CN106324986A

CN106324986A - A photosensitive resin composition, a method for producing a cured film, a cured film, and a liquid crystal display device

Info

Publication number: CN106324986A
Application number: CN201610395970.5A
Authority: CN
Inventors: 山田悟; 金子若彦
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2015-06-30
Filing date: 2016-06-07
Publication date: 2017-01-11
Also published as: KR20170003380A; TW201701066A; JP2017016116A; TWI693470B; JP6437955B2

Abstract

An object of the present invention is to provide a photosensitive resin composition capable of forming an interlayer insulating film which is also an alignment film, a method for producing a cured film using the same, a cured film, and a liquid crystal display device. A photosensitive resin composition comprises a photosensitive resin composition containing a polymer component A1 and a photoacid generator B1, and the polymer component A1 contains a composition comprising a group having a group protected by an acid-decomposable group. The polymer A1-1 of the unit a1 satisfies at least one of the following 1 to 3: 1: the polymer A1-1 further comprises constituent units a2; 2: as the polymer component A1, the polymer A1-1 further comprises the polymer A1-2 of the constituent unit a2 having a crosslinkable group; 3: the polymer A1-1 further further contains a crosslinking agent C1 having a crosslinkable group having a molecular weight of 1,000 or less and satisfies at least one of the following requirements: 4: The polymer A1-1 or the polymer A1-2 comprises the constituent units shown in the following s1, and 5 :the polymer A1 further contains the polymer A1-3 containing the specific constituent unit.

Description

Photosensitive polymer combination, the manufacture method of cured film, cured film and liquid crystal display Device

Technical field

The present invention relates to photosensitive polymer combination, the manufacture method of cured film, cured film and liquid crystal indicator.

Background technology

Liquid crystal indicator can become slim, light weight and the such advantage of low power consumption owing to having, so at various electricity Subset is widely used.

Additionally, liquid crystal indicator is usually provided with the interlayer dielectric formed through pattern.

In the formation of this interlayer dielectric, from few and can obtain and fill for obtaining the process number of required pattern form The such reason of flatness divided is set out, and photosensitive polymer combination is widely used.

Such as, in patent documentation 1, as the photosensitive polymer combination of so-called chemical amplifying type, describe and " contain Have: (A-1) comprise the component of polymer of the polymer of at least one met in following (1) and (2), (B-1) light acid producing agent, (C-1) photosensitive polymer combination of solvent, wherein, (1) has the acidic group base by acid decomposability radical protection containing (a1-1) The Component units of group and (a1-2) have the polymer of the Component units of crosslinkable groups, or (2) have Component units (a1-1) Polymer and there is the polymer of Component units (a1-2) " ([claim 1]), additionally, as NQD (naphthoquinone two nitrine) type Photosensitive polymer combination, describe and " contain: (A-2) comprises (a2-1) and have the Component units of acidic group and (a2-2) has The component of polymer of the Component units of crosslinkable groups, (B-2) quinone diazide, the photosensitive resin composition of (C-2) solvent Thing " ([claim 2]).

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2014-197155 publication

Summary of the invention

Invent problem to be solved

On the other hand, in patent documentation 1, describe and there is the cured film making photosensitive polymer combination solidify and to obtain As the liquid crystal indicator ([0189] [0190]) of interlayer dielectric, including the known liquid crystal of patent documentation 1 In showing device, in order to make the liquid crystal molecule used in liquid crystal cells be orientated, need on interlayer dielectric, arrange alignment films.

Therefore, the problem of the present invention is to provide the photoresist group that can form the interlayer dielectric doubling as alignment films Compound and employ its manufacture method of cured film, cured film and liquid crystal indicator.

For the method solving problem

The present inventors conducts in-depth research to reach above-mentioned problem, it was found that by coordinating containing having fluorine The Component units of the part-structures such as substituted hydrocarbon radical and there is the polymer of Component units of light orientation group, it is possible to formed and double as The interlayer dielectric of alignment films, thus complete the present invention.

That is, find to reach above-mentioned problem by following being configured to.

[1] a kind of photosensitive polymer combination, it is containing component of polymer A1 and the photonasty tree of light acid producing agent B1 Oil/fat composition, described component of polymer A1 contains and comprises the Component units a1 having acidic group by the group of acid decomposability radical protection Polymer A 1-1,

Meet at least one in following 1～3:

1: above-mentioned polymer A 1-1 comprises the Component units a2 with crosslinkable groups further,

2: as above-mentioned component of polymer A1, contain the polymerization comprising the Component units a2 with crosslinkable groups further Thing A1-2,

3: contain the cross-linking agent C1 that molecular weight is 1, less than 000 with crosslinkable groups further,

Further, at least one in following 4 and 5 is met:

4: above-mentioned polymer A 1-1 or above-mentioned polymer A 1-2 comprise the Component units shown in following s1,

5: as above-mentioned component of polymer A1, contain the polymer comprising the Component units shown in following s1 further A1-3,

S1: have and select in the group that free fluorine substituted hydrocarbon radical, siloxane backbone and alkyl that carbon number is 10～30 form The Component units of at least one part-structure and there is the Component units of light orientation group.

[2] according to the photosensitive polymer combination described in [1], wherein, above-mentioned acidic group is by the base of acid decomposability radical protection Group is the acidic group protected group of form with acetal.

[3] a kind of photosensitive polymer combination, it is the photonasty containing component of polymer A2 Two azide of quinone B2 Resin combination, described component of polymer A2 contains polymer A 2-1 comprising the Component units a3 with acidic group,

Meet at least one in following 1～3:

1: above-mentioned polymer A 2-1 comprises the Component units a2 with crosslinkable groups further,

2: as above-mentioned component of polymer A2, contain the polymerization comprising the Component units a2 with crosslinkable groups further Thing A2-2,

3: contain the cross-linking agent C2 that molecular weight is 1, less than 000 with crosslinkable groups further,

Further, at least one in following 4 and 5 is met:

4: above-mentioned polymer A 2-1 or above-mentioned polymer A 2-2 comprise the Component units shown in following s1,

5: as above-mentioned component of polymer A2, contain the polymer comprising the Component units shown in following s1 further A2-3,

[4] according to the photosensitive polymer combination according to any one of [1]～[3], wherein, above-mentioned smooth orientation group is Reacted by photodimerization and give the group of orientation.

[5] according to the photosensitive polymer combination according to any one of [1]～[4], wherein, above-mentioned smooth orientation group is Cinnamic acid ester group or chalcone derivative base.

[6] according to the photosensitive polymer combination according to any one of [1]～[5], wherein, above-mentioned crosslinkable groups is ring Epoxide or oxetanyl.

[7] according to the photosensitive polymer combination according to any one of [1]～[6], wherein, have shown in above-mentioned s1 The content of the polymer of Component units is 0.1～20 mass % relative to all solids composition of compositions.

[8] according to the photosensitive polymer combination according to any one of [1]～[7], wherein, containing organic solvent D.

[9] manufacture method of a kind of cured film, it includes following operation:

The operation that photosensitive polymer combination described in [8] is applied on substrate；

The operation of organic solvent D is removed from the photosensitive polymer combination being coated with；

The operation photosensitive polymer combination eliminating organic solvent D being exposed by activity lonizing radiation；

Utilize the operation that exposed photosensitive polymer combination is developed by developer solution；With

Developed photosensitive polymer combination is carried out heat cure and obtains the operation of cured film.

[10] a kind of cured film, it is to make the photosensitive polymer combination according to any one of [1]～[8] solidify Cured film.

[11] a kind of liquid crystal indicator, it has the cured film described in [10].

Invention effect

In accordance with the invention it is possible to provide can be formed the interlayer dielectric doubling as alignment films photosensitive polymer combination, And employ the manufacture method of its cured film, cured film and liquid crystal indicator.

Detailed description of the invention

Hereinafter, the present invention is described in detail.

The explanation of constitutive requirements set forth below is sometimes based upon the representational embodiment of the present invention and carries out, but this Bright it is not limited to such embodiment.

It addition, in this specification, use "～" numerical range that represents refer to using "～" before and after the numerical value recorded as The scope that lower limit and higher limit comprise.

In the statement of group (atomic group) in this manual, do not record replacement and unsubstituted statement comprises and do not has The group (atomic group) of substituent group, also comprises the group (atomic group) with substituent group simultaneously.Such as so-called " alkyl ", not only wraps Contain the alkyl (unsubstituted alkyl) without substituent group, and comprise the alkyl (replacement alkyl) with substituent group.

In this specification, " (methyl) acrylate " is to represent " acrylate " or the statement of " methacrylate ", " (methyl) acrylic acid " is to represent " acrylic acid " or the statement of " methacrylic acid ", and " (methyl) acryloyl group " is to represent " propylene Acyl group " or the statement of " methylacryloyl ".

In this specification, solid constituent is the solid constituent at 25 DEG C.

In this specification, the weight average molecular weight of polymer and number-average molecular weight are as utilizing GPC (gel permeation chromatography) The polystyrene conversion value measured defines.

The photosensitive polymer combination (following, also referred to as " the 1st mode of the present invention ") described in 1st mode of the present invention For a kind of photosensitive polymer combination, it contains component of polymer A1 and light acid producing agent B1, and described component of polymer A1 contains Comprise polymer A 1-1 that there is acidic group by the Component units a1 of the group of acid decomposability radical protection, meet in described later 1～3 At least one in shown condition, and, meet at least one in the condition shown in described later 4 and 5.

Additionally, the photosensitive polymer combination described in the 2nd mode of the present invention (below, is also referred to as " the 2nd of the present invention Mode ") it is a kind of photosensitive polymer combination, it contains component of polymer A2 Two azide of quinone B2, and described polymer becomes Point A2 contains polymer A 2-1 comprising the Component units a3 with acidic group, meets in the condition shown in described later 1～3 extremely Few one, and, meet at least one in the condition shown in described later 4 and 5.

Photosensitive polymer combination described in 1st mode of the present invention and the 2nd mode is had in s1 described later by cooperation The polymer of shown Component units is as component of polymer A1 or component of polymer A2, it is possible to form the interlayer doubling as alignment films Dielectric film.

Its details is the most unclear, but the present inventors is presumed as follows.

I.e., it is believed that owing to having in the polymer of the Component units shown in s1 described later containing having light orientation group Component units, contain the Component units with part-structures such as fluorine substituted hydrocarbon radicals simultaneously, thus, applied at resin combination After substrate (such as, thin film transistor (TFT) etc.) is upper, comprise the polymer of the Component units with light orientation group to film Near surface is divided a word with a hyphen at the end of a line (oozing out), and after heat cure, light orientation group deflection is present in the near surface of cured film, so also can Enough as alignment films (optical alignment film) function.

