 minutes.Use spectrophotometer (U-3000: Hitachi (share) manufactures), under wavelength 400nm, measure the transmitance of this cured film.Minimum transmitance is shown in (initial (Fresh) transparency) in table.

And then, in an oven with 230 DEG C of heating 2 hours.Similarly measure the transmitance (heat-resisting rear permeability) of this cured film.

< adhesion evaluates >

After each photosensitive polymer combination slot coated is on ITO (tin indium oxide) substrate, Mo (molybdenum) substrate, titanium (Ti) substrate, on hot plate with 90 DEG C of heating 120 seconds, remove solvent thus, and form the photosensitive polymer combination layer that thickness is 4.0 μm.Utilize the PLA-501F exposure machine (extra-high-pressure mercury vapour lamp) that Canon's (share) manufactures, become 300mJ/cm with accumulative exposure ²(illumination: 20mW/cm ², i ray) mode obtained photosensitive polymer combination layer is exposed, thereafter, carry out heating for 1 hour to this substrate with 230 DEG C in an oven and obtain cured film.Use cutter, cut otch in length and breadth to be interposed between 1mm on cured film, then use adhesive tape (Scotch tape) to carry out belt stripping test.The adhesion between cured film and substrate is evaluated according to the area of the cured film being transferred to the adhesive tape back side.The results are shown in following table.Numerical value is less, higher with the adhesion of basal substrate, is preferably A or B.

A: through the area of transfer printing less than 1%

B: the area through transfer printing is more than 1%, less than 5%

C: the area through transfer printing is more than 5%

< keeping quality evaluates >

Obtained photosensitive polymer combination is left standstill 2 weeks in 30 DEG C of calibration cells, again carries out above-mentioned light sensitivity evaluation.The results are shown in following table.Light sensitivity variation is fewer, and the storage stability of resin combination is more excellent.

A: the variation of light sensitivity is less than 5%

B: light sensitivity variation is more than 5%

< comprehensive evaluation >

Being considered as in the light sensitivity of Photosensitve resin composition and cured film, the transparency, adhesion, conservatory situation, carry out following comprehensive evaluation.

5: the best performance, is rich in practicality

4: good performance, can be practical

3: although be usage range, it is desirable to be improved

2: due between maintaining period or purposes limited, be therefore difficult to practicality

1: cannot be practical

[table 3]

As clear and definite according to the above results, photosensitive polymer combination of the present invention is light sensitivity, heat resistant transparent, adhesion, the equal excellent photosensitive polymer combination of keeping quality.In contrast, the photosensitive polymer combination of the comparative example photosensitive polymer combination that to be any one characteristic all significantly not good enough.Specifically, the interpolation of alkali compounds can make light sensitivity decline.In addition, thiourea compound causes light sensitivity to decline because of its alkalescence, and in addition, mercaptan compound existence causes light sensitivity to change this problem because reacting with the transketalation of the resin with ethylidene ether structure.

[embodiment 30]

The organic EL display (with reference to Fig. 1) using thin film transistor (TFT) (Thin Film Transistor, TFT) is made by following method.

Glass substrate 6 is formed the TFT 1 of bottom gate polar form, and formation comprises Si under the state covering this TFT 1 ₃n ₄dielectric film 3.Then, this dielectric film 3 is formed after explanations are omitted hering illustrated contact hole, form via this contact hole the distribution 2 (being highly 1.0 μm) being connected to TFT 1 on the insulating film 3.This distribution 2 is the lines in order to will be connected with TFT 1 between TFT 1 or by the organic EL formed in step thereafter.

And then, in order to make to form produced concavo-convex planarization by distribution 2, imbedding under the concavo-convex state produced by distribution 2, on dielectric film 3, form planarization film 4.Formation towards the planarization film 4 on dielectric film 3 is spun on substrate by the photosensitive polymer combination of embodiment 16, after carrying out prebake conditions (90 DEG C × 2 minutes) on hot plate, uses high-pressure mercury-vapor lamp to irradiate 45mJ/cm on mask ²(illumination is 20mW/cm ²) i ray (365nm), then utilize alkaline aqueous solution to carry out developing and forming pattern, and carry out the heating of 60 minutes at 230 DEG C.

Coating during photosensitive resin coating composition is good, in the cured film obtained, does not see the generation of gauffer or slight crack after exposure, development, calcining.And then the average jump of distribution 2 is 500nm, the thickness of made planarization film 4 is 2,000nm.

Then, obtained planarization film 4 is formed the organic EL of bottom emission type.First, the first electrode 5 comprising ITO is made to be connected to distribution 2 via contact hole 7 and to be formed on planarization film 4.Thereafter, painting erosion resistant agent, and carry out prebake conditions, the mask across desired pattern exposes, and then develops.Using this Resist patterns as mask, carry out pattern processing by using the wet etching of ITO etchant.Thereafter, at 50 DEG C, use anticorrosive additive stripping liquid controlling (Remover 100, peace intelligence electronic material (AZ Electronic Materials) company manufactures) to be peeled off by this Resist patterns.The first electrode 5 obtained in the above described manner is equivalent to the anode of organic EL.