Then, each compositions such as the component of polymer used in the 1st mode of the present invention and the 2nd mode are carried out specifically Bright.

[the 1st mode of the present invention]

1st mode of the present invention contains following component of polymer A1 and light acid producing agent B1.

(component of polymer A1)

The component of polymer A1 contained by 1st mode of the present invention for containing comprise have acidic group by acid decomposability group protect The component of polymer of polymer A 1-1 of the Component units a1 of the group protected.

Wherein, component of polymer A1 is by the work of the acidic materials of the catalytic amount by smooth acid producing agent B1 described later generation With, the sour decomposability group in above-mentioned polymer A 1-1 carries out deprotection reaction, produces acidic group, it is possible to carry out solidification anti- Should.

Additionally, component of polymer A1 means, in addition to comprising above-mentioned polymer A 1-1, also to comprise and be added as needed on The component of polymer of other polymer.

In the present invention, the polymer contained by component of polymer A1 is preferably the polymer of addition polymerization type, more preferably Comprise from (methyl) acrylic acid and/or the polymer of the Component units of its ester.

In addition it is also possible to have the Component units in addition to the Component units from (methyl) acrylic acid and/or its ester, example As from cinnamic Component units or from the Component units etc. of vinyl compound.

Additionally, " from (methyl) acrylic acid and/or the Component units of its ester " is also referred to as " acrylic acid series Component units ".

1st mode of the present invention must be fulfilled in the condition shown in following 1～3 at least one and meet following 4 And at least one in the condition shown in 5.

This represents: comprising polymer A 1-1 having acidic group by the Component units a1 of the group of acid decomposability radical protection In or have with being different from polymer A 1-1 and contribute to the position of crosslinkable groups of solidification or composition is necessary；With comprise The component of polymer of the Component units with light orientation group and the Component units being present in surface for making it be partial to is must Must.

Therefore, in the following description, it is not centered by every kind of polymer, but using necessary as component of polymer Polymer in Component units centered by illustrate.

(condition)

Component of polymer A1 comprises and at least contains the Component units a1 having acidic group by the group of acid decomposability radical protection Polymer A 1-1.Polymer A 1-1 with Component units a1 is comprised, it is possible to make sensitivity high by component of polymer A1 The resin combination of chemical amplifying type.

About " acidic group is by the group of acid decomposability radical protection " in the present invention, can as acidic group and acid decomposability group To use known group, it is not particularly limited.

As acidic group, such as carboxyl, phenolic hydroxyl group etc. preferably can be listed.

Additionally, as acid decomposability group, group (the ester the most described later knot being easier to decomposition by acid ratio can be listed The functional groups of acetal system such as structure, Pentamethylene oxide. ester group or oxolane ester group) or by group (the such as uncle of the more difficult decomposition of acid ratio The carbonic acid tertiary alkyl ester groups such as tertiary alkyl ester group, t-butyl carbonate base such as butyl ester base) etc..

There is acidic group and preferably be there is carboxyl by acid decomposability by the Component units a1 of the group of acid decomposability radical protection The Component units of the protection carboxyl of radical protection is (hereinafter also referred to as " having by the structure of the protection carboxyl of acid decomposability radical protection Become unit ") or have phenolic hydroxyl group by acid decomposability radical protection protection phenolic hydroxyl group Component units (hereinafter also referred to as " have by the Component units of protection phenolic hydroxyl group of acid decomposability radical protection ").

Hereinafter, the Component units a1-1 of carboxyl is protected to be divided by acid with having having by acid decomposability radical protection successively The Component units a1-2 of the protection phenolic hydroxyl group of solution property radical protection illustrates respectively.

<<having by the Component units a1-1 of the protection carboxyl of acid decomposability radical protection>>

The above-mentioned Component units a1-1 having by the protection carboxyl of acid decomposability radical protection is containing the structure with carboxyl Become the carboxyl Component units by the protection carboxyl of sour decomposability radical protection described further below of unit.

As may be used for the above-mentioned of the above-mentioned Component units a1-1 having by the protection carboxyl of acid decomposability radical protection There is the Component units of carboxyl, known Component units can be used without particular limitation.Can list such as from insatiable hunger With the unsaturated carboxylic acid etc. that monocarboxylic acid, unsaturated dicarboxylic, unsaturated tricarboxylic acids etc. have at least one carboxyl in the molecule Component units a1-1-1 or there is ethylenically unsaturated group and the Component units a1-1-2 of the structure from anhydride simultaneously.

Hereinafter, the a1-1-1 used as the above-mentioned Component units with carboxyl is i.e. had at least one in molecule The Component units of the unsaturated carboxylic acid etc. of individual carboxyl and a1-1-2 have ethylenically unsaturated group and the knot from anhydride the most simultaneously The Component units of structure illustrates the most successively.

<<<there is in molecule the Component units a1-1-1 of the unsaturated carboxylic acid etc. of at least one carboxyl>>>

About as the above-mentioned Component units a1-1-1 from the unsaturated carboxylic acid etc. in molecule with at least one carboxyl And the unsaturated carboxylic acid used in the present invention, the paragraph 0043 of such as Japanese Unexamined Patent Publication 2014-238438 publication can be listed Described in compound.

Wherein, from the viewpoint of developability, in order to form above-mentioned Component units a1-1-1, acrylic acid, first are preferably used Base acrylic acid, 2-(methyl) acryloyl-oxyethyl-succinic acid, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl-phthalic acid or the acid anhydride etc. of unsaturated polybasic carboxylic acid, more preferably use acrylic acid, first Base acrylic acid, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid.

The above-mentioned Component units a1-1-1 from the unsaturated carboxylic acid etc. having at least one carboxyl in molecule can be by one Plant and be separately formed, it is also possible to be made up of two or more.

<<<there is ethylenically unsaturated group and the Component units a1-1-2 of structure from anhydride simultaneously>>>

There is ethylenically unsaturated group simultaneously and the Component units a1-1-2 from the structure of anhydride is preferably from making tool The unit of the monomer having a hydroxyl and anhydride reaction present in the Component units of ethylenically unsaturated group and obtain.

As above-mentioned anhydride, it is possible to use known anhydride, specifically, maleic anhydride, succinic anhydrides, clothing can be listed The dibasic acid anhydrides such as health anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride；Benzene partially The anhydride such as three anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic anhydride, biphenyltetracarboxyacid acid acid anhydride.In them, from the viewpoint of developability Set out, preferably phthalic anhydride, tetrabydrophthalic anhydride or succinic anhydrides.

The response rate relative to hydroxyl of above-mentioned anhydride, from the viewpoint of developability, preferably 10～100 moles %, More preferably 30～100 moles of %.

(may be used for the sour decomposability group of Component units a1-1)

As may be used for the above-mentioned of the above-mentioned Component units a1-1 having by the protection carboxyl of acid decomposability radical protection Acid decomposability group, it is possible to use above-mentioned sour decomposability group.

In these acid decomposability groups, carboxyl is the protected protection carboxyl of the form with acetal, and this is from resin combination Basic physical properties, particularly sensitivity or pattern form, the formative of contact hole, the viewpoint of storage stability of resin combination go out It is preferred for sending out.And then in acid decomposability group, carboxyl is that the form with acetal represented by following formula a1-10 is protected Protection carboxyl, this from the viewpoint of sensitivity more preferably.It addition, when carboxyl be represented by following formula a1-10 with the shape of acetal During formula protected protection carboxyl, as the entirety of protection carboxyl, become-(C=O)-O-CR¹⁰¹R¹⁰²(OR¹⁰³) structure.

[chemical formula 1]

In formula a1-10, R¹⁰¹And R¹⁰²Separately represent hydrogen atom or alkyl, wherein, by R¹⁰¹With R¹⁰²It is hydrogen former Except the situation of son.R¹⁰³Represent alkyl.R¹⁰¹Or R¹⁰²With R¹⁰Can also link and form cyclic ether.

In above-mentioned formula a1-10, R¹⁰¹～R¹⁰³Separately representing hydrogen atom or alkyl, abovementioned alkyl can be straight chain Shape, branched, ring-type in any one.Wherein, will not R¹⁰¹And R¹⁰²Both expression hydrogen atom, but R¹⁰¹And R¹⁰²In extremely Few one represents alkyl.

In above-mentioned formula a1-10, work as R¹⁰¹、R¹⁰²And R¹⁰³Represent alkyl time, abovementioned alkyl can be straight-chain, branched or Any one in ring-type.

Be 1～12 as above-mentioned straight-chain or the alkyl of branched, preferably carbon number, more preferably carbon number be 1～ 6, further preferred carbon number is 1～4.Specifically, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, different can be listed Butyl, sec-butyl, the tert-butyl group, n-pentyl, neopentyl, n-hexyl, tertiary hexyl (2,3-dimethyl-2-butyl), n-heptyl, the most pungent Base, 2-ethylhexyl, n-nonyl, positive decyl etc..

Being 3～12 as above-mentioned cyclic alkyl, preferably carbon number, more preferably carbon number is 4～8, further preferably Carbon number is 4～6.As above-mentioned cyclic alkyl, such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, cycloheptyl can be listed Base, ring octyl group, norborny, isobornyl etc..

Abovementioned alkyl can also have substituent group, alternatively base, can exemplify halogen atom, aryl, alkoxyl.At tool When having halogen atom alternatively base, R¹⁰¹、R¹⁰²、R¹⁰³Become haloalkyl, when having aryl alternatively base, R¹⁰¹、 R¹⁰²、R¹⁰³Become aralkyl.

As above-mentioned halogen atom, can exemplify fluorine atom, chlorine atom, bromine atoms, atomic iodine, in them, preferably fluorine is former Son or chlorine atom.

Additionally, be the virtue of 6～12 as the aryl that above-mentioned aryl, preferably carbon number are 6～20, more preferably carbon number Base.Specifically, phenyl, Alpha-Methyl phenyl, naphthyl etc. can be exemplified, as the alkyl entirety being substituted with aryl, i.e. aralkyl, Benzyl, α-methylbenzyl, phenethyl, naphthyl methyl etc. can be exemplified.

It is the alcoxyl of 1～4 as the alkoxyl that above-mentioned alkoxyl, preferably carbon number are 1～6, more preferably carbon number Base, more preferably methoxy or ethoxy.

Additionally, when abovementioned alkyl is cycloalkyl, above-mentioned cycloalkyl can also have the straight-chain that carbon number is 1～10 Or the alkyl of branched alternatively base, in the case of the alkyl that alkyl is straight-chain or branched, it is possible to have carbon is former Subnumber is the cycloalkyl alternatively base of 3～12.

These substituent groups can also be further substituted with by above-mentioned substituent group.

In above-mentioned formula a1-10, work as R¹⁰¹、R¹⁰²And R¹⁰³When representing aryl, the preferred carbon number of above-mentioned aryl is 6～12, more Preferably carbon number is 6～10.Above-mentioned aryl can also have substituent group, as above-mentioned substituent group, preferably exemplifies carbon former Subnumber is the alkyl of 1～6.As aryl, such as phenyl, tolyl, xylyl, cumenyl, 1-naphthyl etc. can be exemplified.

Additionally, R¹⁰¹、R¹⁰²And R¹⁰³Formed together with the carbon atom that can bond together and be bonded with them or oxygen atom Ring.As R¹⁰¹With R¹⁰²、R¹⁰¹With R¹⁰³Or R¹⁰²With R¹⁰³Ring structure during bonding, can list such as cyclobutyl, cyclopenta, ring Hexyl, suberyl, tetrahydrofuran base, adamantyl and THP trtrahydropyranyl etc..

It addition, in above-mentioned formula a1-10, preferably R¹⁰¹And R¹⁰²In any one be hydrogen atom or methyl.

Use to form the Component units with the protection carboxyl represented by above-mentioned formula a1-10 is free-radical polymerised Monomer can use commercially available product, it is possible to use the free radical polymerization monomer synthesized by known method.Such as can be in order to Synthesize by the synthetic method etc. described in the paragraph 0037～0040 of Japanese Unexamined Patent Publication 2011-221494 publication.

Under first optimal way of the above-mentioned Component units a1-1 having by the protection carboxyl of acid decomposability radical protection is State the Component units represented by formula.

[chemical formula 2]

In formula, R¹And R²Separately represent hydrogen atom, alkyl or aryl, at least R¹And R²In any one be alkyl Or aryl, R³Represent alkyl or aryl, R¹Or R²With R³Can also link and form cyclic ether, R⁴Represent hydrogen atom or methyl, X table Show singly-bound or arlydene.

Work as R¹And R²During for alkyl, preferably carbon number is the alkyl of 1～10.Work as R¹And R²During for aryl, preferably benzene Base.R¹And R²Separately it is preferably hydrogen atom or alkyl that carbon number is 1～4.

R³Representing the alkyl that alkyl or aryl, preferably carbon number are 1～10, more preferably carbon number is the alkane of 1～6 Base.

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

Under second optimal way of the above-mentioned Component units a1-1 having by the protection carboxyl of acid decomposability radical protection is State the Component units represented by formula.

[chemical formula 3]

In formula, R¹²¹Represent hydrogen atom or the alkyl that carbon number is 1～4, L¹Represent carbonyl or phenylene, R¹²²～R¹²⁸ Separately represent hydrogen atom or the alkyl that carbon number is 1～4.

R¹²¹It is preferably hydrogen atom or methyl.

L¹It is preferably carbonyl.

R¹²²～R¹²⁸It is preferably hydrogen atom.

Preferred concrete example as the above-mentioned Component units a1-1 having by the protection carboxyl of acid decomposability radical protection Son, can exemplify following Component units.It addition, R represents hydrogen atom or methyl.

[chemical formula 4]

<<having by the Component units a1-2 of protection phenolic hydroxyl group of acid decomposability radical protection>>

As the Component units a1-2 of the above-mentioned protection phenolic hydroxyl group having by acid decomposability radical protection, hydroxyl can be listed Component units in base polystyrene Component units or novolaks system resin.

In them, the Component units from hydroxy styrenes or Alpha-Methyl hydroxy styrenes is from the viewpoint of sensitivity Preferably.

Additionally, as having the Component units of phenolic hydroxyl group, the paragraph 0065 of Japanese Unexamined Patent Publication 2014-238438 publication～ Component units described in 0073 is also preferred from the viewpoint of sensitivity.

(optimal way of Component units a1)

When the polymer with above-mentioned Component units a1 does not the most have following Component units a2, Component units a1 exists Have in the polymer of above-mentioned Component units a1 and be preferably 20～100 moles of %, more preferably 30～90 moles %.

When the polymer with above-mentioned Component units a1 has following Component units a2, Component units a1 have above-mentioned In the polymer of Component units a1 and Component units a2, preferably 3～70 moles of % from the viewpoint of sensitivity, more preferably 10 ～60 moles of %.Additionally, be particularly the form protected protection carboxyl that there is carboxyl with acetal as above-mentioned Component units a1 Component units time, preferably 20～50 moles %.

It addition, in the present invention, when the content of " Component units " is carried out regulation with mol ratio, " Component units " and " monomer Unit " implication is identical.Additionally, in the present invention, " monomeric unit " can also be modified after polymerisation by high molecular weight reactive etc..With Under too.

If above-mentioned have by acid decomposability radical protection protection carboxyl Component units a1-1 with above-mentioned have divided by acid The Component units a1-2 of the protection phenolic hydroxyl group of solution property radical protection compares, then have feature faster of developing.Thus, it is being intended to quickly In the case of development, it is however preferred to have by the Component units a1-1 of the protection carboxyl of acid decomposability radical protection.It is being intended on the contrary Slow down in the case of development, the Component units a1-2 with protection phenolic hydroxyl group by acid decomposability radical protection is preferably used.

Component of polymer A1 preferably comprises the polymer comprising the Component units a2 with crosslinkable groups.It addition, as above As shown in the condition 1～3 stated, when not containing cross-linking agent C1 described later, at least contain and there is acidic group by acid decomposability Polymer A 1-1 of the Component units a1 of the group of radical protection comprise further have crosslinkable groups Component units a2 or It is necessary that person contains other polymer A 1-2 comprising the Component units a2 with crosslinkable groups.

As long as above-mentioned crosslinkable groups for causing the group of curing reaction by heat treated, it is not particularly limited.

As the mode of the Component units with preferred crosslinkable groups, can list and comprise choosing free epoxy radicals, oxygen Azetidinyl ,-NH-CH₂Group represented by-O-R (R represents hydrogen atom or the alkyl that carbon number is 1～20), olefinic are not The Component units of at least one group in the group of saturated group and the basis set one-tenth of blocked isocyanate, preferably comprises choosing freely Epoxy radicals, oxetanyl ,-NH-CH₂Base represented by-O-R (R represents hydrogen atom or the alkyl that carbon number is 1～20) The Component units of at least one group in the group of group, (methyl) acryloyl group and the basis set one-tenth of blocked isocyanate, more preferably Comprise the free epoxy radicals of choosing, oxetanyl and-NH-CH₂(R represents hydrogen atom or the alkane that carbon number is 1～20 to-O-R Base) represented by group composition group in the Component units of at least one group.

<<there is the Component units a2-1 of epoxy radicals and/or oxetanyl>>

Component of polymer A1 preferably comprises and comprises Component units a2-1 poly-with epoxy radicals and/or oxetanyl Compound.It addition, the cyclic ether group of 3 rings is also referred to as epoxy radicals, the cyclic ether group of 4 rings is also referred to as oxetanyl.

As long as the above-mentioned Component units a2-1 with epoxy radicals and/or oxetanyl has in a Component units At least one epoxy radicals or oxetanyl, it is possible to have more than one epoxy radicals and more than one oxa-ring Butane group, plural epoxy radicals or plural oxetanyl, be not particularly limited, but preferably has total 1 Individual～3 epoxy radicals and/or oxetanyl, more preferably have total 1 or 2 epoxy radicals and/or oxetanyl, Further preferably there is an epoxy radicals or oxetanyl.

As the object lesson of the free radical polymerization monomer used to form the Component units with epoxy radicals, can List such as glycidyl acrylate, glycidyl methacrylate, α-ethylacrylate ethylene oxidic ester, α-positive third Base glycidyl acrylate, α-n-butyl acryloyloxy ethyl acid glycidyl ester, acrylic acid-3,4-epoxy butyl ester, methacrylic acid-3, 4-epoxy butyl ester, acrylic acid-3,4-epoxycyclohexanecarboxylate, methacrylic acid-3,4-epoxycyclohexanecarboxylate, α-ethyl propylene Acid-3,4-epoxycyclohexanecarboxylate, adjacent vinylbenzyl glycidyl ether, a vinylbenzyl glycidyl ether, to vinyl Benzyl glycidyl ether, No. 4168443 publications of Japanese Patent No. paragraph 0031～0035 described in containing ester ring type epoxy The compound etc. of skeleton, these contents are included in present specification.

Concrete as the free radical polymerization monomer used to form the Component units with oxetanyl Example, can list and have oxa-ring described in the paragraph 0011～0016 of such as Japanese Unexamined Patent Publication 2001-330953 publication (methyl) acrylate etc. of butane group, these contents are included in present specification.

As the freedom used to form the above-mentioned Component units a2-1 with epoxy radicals and/or oxetanyl The object lesson of base polymerizable monomer, the preferably monomer containing metacrylic acid ester structure, the list containing acrylate structural Body.

Preferably glycidyl methacrylate, acrylic acid 3,4-epoxycyclohexanecarboxylate, metering system in them Acid 3,4-epoxycyclohexanecarboxylate, acrylic acid (3-Ethyloxetane-3-base) methyl ester and methacrylic acid (3-ethyl oxygen Azetidine-3-base) methyl ester.These Component units can be used alone one or are used in combination of two or more.

As the preferred object lesson of the Component units a2-1 with epoxy radicals and/or oxetanyl, can illustrate Go out following Component units.It addition, R represents hydrogen atom or methyl.

[chemical formula 5]

<<there is the Component units a2-2 of ethylenically unsaturated group>>

As other example of the above-mentioned Component units a2 with crosslinkable groups, can list and there is olefinic unsaturated group The Component units a2-2 of group.As the above-mentioned Component units a2-2 with ethylenically unsaturated group, it is preferably and has on side chain The Component units of ethylenically unsaturated group, more preferably end have ethylenically unsaturated group and have carbon number be 3～ The Component units of the side chain of 16.

Additionally, about having the Component units a2-2 of ethylenically unsaturated group, be referred to Japanese Unexamined Patent Publication 2011-215580 The record of the paragraph 0072～0090 of number publication and the note of the paragraph 0013～0031 of Japanese Unexamined Patent Publication 2008-256974 publication Carrying, these contents are included in present specification.

< < there is-NH-CH₂The structure of the group represented by-O-R (R represents hydrogen atom or the alkyl that carbon number is 1～20) Become unit a2-3 > >

As other example of the above-mentioned Component units a2 with crosslinkable groups, preferably also there is-NH-CH₂-O-R The Component units a2-3 of the group represented by (R represents hydrogen atom or the alkyl that carbon number is 1～20).By single containing constituting Unit a2-3, can cause curing reaction by heat treated slowly, it is possible to obtain the cured film of various excellents.Its In, R preferably carbon number be the alkyl of 1～20, more preferably carbon number be the alkyl of 1～9, more preferably carbon is former Subnumber is the alkyl of 1～4.Additionally, alkyl can be any one of straight chain, side chain or ring-type alkyl, but preferably straight chain or The alkyl of side chain.Component units a2-3 more preferably has the Component units of the group represented by following formula a2-30.