Then, the dielectric film 8 of the shape of the periphery of covering first electrode 5 is formed.The photosensitive polymer combination of embodiment 18 is used for dielectric film 8, forms dielectric film 8 in the same way as described above.By arranging this dielectric film 8, the short circuit between the second electrode of being formed in the first electrode 5 and step thereafter can be prevented.

And then, in vacuum deposition apparatus, carry out evaporation successively via desired pattern mask to arrange hole transmission layer, organic luminous layer, electron transfer layer.Then, whole of surface forms the second electrode comprising A1.In evaporator, taking out obtained aforesaid substrate, being undertaken fitting sealing by using glass for sealing plate and ultraviolet ray hardening type epoxy resin.

As described above, the organic EL display of the active array type connecting the TFT 1 in order to drive it on each organic EL is obtained.Execute alive result via driving circuit, known its is manifest good display characteristic and the high organic EL display of reliability.

[embodiment 31]

In active array type LCD described in Fig. 1 of Jap.P. No. 3321003 publication, form cured film 17 as follows as interlayer dielectric, and obtain the liquid crystal indicator of embodiment 31.

That is, use the photosensitive polymer combination of embodiment 18, with the method that the formation method of the planarization film 4 with the organic EL display in above-described embodiment is identical, form cured film 17 as interlayer dielectric.

Apply the result of driving voltage to obtained liquid crystal indicator, known its is manifest good display characteristic and the high liquid crystal indicator of reliability.

The explanation of symbol

1:TFT (thin film transistor (TFT))

2: distribution

3: dielectric film

4: planarization film

5: the first electrodes

6: glass substrate

7: contact hole

8: dielectric film

10: liquid crystal indicator

12: back light unit

14,15: glass substrate

16：TFT

17: cured film

18: contact hole

19:ITO transparency electrode

20: liquid crystal

22: colored filter

Claims

1. a photosensitive polymer combination, it comprises: (A) containing the component of polymer of the polymkeric substance of at least one meeting following (1) and following (2),

(B) light acid producing agent;

(C) compound represented by following general formula (I); And

(D) solvent;

General formula (I)

[changing 1]

2. photosensitive polymer combination according to claim 1, wherein, in general formula (I), R ¹¹and R ¹²be respectively aliphatic alkyl or aromatic hydrocarbyl.

3. photosensitive polymer combination according to claim 1, wherein, in general formula (I), R ¹¹and R ¹²be respectively the alkyl of carbon number 1 ~ 10 or the aryl of carbon number 6 ~ 11.

4. photosensitive polymer combination according to claim 1, wherein, (C) compound represented by general formula (I) is represented by following general formula (II):

[changing 2]

R ²¹-L ¹¹-L ¹-S-S-L ²-L ¹²-R ²² (II)

5. photosensitive polymer combination according to any one of claim 1 to 4, wherein, the Component units of residue of described Component units (a1) for there is carboxyl being protected by the form of acetal.

6. photosensitive polymer combination according to any one of claim 1 to 4, wherein, described Component units (a1) is the Component units represented by following formula (A2 '):

Formula (A2 ')

[changing 3]

7. photosensitive polymer combination according to any one of claim 1 to 6, wherein, described bridging property base is for being selected from epoxy radicals, oxetanyl ,-NH-CH ₂at least a kind in-OR (R is the alkyl of carbon number 1 ~ 20).

8. photosensitive polymer combination according to any one of claim 1 to 7, wherein, described photosensitive polymer combination is chemical amplification positive photosensitive polymer combination.

9. photosensitive polymer combination according to any one of claim 1 to 8, wherein, (B) light acid producing agent is oxime sulfonate compounds or salt compound.

10. a manufacture method for cured film, it comprises:

(1) photosensitive polymer combination according to any one of claim 1 to 9 is applied to the step on substrate;

(3) active radioactive ray are utilized to carry out the step exposed;

(5) the rear baking procedure of thermmohardening is carried out.

The manufacture method of 11. cured films according to claim 10, after it is included in described development step, before described rear baking procedure, carries out the step of blanket exposure.

The manufacture method of 12. cured films according to claim 10 or 11, wherein, described substrate is metal substrate.

13. 1 kinds of cured films, it makes photosensitive polymer combination according to any one of claim 1 to 9 harden and be formed.

14. cured films according to claim 13, it is interlayer dielectric.

15. 1 kinds of liquid crystal indicators or organic electroluminescence display device and method of manufacturing same, it comprises the cured film according to claim 13 or 14.