[chemical formula 6]

In formula a2-30, R³¹Represent hydrogen atom or methyl, R³²Represent the alkyl that carbon number is 1～20.

R³²Being preferably the alkyl that carbon number is 1～9, more preferably carbon number is the alkyl of 1～4.Additionally, alkane Base can be any one of straight chain, side chain or ring-type alkyl, but the alkyl of preferably straight or branched.

As R³²Object lesson, methyl, ethyl, normal-butyl, isobutyl group, cyclohexyl and n-hexyl can be listed.Its In, preferably isobutyl group, normal-butyl, methyl.

(optimal way of Component units a2)

In the case of the polymer with above-mentioned Component units a2 does not have Component units a1, Component units a2 is containing The polymer of above-mentioned Component units a2 is preferably 5～90 moles of %, more preferably 20～80 moles %.

In the case of the polymer with above-mentioned Component units a2 has above-mentioned Component units a1, Component units a2 contains Amount is preferably 1～70 mole of % in the polymer with Component units a1 and Component units a2, and more preferably 3～60 rub You are %.

In the present invention, and then, no matter it is which mode, in whole Component units of component of polymer A1, preferably comprises 0 ～the Component units a2 of 70 moles of %, more preferably contain 0～50 mole of %.It addition, as it has been described above, when the content of Component units a2 When being 0 mole of %, it is necessary to containing cross-linking agent C1 described later.

If in the range of above-mentioned numerical value, then by the cured film that obtained by resin combination by the stacking of rear operation institute Inoranic membrane on etching resist peel off after the etching resist residue on cured film surface few, become good.

Component of polymer A1 contains and comprises the Component units (hereinafter also referred to as " Component units s1 ") shown in following s1 Polymer.It addition, as shown in condition 4 and 5 described above, Component units s1 can be that (i) at least contains and have acidic group By polymer A 1-1 of Component units a1 of the group of acid decomposability radical protection have further Component units s1 mode, (ii) other polymer A 1-2 containing the Component units a2 with crosslinkable groups has the side of Component units s1 further Other polymer A 1-3 of formula and (iii) has any one in the mode of Component units s1.

S1: have and select in the group that free fluorine substituted hydrocarbon radical, siloxane backbone and alkyl that carbon number is 10～30 form The Component units of at least one part-structure (hereinafter also referred to as " deflection existence group ") and there is light orientation base The Component units of group

<<there is the Component units of the part-structure of fluorine substituted hydrocarbon radical>>

As long as the alkyl that fluorine substituted hydrocarbon radical is replaced by least one fluorine atom, can list alkyl or At least one hydrogen atom in alkylidene (following, to be abbreviated as " alkyl etc. " in this paragraph) is substituted by the alkyl etc. of fluorine atom, more It is preferably the alkyl etc. that whole hydrogen atoms of alkyl etc. are substituted by fluorine atom.

From the viewpoint of deflection existence, such fluorine substituted hydrocarbon radical is preferably the group represented by following formula I.

[chemical formula 7]

(formula I)

In formula I, R²Representing hydrogen atom or the alkyl that carbon number is 1～4, * represents the linking part to polymer chain Position.X represents the link group of singly-bound or divalent, and m represents the integer of 1～3, and n represents the integer of more than 1, r represent 0 or 1～2 whole Number.It addition, when m is 1, multiple R²Respectively can be identical, it is also possible to different.

M in formula I represents the integer of 1～3, preferably 1 or 2.

N in formula I represents the integer of more than 1, the integer of preferably 1～10, and the integer of more preferably 1～4 is the most excellent Elect 1 or 2 as.

R in formula I represents 0 or the integer of 1～2, preferably 1 or 2, more preferably 2.

Additionally, represented by * can be with the master of the polymer such as above-mentioned polymer A 1-1 to the bond sites of polymer chain Chain Direct Bonding, it is also possible to via polyoxy alkylidene, alkylidene, ester group, carbamate groups, heteroatomic ring-type Asia can be comprised The link group of the divalent such as alkyl, poly-(caprolactone), amino and be bonded.Preferably it is bonded via polyoxy alkylidene.

As R in formula I²The represented alkyl that carbon number is 1～4, can list methyl, ethyl, propyl group, different Propyl group, normal-butyl, isobutyl group, the tert-butyl group etc., preferably hydrogen atom or methyl, more preferably hydrogen atom.

In formula I, when X is singly-bound, it is meant that main polymer chain and R²The carbon atom being bonded directly links.

Additionally, in the case of the link group that X is divalent, as this link group ,-O-,-S-,-N can be listed (R⁴)-,-CO-etc..In them, more preferably-O-.Wherein, R⁴Represent hydrogen atom or the alkyl that carbon number is 1～4.As Alkyl, can list methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, the tert-butyl group etc., preferably hydrogen atom, methyl.

As fluorine substituted hydrocarbon radical being imported the method in polymer, can list: by high molecular weight reactive, fluorine is replaced hydrocarbon Base imports the method in polymer；To have the monomer (hereinafter referred to as " containing the monomer of fluorine substituted hydrocarbon radical ") of fluorine substituted hydrocarbon radical Carry out copolymerization and import the method etc. of the Component units with fluorine substituted hydrocarbon radical in the polymer.

The structure with fluorine substituted hydrocarbon radical is imported in the polymer as the monomer containing fluorine substituted hydrocarbon radical is carried out copolymerization Becoming the monomer containing fluorine substituted hydrocarbon radical in the method for unit, the monomer represented by following formula II can arrange as preferred monomer Enumerate.

[chemical formula 8]

(formula II)

In formula II, R¹Represent hydrogen atom, halogen atom, can have the methyl of substituent group, maybe can have the second of substituent group Base.Additionally, R², X, m, n and r all with the R in formula I², X, m, n and r implication identical, preferred example is the most identical.

It addition, as R in formula II¹Represented halogen atom, can list such as fluorine atom, chlorine atom, bromine atoms.

It addition, about the autofrettage of such monomer containing fluorine substituted hydrocarbon radical, such as at " Off ッ element compou nd synthesis と can " page 117～118 of (supervision: Ishikawa prolongs man, distribution: Co., Ltd. シエ system シ, 1987) or " Chemistry of Organic Fluorine Compounds II " (Monograph187, Ed by Milos Hudlicky and Attila E.Pavlath, American Chemical Society1995) page 747～752 in have Record.

Additionally, as the object lesson of the monomer represented by formula II, the methyl represented by following formula (IIa) can be listed Methacrylic acid hexafluoro isopropyl ester etc. represented by acrylic acid tetrafluoro isopropyl esters, following formula (IIb).

Additionally, as other object lesson, can list Japanese Unexamined Patent Publication 2010-18728 publication paragraph (0058)～ (0061) compound described in.They are preferably the structure being bonded with fluorine substituted hydrocarbon radical on polyoxy alkylidene.

[chemical formula 9]

<<there is the Component units of the part-structure of siloxane backbone>>

As long as siloxane backbone has "-Si-O-Si-", then it is not particularly limited, preferably comprises polyoxy alkylidene.

In the present invention, from the viewpoint of deflection existence, siloxane backbone is preferably will have (methyl) acryloyl-oxy The compound of base and alkoxysilyl carries out copolymerization, imports the structure of the part-structure with siloxane backbone in polymer Become unit.

Wherein, as alkoxysilyl, it is preferably the group represented by the most following formula (X).

[chemical formula 10]

In above-mentioned formula (X), R³～R⁵Separately represent hydrogen atom, hydroxyl, halogen atom, alkyl or alkoxyl, extremely Few one is alkoxyl.* bonding position is represented.

In above-mentioned formula (X), R³～R⁵In at least one be alkoxyl, as alkoxyl, preferably carbon number be 1～ The alkoxyl of 15, more preferably carbon number are the alkoxyl of 1～8, and more preferably carbon number is the alkoxyl of 1～4, Particularly preferably ethyoxyl or methoxyl group.

In the present invention, preferably R³～R⁵In two be alkoxyl and situation that one is alkyl or three be alkoxyl Situation.Wherein, more preferably three is the mode of alkoxyl, i.e. trialkoxysilyl.

As having the compound of such alkoxysilyl and (methyl) acryloxy, specifically, can arrange Enumerate such as 3-(methyl) acryloxypropyl dimethoxysilane, 3-(methyl) acryloxypropyl trimethoxy Silane, 3-(methyl) acryloxypropyl diethoxy silane, 3-(methyl) acryloxypropyl triethoxysilicane Alkane etc..

Additionally, in the present invention, from the viewpoint of deflection existence, siloxane backbone is preferably by following structural formula (A) institute The compound (hereinafter also referred to as " particular silicone compound ") represented carries out being polymerized and siloxane backbone is imported polymer In.

[chemical formula 11]

In structure above (A), R⁷Expression can have the carbon number of the substituent groups such as hydroxyl, amido, halogen atom be 2～ The link group of the divalent represented by the alkylidene of the straight or branched of 6 or following structural formula (B).

[chemical formula 12]

In structure above (B), R⁴Represent hydrogen atom, methyl, ethyl.N1, n2 and n3 are separately 0～100 Integer.Wherein, R⁴Two or more is there is in structural formula (B), but respectively can be different, in addition it is also possible to identical.

In structure above (A), x1, x2 and x3 are the integer of their total satisfied 1～100.

Additionally, the integer that y1 is 1～30.

In structure above (A), X²The group of the divalent represented by singly-bound or following structural formula (C).

[chemical formula 13]

In structure above (C), R⁸Expression can have the carbon number of the substituent groups such as hydroxyl, amido, halogen atom be 1～ The alkylidene of the straight or branched of 6, Q¹And Q²Represent oxygen atom, sulphur atom or-NRB-, Q¹、Q²Respectively can be different, additionally, Can also be identical.RB represents hydrogen atom or the alkyl that carbon number is 1～4.

In structure above (C), Q²With the R in structure above (A)⁷Bonding.

In structure above (A), Y²The group of 1 valency represented by expression following structural formula (D)～following structural formula (F).

[chemical formula 14]

In structure above (D)～(F), R⁵Represent hydrogen atom or straight-chain that carbon number is 1～6 or branched Alkyl.

In structure above (A), Z¹、Z²、Z³Separately represent the group of 1 valency represented by following structural formula (G).

[chemical formula 15]

In structure above (G), R⁶Represent the unsubstituted alkyl that carbon number is 1～4, y²Represent the integer of 1～100, It is preferably the integer of 1～50, the integer of more preferably 1～20.

Additionally, as siloxane backbone, in the paragraph (0092) of Japanese Unexamined Patent Publication 2010-18728 publication～(0094) The structure recorded can list as the object lesson of above-mentioned formula (A), but is not limited to them.

In them, preferably siloxane structure is via the structure of polyoxy alkylidene Yu polymer-bound.

<<there is the Component units of the part-structure of the alkyl that carbon number is 10～30>>

Carbon number be 10～30 alkyl can also comprise branched structure or circulus, but the portion of preferred linear chain structure Point carbon number in the range of 10～30, the most all linear chain structure.

Additionally, the carbon number of alkyl is preferably 10～20.

Specifically, preferably there is on the side chain of polymer the group represented by following formula (a3-1).

[chemical formula 16]

In formula (a3-1), n_a3Representing the integer of 10～30, * represents the position that the main chain with polymer or side chain link. n_a3It is preferably the integer of 10～20.

The method of main chain or side chain for the structure of above-mentioned formula (a3-1) is imported polymer is not particularly limited, but As long as such as suitably select and be suitable for the monomer of the structure with (a3-1) when synthesis, then can be at obtained polymer Repetitive imports the structure of (a3-1).

Additionally, the monomer with the structure of above-mentioned formula (a3-1) can use commercially available compound but it also may to not The commercially available monomer of the structure with (a3-1) suitably imports the desired structure comprised in (a3-1) and uses.For in city The method of the structure importing (a3-1) in the monomer sold does not limits, as long as being suitably suitable for known method.

The monomer of the structure with above-mentioned formula (a3-1) suitably can select according to the backbone structure of polymer, if such as It is the polymer on main chain with (methyl) acrylic acid structure, then monomer following formula (a3-2) represented by is preferably used.

[chemical formula 17]

In above-mentioned formula (a3-2), R³²Represent hydrogen atom, methyl, ethyl or halogen atom, X³¹Represent the concatenating group of divalent Group, R³³Represent singly-bound or alkylidene epoxide.Additionally, n_a3Identical with above-mentioned formula (a3-1) implication, preferred scope is the most identical.

In formula (a3-2), R³²For hydrogen atom, methyl, ethyl or halogen atom, more preferably hydrogen atom or methyl, enter One step is preferably methyl.

In formula (a3-2), as X³¹The link group of divalent ,-O-,-S-,-N (R can be listed⁴)-etc..In them more It is preferably-O-.

Wherein, R⁴Represent hydrogen atom or the alkyl that carbon number is 1～4.As alkyl, can be linear chain structure, also Can be branched structure, methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, the tert-butyl group etc., preferably hydrogen can be listed Atom, methyl.

Additionally, as R³³Alkylidene epoxide, preferably carbon number is 1～4.Alkylidene epoxide can also have a link Structure.Furthermore, it is possible to have substituent group, it is also possible to be unsubstituted.As the substituent group that can also have, halogen atom can be listed Deng.As the object lesson of alkylidene epoxide, methylene epoxide, ethyleneoxy group, propylidene epoxide, butylene oxide can be exemplified Base etc..

In them, R³³It is preferably unsubstituted straight-chain alkyl-sub-epoxide or singly-bound that carbon number is 1～4, more preferably Singly-bound.

By using the monomer represented by above-mentioned formula (a3-2), it is possible to obtain have following formula (U-a3-1) institute table The polymer of the repetitive shown.

It is one of preferred form that such polymer has the repetitive represented by formula (U-a3-1).

[chemical formula 18]

In above-mentioned formula (U-a3-1), n_a3Identical with above-mentioned formula (a3-1) implication, preferred scope is the most identical, R³²、 X³¹, and R³³Identical with above-mentioned formula (a3-2) implication, preferred scope is the most identical.

Below, it is shown that the object lesson of the monomer represented by formula (a3-2).But, the present invention is not limited to them.

[chemical formula 19]

<<there is the Component units of light orientation group>>

Component of polymer A1 contains above-mentioned comprising and has the free fluorine substituted hydrocarbon radical of choosing, siloxane backbone and carbon number are The Component units of at least one part-structure in the group of the alkyl composition of 10～30 and there is the composition of light orientation group The polymer of unit.

Wherein, light orientation group refer to be reacted by photodimerization or photoisomerization reaction and to give the light of orientation anti- Answering property group.

Additionally, give the group of orientation as being reacted by photodimerization, can list such as by selecting free Malaysia The group that at least one derivant in the group of imide derivative, cinnamic acid derivative and coumarin derivative composition imports Deng, specifically, can suitably list cinnamic acid ester group, chalcone derivative base.It addition, as cinnamic acid ester group and chalcone derivative base, example As imported following structure, (in following formula, * represents the bond sites to polymer chain, and R represents having of hydrogen atom or 1 valency Machine group), additionally, represented by * can be with the master of the polymer such as above-mentioned polymer A 1-1 to the bond sites of polymer chain Chain Direct Bonding, it is also possible to be bonded via the link group of divalent.As the organic group of 1 valency represented by R, preferably alkane Base or aryl.Additionally, the carbon number of the organic group of 1 valency represented by R is preferably 1～10, more preferably 1～7.

[chemical formula 20]

On the other hand, as being carried out the reactive group of isomerization by the effect of light, specifically, can suitably list Bone by least one compound in the choosing group that freely such as azobenzene compound, stilbene compounds and spiropyran compounds form The group etc. being configured to.

In them, from the viewpoint of patterned exposure with the difference performance of orientation exposure, preferably by with more shortwave The photodimerizationization that light carries out reacting is reacted and is given the group of orientation, more preferably cinnamic acid ester group or chalcone derivative base.It addition, Wherein, so-called patterned exposure is identical with the exposure process implication in the manufacture method of the solidfied material of the present invention described later, so-called Orientation exposure, after being applied on substrate for resin combination, the exposure carried out to give orientation, send out with described later Light orientation process implication in the manufacture method of bright solidfied material is identical.

About the polymer containing the Component units with light orientation group, its main chain backbone is not particularly limited, but Become various from the MOLECULE DESIGN of side chain, utilize the main chain of the Raolical polymerizable of alefinically unsaturated compounds to form simplicity Reason is set out, it is however preferred to have the polymer of the repetitive represented by following logical formula (III).

[chemical formula 21]

(general formula III)

(in logical formula (III), R¹Represent hydrogen atom or alkyl.X represents arlydene ,-(C=O)-O-or-(C=O)-NR- (R represents hydrogen atom or the alkyl that carbon number is 1～4).L represents the link group of singly-bound or divalent, and P represents light orientation Group)

Wherein, in logical formula (III), R¹Represent hydrogen atom or alkyl, as the alkane that alkyl, preferably carbon number are 1～4 Base (such as, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl etc.).R¹It is preferably hydrogen atom or methyl.

Additionally, in logical formula (III), L represents the link group of singly-bound or divalent, as the link group of divalent, be preferably- O-,-S-, alkylidene, arlydene or by they multiple groups combined.As the alkylidene represented by L, can be straight Chain, side chain or circulus, but preferably linear chain structure.The carbon number of the alkylidene represented by L is preferably 1～10, more excellent Elect 1～6 as, more preferably 2～4.Additionally, as the arlydene represented by L, phenylene, xylylene, benzene can be listed Support dimethyl etc., preferably phenylene.

In logical formula (III), P represents light orientation group, as its object lesson, can suitably list chalcone derivative base, meat Cinnamic acid ester group, stilbene radicals, dimaleoyl imino, azo benzyl.Wherein, more preferably chalcone derivative base, cinnamic acid ester group.Additionally, P institute As long as the light orientation group represented does not loses light orientation, then can also have substituent group.As concrete substituent group, can arrange Enumerate such as halogeno-group, alkyl, aryl etc., preferably alkyl or aryl.The carbon number of above-mentioned alkyl or aryl is preferably 1 ～10, more preferably 1～7.

The preferred object lesson of the polymer of the repetitive having represented by logical formula (III) described below, but this Bright it is not limited to them.

[chemical formula 22]

[chemical formula 23]

[chemical formula 24]

[chemical formula 25]

[chemical formula 26]

[chemical formula 27]

[chemical formula 28]

[chemical formula 29]

Have the repetitive represented by logical formula (I) polymer can by (a) make correspondence monomer be polymerized and direct The method of importing photoreactive group synthesizes, it is also possible to is polymerized at the monomer will with arbitrary functional group by (b) and obtains To polymer in imported the method for photoreactive group by high molecular weight reactive and synthesize.In addition it is also possible to by (a) and B the Combination of Methods of () synthesizes.

Wherein, as the polyreaction that can utilize in the method at above-mentioned (a) and (b), radical polymerization can be listed Conjunction, cationic polymerization and anionic polymerisation etc..

Additionally, the polymer with the repetitive represented by logical formula (I) can be by the weight represented by multiple logical formula (I) The copolymer that multiple unit is constituted, in addition it is also possible to be to comprise the repetitive beyond logical formula (I) (the most not comprise olefinic insatiable hunger Repetitive with group) copolymer.

(optimal way of Component units s1)

Above-mentioned Component units s1 is preferably 0.01～10 mole of % relative to the Component units of whole component of polymer, more excellent Elect 0.1～5 mole of %, more preferably 0.1～3 mole of % as, particularly preferably 0.1～2 mole %, most preferably 0.5 ～2 moles of %.

When the polymer with above-mentioned Component units s1 has Component units a1 and Component units a2, Component units s1's Content is preferably 20～90 moles of %, more preferably 20～80 moles % relative to whole Component units of above-mentioned polymer, enters One step is preferably 20～70 moles of %.

When any one during the polymer with above-mentioned Component units s1 only has Component units a1 and Component units a2, The content of Component units s1 is preferably 30～90 moles of % relative to whole Component units of above-mentioned polymer, more preferably 30～ 80 moles of %, more preferably 30～70 moles of %.

When any one during the polymer with above-mentioned Component units s1 does not have Component units a1 and Component units a2, The content of Component units s1 is preferably 40～95 moles of % relative to whole Component units of above-mentioned polymer, more preferably 40～ 90 moles of %, more preferably 40～80 moles of %.

In the 1st mode, component of polymer A1 can also be containing except above-mentioned Component units a1, Component units a2 and composition Possibly together with having the Component units a3 of acidic group or the polymer of the Component units a4 beyond them beyond unit s1.

<<Component units a3>>

From not only becoming easily to dissolve the developer solution of alkalescence, developability becomes good, and sensitivity is excellent, Jin Erxian The reason that the fine rule adaptation of the solidfied material of movie queen is also excellent is set out, and component of polymer A1 preferably comprises and comprises the structure with acidic group Become the polymer of unit a3.

Acidic group in the present invention refers to the proton dissociation group that pKa is less than 11.Acidic group generally uses and can form acidic group Monomer, is assembled in polymer as the Component units comprising acidic group.Such acidic group is comprised by comprising in the polymer Component units, exist relative to alkalescence developer solution become to hold diffluent tendency.

As the acidic group used in the present invention, carboxylic acid group, sulfoamido, phosphonate group, sulfonic group, phenol hydroxyl can be exemplified Base, sulfoamido, sulphonyl imine base and the anhydride group of these acidic groups and these acidic groups are neutralized and make salt structure Group etc., preferably carboxylic acid group and/or phenolic hydroxyl group.As above-mentioned salt, it is not particularly limited, but preferably exemplifies alkali metal Salt, alkali earth metal salt and organic ammonium salt.

The Component units comprising acidic group used in the present invention is more preferably from cinnamic Component units or from second The Component units of alkenyl compound, Component units from (methyl) acrylic acid and/or its ester.Such as can use Japanese Unexamined Patent Publication The paragraph 0021 of 2012-88459 publication～0023 and the compound recorded of paragraph 0029～0044, this content is included into this Shen Please be in description.Wherein, it is preferably from 4-Vinyl phenol, (methyl) acrylic acid, maleic acid, the composition list of maleic anhydride Unit.

As having the Component units a3 of acidic group, from the viewpoint of sensitivity, it is however preferred to have the Component units of carboxyl or There is the Component units of phenolic hydroxyl group, more preferably there is the Component units of carboxyl.

As having the Component units a3 of acidic group, specifically, can list and above-mentioned in molecule, have at least one The Component units a1-1-1 of the unsaturated carboxylic acid etc. of individual carboxyl, there is ethylenically unsaturated group and the structure from anhydride simultaneously Component units a1-1-2, having the Component units a1-2-1 of phenolic hydroxyl group, preferred mode is the most identical.

Wherein, as having the Component units a3 of acidic group, it is preferably from selecting free methacrylic acid, acrylic acid and to hydroxyl Component units (any one represented composition in following formula a3-1～formula a3-3 of compound in the group of base styrene composition Unit), more preferably from the Component units (Component units represented by following formula a3-1) of methacrylic acid or from propylene The Component units (Component units represented by following formula a3-2) of acid, more preferably from the Component units of methacrylic acid (Component units represented by following formula a3-1).

[chemical formula 30]

(optimal way of Component units a3)

The Component units a3 comprising acidic group is preferably 1～80 mole of % relative to the Component units of whole component of polymer, More preferably 1～50 mole of %, more preferably 5～40 moles of %, particularly preferably 5～30 moles %, most preferably 5～ 20 moles of %.

When the polymer with above-mentioned Component units a3 has Component units a1 and Component units a2, Component units a3's Content is preferably 1～30 mole of %, more preferably 3～20 moles % relative to whole Component units of above-mentioned polymer, enters one Step is preferably 5～15 moles of %.

When any one during the polymer with above-mentioned Component units a3 only has Component units a1 and Component units a2, The content of Component units a3 is preferably 1～50 mole of %, more preferably 5～45 relative to whole Component units of above-mentioned polymer Mole %, more preferably 10～40 moles of %.

When any one during the polymer with above-mentioned Component units a3 does not have Component units a1 and Component units a2, The content of Component units a3 is preferably 1～50 mole of %, more preferably 2～40 relative to whole Component units of above-mentioned polymer Mole %, more preferably 3～30 moles of %.

<<Component units a4>>

As the structure become in addition to above-mentioned Component units a1, Component units a2, Component units s1 and Component units a3 Become the monomer of unit a4, be not particularly limited, such as phenylethylene, (methyl) alkyl acrylate, (methyl) third can be listed Olefin(e) acid cyclic alkyl ester, (methyl) benzyl acrylate, unsaturated dicarboxylic diester, bicyclo-unsaturated compound class, maleoyl Group with imine moiety class, unsaturated aromatic compound.

The monomer forming other Component units a4 can be used alone one or is used in combination of two or more.

About other Component units a4, specifically, can list and utilize styrene, methyl styrene, Alpha-Methyl benzene second Alkene, acetoxy-styrene, methoxy styrene, ethoxystyrene, chlorostyrene, vinylbenzoate, vinyl Ethyl benzoate, 4-HBA (3-methacryloxypropyl) ester, (methyl) acrylic acid methyl ester., (methyl) acrylic acid Ethyl ester, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) propylene Acid 2-hydroxy propyl ester, (methyl) benzyl acrylate, (methyl) isobornyl acrylate, acrylonitrile, ethylene glycol single acetyl acetas The Component units of single (methyl) acrylate etc..Additionally, the paragraph 0021 of Japanese Unexamined Patent Publication 2004-264623 publication can be listed ～the compound described in 0024.

Additionally, as other Component units a4, from phenylethylene or the composition of the monomer with aliphatic ring type skeleton Unit is preferred from the viewpoint of electrical characteristics.Specifically, styrene, methyl styrene, Alpha-Methyl benzene second can be listed Alkene, (methyl) acrylic acid bicyclo-pentyl ester, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid Benzyl ester etc..

And then additionally, as other Component units a4, from the Component units of (methyl) alkyl acrylate from adaptation From the viewpoint of be preferred.Specifically, (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) can be listed Propyl acrylate, (methyl) n-butyl acrylate etc., more preferably (methyl) acrylic acid methyl ester..Constitute whole compositions of polymer In unit, the containing ratio of above-mentioned Component units a4 is preferably 60 moles of below %, more preferably 50 moles below %, further It is preferably 40 moles of below %.As lower limit, it is also possible to be 0 mole of %, but such as it is preferably set to 1 mole of more than %, more It is preferably set to 5 moles of more than %.If in the range of above-mentioned numerical value, then the cured film obtained by resin combination various Characteristic becomes good.

There is above-mentioned Component units a1, Component units a2 and Component units s1 and Component units a3 and Component units a4 As long as polymer meet the polymer of above-mentioned condition 1～5, then the combination of Component units or the number of polymer do not have It is particularly limited to.It addition, as shown in condition 1～3 described above, when not containing cross-linking agent C1 described later, include at least There is acidic group contained further by polymer A 1-1 of Component units a1 of the group of acid decomposability radical protection there is bridging property The Component units a2 of group or be must containing comprising other polymer A 1-2 of the Component units a2 with crosslinkable groups Must.

Accordingly, as component of polymer A1, it is also possible to be the mode becoming following polymer: such as contain only to comprise and have Acidic group is by polymer A 1-1 of Component units a1 of the group of acid decomposability radical protection, and this polymer A 1-1 comprises and has friendship The connection property Component units a2 of group, Component units s1 and to have the Component units a3 of acidic group whole.

Additionally, as component of polymer A1, it is also possible to it is the mode becoming following polymer: containing comprising, there is acidic group quilt Polymer A 1-1 of the Component units a1 of the group of acid decomposability radical protection, contains simultaneously and comprises the structure with crosslinkable groups Become other polymer A 1-2 of unit a2, and this polymer A 1-2 comprises Component units s1 and has the Component units of acidic group a3。

Additionally, as component of polymer A1, it is also possible to it is in the following manner: there is acidic group by acid decomposability group containing comprising Polymer A 1-1 of the Component units a1 of the group of protection, comprise other the polymerization of the Component units a2 with crosslinkable groups Thing A1-2 and comprise other polymer A 1-3 of Component units s1.

During additionally, contain cross-linking agent C1 described later as resin combination, as component of polymer A1, it is also possible to be containing Comprise and there is acidic group by polymer A 1-1 of Component units a1 of the group of acid decomposability radical protection and comprise Component units s1 The mode of other polymer A 1-3.

In 1st mode of the present invention, as component of polymer A1, it is also possible to comprise only have above-mentioned Component units a3 and The polymer of Component units a4.

As such polymer, preferably there is on side chain the resin of carboxyl.Can list such as in Japanese Laid-Open Patent Publication No. 59-44615, Japanese Patent Publication 54-34327, Japanese Patent Publication 58-12577, Japanese Patent Publication No. 54-25957, day This JP 59-53836, Japanese Laid-Open Patent Publication 59-71048 each publication described in such methacrylic acid copolymer, Acrylic copolymer, itaconic acid copolymer, crotonic acid-copolymers, maleic acid, partial esterification maleic acid etc., with And have on side chain the acid cellulose derivant of carboxyl, on the polymer have hydroxyl the material of addition anhydride Deng, and then also can list and there is on side chain the high molecular polymer of (methyl) acryloyl group as preferred material.So-called Contain substantially no, refer to that the part by weight in polymer is below 1 mass %.

Such as (methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) acrylic acid 2-hydroxyl second can be listed (methyl) described in ester/(methyl) benzyl acrylate/(methyl) acrylic copolymer, Japanese Unexamined Patent Publication 7-140654 publication Acrylic acid 2-hydroxy propyl ester/Group-capped Polystyrene Macromer/benzyl methacrylate/methacrylic acid copolymer, acrylic acid 2- Hydroxyl-3-phenoxy-propyl/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/Group-capped Polystyrene Macromer/methyl methacrylate/methacrylic acid copolymer, methyl Acrylic acid 2-hydroxy methacrylate/Group-capped Polystyrene Macromer/benzyl methacrylate/methacrylic acid copolymer etc..

In addition, it is also possible to use Japanese Unexamined Patent Publication 7-207211 publication, Japanese Unexamined Patent Publication 8-259876 publication, Japanese Unexamined Patent Publication 10-300922 publication, Japanese Unexamined Patent Publication 11-140144 publication, Japanese Unexamined Patent Publication 11-174224 public affairs Report, Japanese Unexamined Patent Publication 2000-56118 publication, Japanese Unexamined Patent Publication 2003-233179 publication, Japanese Unexamined Patent Publication 2009-52020 public affairs Known macromolecular compound described in report etc., these contents are included in present specification.

These polymer can only comprise one, it is also possible to comprises two or more.

As these polymer, it is possible to use commercially available SMA 1000P, SMA 2000P, SMA3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (being Sartomer system above), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (is east above Sub-synthesis Co., Ltd. system), JONCRYL 690, JONCRYL 678, JONCRYL 67, JONCRYL 586 (be BASF above System) etc..

The molecular weight of the polymer in component of polymer A1 with polystyrene conversion Weight-average molecular gauge be preferably 1,000～ 200,000, more preferably 2,000～50,000, the more preferably scope of 10,000～20,000.If above-mentioned numerical value In the range of, the most various characteristics are good.The ratio (dispersion, Mw/Mn) of number-average molecular weight Mn and weight average molecular weight Mw is preferably 1.0 ～5.0, more preferably 1.5～3.5.

It addition, the mensuration of weight average molecular weight in the present invention or number-average molecular weight is preferably by gel permeation chromatography (GPC) Method is measured.The mensuration utilizing gel permeation chromatography in the present invention is preferably used HLC-8020GPC (TOSOH Co., Ltd System), use TSKgel Super HZ M-H, TSK gel Super HZ4000, TSKgel SuperHZ200 (east Cao as post Co., Ltd.'s system, 4.6mmID × 15cm), use THF (oxolane) as eluent.

Synthetic method for the polymer in component of polymer A1, it is known to various methods, if but list an example, Then can be by the radical polymerization by comprising the free radical polymerization monomer used to form above-mentioned each Component units Property monomer mixture uses radical polymerization initiator to carry out being polymerized to synthesize in organic solvent.In addition it is also possible to pass through institute The high molecular weight reactive of meaning synthesizes.

In the 1st mode of the present invention, the content of component of polymer A1 is relative to all solids composition of resin combination It is preferably 20～95 mass %, more preferably 50～95 mass %, more preferably 55～95 mass %.If content is this model Enclose, then can obtain the organic membrane that curable is good.

Additionally, in the 1st mode of the present invention, there is the content of polymer of Component units s1 relative to resin combination All solids composition be preferably 0.1～20 mass %, more preferably 0.1～10 mass %.

(light acid producing agent B1)

1st mode of the present invention contains light acid producing agent B1.

As light acid producing agent B1, the active light that to be preferably wavelength be more than 300nm, optimal wavelength is 300～450nm Line senses and produces the compound of acid, but does not limit for its chemical constitution.Additionally, about being more than 300nm's to wavelength The light acid producing agent that active ray the most directly senses, as long as by with sensitizer and with and be the work of more than 300nm to wavelength Property light sensing and produce acid compound, then can also with sensitizer combination and be preferably used.As what the present invention used Light acid producing agent, is preferably the light acid producing agent producing the acid that pKa is less than 4, more preferably produces the acid that pKa is less than 3 Light acid producing agent, most preferably produces the light acid producing agent of the acid that pKa is less than 2.It addition, in the present invention, pKa refers to 25 substantially DEG C water in pKa.In water, unmeasured pKa measures, in referring to the solvent being altered to be suitable to measure, the pKa obtained.Specifically For, it is referred to the pKa described in chemistry brief guide etc..It is the acid of less than 3, preferably sulfonic acid or phosphonic acids as pKa, more preferably For sulfonic acid.

As the example of light acid producing agent B1, salt compound, trichloromethyl-s-triazine class, sulfonium salt, iodine can be listed Salt, quaternary ammonium salt, diazomethane compound, acid imide sulfonate compound and oxime sulfonate compounds etc..In them, preferably Salt compound, acid imide sulfonate compound, oxime sulfonate compounds, particularly preferred salt compound, oxime sulfonates chemical combination Thing.Light acid producing agent can be used alone one or is used in combination of two or more.

As trichloromethyl-s-triazine class, Diaryl iodonium salt, triaryl matte salt, quaternary ammonium salt and Azimethylene. The object lesson of compound, can exemplify described in the paragraph 0083～0088 of Japanese Unexamined Patent Publication 2011-221494 publication The compound described in paragraph 0013～0049 of compound or Japanese Unexamined Patent Publication 2011-105645 publication, these content quilts Include in present specification.

As the object lesson of acid imide sulfonate compound, the paragraph of WO2011/087011 publication can be exemplified Compound described in 0065～0075, these contents are included in present specification.

As salt, preferably exemplify Diaryl iodonium salt, triaryl matte salt.

As Diaryl iodonium salt, diphenyl iodine trifluoroacetate, diphenyl iodine fluoroform preferably can be listed Alkyl sulfonate, 4-methoxyphenyl phenyl-iodide trifluoro-methanyl sulfonate, 4-methoxyphenyl phenyl-iodide trifluoroacetate, benzene Base-4-(2 '-hydroxyl-1 '-tetradecyloxyaniline) phenyl-iodide trifluoro-methanyl sulfonate, 4-(2 '-hydroxyl-1 '-tetradecyloxyaniline) Phenyl-iodide hexafluoro antimonate, phenyl-4-(2 '-hydroxyl-1 '-tetradecyloxyaniline) phenyl-iodide-tosilate.

As triaryl matte salt, triphenylsulfonium triflate alkyl sulfonate, triphenylsulfonium trifluoroacetic acid preferably can be listed Salt, 4-methoxyphenyl diphenyl sulfonium trifluoro-methanyl sulfonate, 4-methoxyphenyl diphenyl sulfonium trifluoroacetate, 4-phenyl sulfur For phenyl diphenyl sulfonium trifluoro-methanyl sulfonate or 4-phenylthiophenyl diphenyl sulfonium trifluoroacetate.

As oxime sulfonate compounds, the compound i.e. with oxime sulfonates structure, preferably exemplify containing following logical The compound of the oxime sulfonates structure represented by formula (B1-1).

Formula (B1-1)

[chemical formula 31]

In formula (B1-1), R²¹Represent alkyl or aryl.Wave represents and being bonded of other group.

In formula (B1-1), all groups all can be replaced, R²¹In alkyl can be straight-chain, it is also possible to be side chain Shape, it is also possible to be ring-type.The substituent group allowed is described below.

As R²¹Alkyl, preferably carbon number is the alkyl of straight or branched of 1～10.R²¹Alkyl can also By alkoxyl that aryl that halogen atom, carbon number are 6～11, carbon number are 1～10 or ring-type alkyl (comprise 7, The bridge linking type alcyls, preferably bicyclic alkyl etc. such as 7-dimethyl-2-oxo norborny) replace.

As R²¹Aryl, preferably carbon number is the aryl of 6～11, more preferably phenyl or naphthyl.R²¹Aryl Can also be replaced by low alkyl group, alkoxy or halogen atom.

Above-claimed cpd containing the oxime sulfonates structure represented by above-mentioned formula (B1-1) is preferably also Japanese Unexamined Patent Publication Oxime sulfonate compounds described in 2014-238438 publication paragraph 0108～0133.

As acid imide sulphonic acid ester based compound, preferably naphthalimide based compound, is referred to International Publication WO11/ The record of No. 087011 pamphlet, these contents are included in present specification.The present invention particularly preferably can list three Methyl fluoride sulfonyloxy bicyclo-[2.2.1] hept-5-alkene dicarboximide, butanimide trifluoromethane sulfonic acid ester, adjacent benzene two Carboximide trifluoromethane sulfonic acid ester, N-hydroxyl naphthalimide methane sulfonate, N-hydroxyl-5-norborene-2,3-two Carboxyl acid imide propane sulfonic acid ester.

In the 1st mode of the present invention, the content of light acid producing agent B1 is relative to all solids composition of resin combination 100 mass parts are preferably 0.1～20 mass parts.Lower limit is more preferably more than such as 0.2 mass parts, more preferably 0.5 matter More than amount part.The upper limit is more preferably below such as 10 mass parts, more preferably below 5 mass parts.

(cross-linking agent C1)

1st mode of the present invention being unsatisfactory for the above-mentioned situation of condition 1 and 2, i.e. component of polymer A1 does not contains and has In the case of the polymer of crosslinkable groups, containing the cross-linking agent C1 that molecular weight is 1, less than 000.Even it addition, on Man Zuing In the case of the condition 1 or 2 stated, it is also possible to containing cross-linking agent C1.

As cross-linking agent C1, as long as then can be used without limitation by the material of thermally-induced cross-linking reaction.

For example, it is preferable to be that the free intramolecular the most described below of choosing has plural epoxy radicals or oxetanyl Compound, blocked isocyanate compounds (there is the compound of protected isocyanato-base), containing alkoxy methyl In the group of compound or the composition of the compound containing at least one ethylenical unsaturated double bonds (ethylenically unsaturated group) at least one Kind, more preferably select free intramolecular to have plural epoxy radicals or the compound of oxetanyl, end-blocking Carbimide. At least one in the group of ester compounds composition.

The addition of cross-linking agent C1 is preferably 0～30 matter relative to all solids composition 100 mass parts of resin combination Amount part, more preferably 1～20 mass parts.It addition, cross-linking agent can also be by multiple and use, by cross-linking agent is whole in the case of being somebody's turn to do The total content added up to and obtain is to calculate addition.

Hereinafter, the above-mentioned cross-linking agent C1 being preferably used in the present invention is illustrated.

The compound of plural epoxy radicals or oxetanyl<intramolecular have>

As cross-linking agent C1, the most polyfunctional little ring cyclic ether compound can be listed.

That is, refer to that 1 intramolecular has the compound of two or more epoxy radicals and/or oxetanyl.

There is as intramolecular the object lesson of the compound of plural epoxy radicals, aliphatic epoxy can be listed Compound etc..

They can obtain as commercially available product.Such as Denacol EX-611, EX-612, EX-614, EX-can be listed 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 (above Nagase Chemtex Corporation system), CELLOXIDE 2021P、2081、3000、EHPE3150、Epolead GT400、CELVENUS B0134、B0177(Daicel Corporation system) etc..

They can be used alone one or are used in combination of two or more.

There is the object lesson of the compound of plural oxetanyl as intramolecular, it is possible to use Aron Oxetane OXT-121, OXT-221, OX-SQ, PNOX (above, Toagosei Co., Ltd's system).

Additionally, the compound comprising oxetanyl is preferably used alone or mixes with the compound comprising epoxy radicals and makes With.

As cross-linking agent C1, it is also possible to preferably employ blocked isocyanate based compound.

As long as blocked isocyanate compounds has the blocked isocyanate base that NCO is chemically protected Compound be then not particularly limited, but from the viewpoint of curable, it is different that preferably 1 intramolecular has plural end-blocking The compound of cyanic acid ester group.

It addition, the blocked isocyanate base in the present invention is can be by being thermally generated the group of NCO, preferable example The group such as making end-capping reagent and NCO react and to be protected by NCO is shown.Additionally, above-mentioned end-blocking Carbimide. Ester group preferably can generate the group of NCO by 90 DEG C～the heat of 250 DEG C.

Additionally, as blocked isocyanate compounds, its skeleton is not particularly limited, as long as have in 1 molecule Two NCOs, then can be arbitrary compound, can be aliphatic, alicyclic or aromatic polyisocyanates, But can suitably use such as 2,4 toluene diisocyanate, 2,6-toluene di-isocyanate(TDI), isophorone diisocyanate, 1,6- Hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethyl Hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, 1,9-nine methylene diisocyanate, 1, 10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2 '-Anaesthetie Ether diisocyanate, diphenylmethyl Alkane-4,4 '-diisocyanate, o-Dimethylbenzene diisocyanate, m xylene diisocyanate, xylol diisocyanate, Di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), hexamethylene-1,3-dimethylene diisocyanate, hexamethylene-1,4-dimethylene two Isocyanates, 1,5-naphthalene diisocyanate, to phenylene vulcabond, 3,3 '-xylene-4,4 '-two Carbimide. Ester, 4,4 '-diphenyl ether diisocyanate, tetrachloro phenylene vulcabond, norbornene alkyl diisocyanate, hydrogenation 1,3-benzene Dimethyl diisocyanate, the hydrogenation isocyanate compound such as 1,4-xylylene diisocyanate and derived from by these compounds The compound of skeleton of prepolymer type.In them, particularly preferably toluene di-isocyanate(TDI) (TDI) or diphenyl methane two is different Cyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI).

As the parent structure of the blocked isocyanate compounds in the solidification compound used in the present invention, can list Biuret form, isocyanurate type, adduct type, 2 functional prepolymer types etc..

As forming the end-capping reagent of closed-end structure of above-mentioned blocked isocyanate compounds, oxime compound, interior can be listed Amide compound, phenolic compounds, alcoholic compound, amines, activity methene compound, pyrazole compound, mercaptan compound, Imidazole compound, imide series compound etc..In them, particularly preferably close selected from oxime compound, lactam compound, phenolate End-capping reagent in thing, alcoholic compound, amines, activity methene compound, pyrazole compound.

As above-mentioned oxime compound, oxime and ketoxime can be listed, specifically, acetone oxime, formaldoxime, ring can be exemplified Hexane oxime, methyl ethyl ketone oxime, cyclohexanone-oxime, diphenyl-ketoxime, acetone oxime etc..

As above-mentioned lactam compound, epsilon-caprolactams, butyrolactam etc. can be exemplified.

As above-mentioned phenolic compounds, phenol, naphthols, cresol, xylenols, halogen substiuted phenol etc. can be exemplified.

As above-mentioned alcoholic compound, can exemplify methanol, ethanol, propanol, butanol, Hexalin, ethylene glycol monoalkyl ether, third Glycol monoalkyl ether, lactic acid alkyl ester etc..

As above-mentioned amines, primary amine and secondary amine can be listed, can be aromatic amine, aliphatic amine, cycloaliphatic amines In any one, aniline, diphenylamine, aziridine, polymine etc. can be exemplified.

As above-mentioned activity methene compound, diethyl malonate, dimethyl malenate, acetoacetic acid second can be exemplified Ester, methyl acetoacetate etc..As above-mentioned pyrazole compound, pyrazoles, methylpyrazole, dimethyl pyrazole etc. can be exemplified.

As above-mentioned mercaptan compound, alkyl hydrosulfide, aryl mercaptan etc. can be exemplified.

The blocked isocyanate compounds that can use in the solidification compound used in the present invention can be as commercially available product Obtain, preferably use such as Coronate AP stable M, Coronate2503,2515,2507,2513,2555, Millionate MS-50 (being Nippon Polyurethane Industry CO. above, LTD. system), Takenate B- 830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (are Mitsui Chemicals, Inc above System), Duranate17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF- K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (are Asahi Kasei Chemicals Corporation above System), Desmodule BL1100, BL1265MPA/X, BL3575/1, BL3272MPA, BL3370MPA, BL3475BA/SN, BL5375MPA, VPLS2078/2, BL4265SN, PL340, PL350, Sumidule BL3175 (is Sumika Bayer above Urethane Co., Ltd. system) etc..

As the compound containing alkoxy methyl, preferably alkoxymethylated melamine, aikoxymethytated benzo Guanamines, aikoxymethytated glycolurils and aikoxymethytated carbamide etc..They are respectively by by methylolated melamine, hydroxyl first The methylol of base benzoguanamine, methylolation glycoluril or methylolated urea is converted into alkoxy methyl and obtains.For this The kind of alkoxy methyl is not particularly limited, and can list such as methoxy, ethoxyl methyl, propoxy methyl, fourth Epoxide methyl etc., but from the viewpoint of the generation amount of aerofluxus, particularly preferred methoxy.

In these compounds, alkoxymethylated melamine, aikoxymethytated benzoguanamine, aikoxymethytated sweet Urea can list as preferred compound, from the viewpoint of the transparency, and particularly preferred aikoxymethytated glycolurils.

The compound that its molecular weight is less than 1,000 is also used for solidification compound by the cross-linking agent containing alkoxy methyl In.

These compounds containing alkoxy methyl can obtain as commercially available product, it may be preferred to use such as CYMEL 300, 301、303、370、325、327、701、266、267、238、1141、272、202、1156、1158、1123、1170、1174、 UFR65,300 (more than, Mitsui Cyanamid Co., Ltd. system), NIKALAC MX-750 ,-032 ,-706 ,-708 ,- 40 ,-31 ,-270 ,-280 ,-290, NIKALAC MS-11, NIKALAC MW-30HM ,-100LM ,-390, (more than, SANWA Chemical Co., Ltd. system) etc..

[the 2nd mode of the present invention]

2nd mode of the present invention contains following component of polymer A2 Two azide of quinone B2.

(component of polymer A2)

The component of polymer A2 contained by 2nd mode of the present invention is containing comprising the poly-of the Component units a3 with acidic group The component of polymer of compound A2-1.

Additionally, component of polymer A2 refers in addition to comprising above-mentioned polymer A 2-1, also comprise and be added as needed on The component of polymer of other polymer.

It addition, the polymer contained by component of polymer A2 and the polymer contained by component of polymer A1 of the 1st mode Preferably again the polymer of addition polymerization type, more preferably comprises the Component units from (methyl) acrylic acid and/or its ester Polymer.

2nd mode of the present invention must be fulfilled in the condition shown in following 1～3 at least one, and meet following 4 And at least one in the condition shown in 5.

This represent: in polymer A 2-1 comprising the Component units a3 with acidic group or be different from polymer A 2-1 ground Position or the composition with the crosslinkable groups contributing to solidification are necessary；With comprise the composition list with light orientation group The component of polymer of Component units that is first and that be present in surface for making it be partial to is necessary.

Therefore, in the following description, it is not centered by every kind of polymer, but using needed for component of polymer Illustrate centered by Component units in polymer.

(condition)

Component of polymer A2 comprises polymer A 2-1 at least containing the Component units a3 with acidic group.

Wherein, there is the composition list with acidic group in the Component units a3 of acidic group and the component of polymer A1 of the 1st mode Unit's a3 implication is identical, and preferred scope is the most identical.

In the 2nd mode, in whole Component units of polymer, Component units a3 preferably comprises 3～70 moles of %, more Preferably comprise 5～60 moles of %, further preferably containing 10～50 moles of %.By the use ratio of Component units a3 is set For above-mentioned scope, by dissolubility optimization, obtain the resin combination that sensitivity is excellent simultaneously.

Component of polymer A2 preferably comprises the polymer comprising the Component units a2 with crosslinkable groups.It addition, as above As shown in the condition 1～3 stated, when not containing cross-linking agent C2 described later, at least contain the Component units a3 with acidic group Polymer A 2-1 contain further and there is the Component units a2 of crosslinkable groups or containing comprising the structure with crosslinkable groups Other polymer A 2-2 becoming unit a2 is necessary.

Wherein, have and the Component units a2 of crosslinkable groups and the component of polymer A1 of the 1st mode has bridging property The Component units a2 implication of group is identical, and preferred scope is the most identical.

In the 2nd mode, in whole Component units of polymer, Component units a2 preferably comprises 0～70 mole of %, more Preferably comprise 0～50 mole of %.By the use ratio of Component units a2 is set as above-mentioned scope, it is possible to form various characteristic Excellent cured film.It addition, as it has been described above, when the content of Component units a2 is 0 mole of %, it is necessary to containing cross-linking agent described later C2。

Component of polymer A2 contains the polymer comprising the Component units s1 shown in following s1.It addition, bar described above As shown in part 4 and 5, Component units s1 can be polymer A 2-that (i) at least contains the Component units a3 with acidic group 1 has the mode of Component units s1, (ii) other polymer containing the Component units a2 with crosslinkable groups further A2-2 has other polymer A 2-3 of the mode of Component units s1 and (iii) further and has in the mode of Component units s1 Any one.

Wherein, the Component units s1 implication in the component of polymer A1 of Component units s1 and the 1st mode is identical, preferred model Enclose the most identical.

In the 2nd mode of the present invention, as the 1st mode, have Component units s1 polymer content relative to The all solids composition of resin combination is preferably 0.1～20 mass %, more preferably 0.1～10 mass %.

In the 2nd mode, component of polymer A2 can also be containing except above-mentioned Component units a3, Component units a2 and structure Become the polymer also beyond unit s1 with the Component units a5 in addition to them.

As becoming the monomer of Component units a5, as long as the unsaturation beyond above-mentioned Component units a3 and Component units a2 Compound is then not particularly limited.

As the object lesson of the free radical polymerization monomer used to form Component units a5, can list such as Methacrylic acid chain-like alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid chain-like alkyl ester, acrylic acid cyclic alkyl ester, Aryl methacrylate, benzyl acrylate, unsaturated dicarboxylic diester, bicyclo-unsaturated compound, maleimation Compound, unsaturated aromatic compound, conjugated diene, oxolane skeleton, furan skeleton, Pentamethylene oxide. skeleton, pyrans skeleton, Unsaturated compound and other unsaturated compound of comprising skeleton represented by following formula (4) etc..As in order to form composition Unit a5 and the object lesson of free radical polymerization monomer that uses, it is possible to use the section of Japanese Unexamined Patent Publication 2012-88459 publication The compound etc. that the number of falling 0046～0065 is recorded, this content is included in present specification.

[chemical formula 32]

In above-mentioned formula (4), R²³For hydrogen atom or methyl.S is the integer of more than 1.

In these Component units a5, preferably methacrylic acid chain-like alkyl ester, methacrylic acid cyclic alkyl ester, Malaysia Imide compound, oxolane skeleton, furan skeleton, Pentamethylene oxide. skeleton, pyrans skeleton, to have above-mentioned formula (4) represented The unsaturated compound of skeleton, unsaturated aromatic compound, acrylic acid cyclic alkyl ester, acryloyl morpholine.In them, The positive lauryl of styrene, methyl methacrylate, Tert-butyl Methacrylate, methacrylic acid, methacrylic acid three ring [5.2.1.02,6] decane-8-base, to methoxy styrene, acrylic acid 2-methylcyclohexyl ester, N-phenylmaleimide, N- N-cyclohexylmaleimide, (methyl) acrylic acid tetrahydro furfuryl ester, Polyethylene Glycol (n=2～10) single (methyl) acrylate, 3- (methyl) acryloxy oxolane-2-ketone, acryloyl morpholine are from copolyreaction and relative to the dissolving of aqueous alkali The aspect of property is set out more preferably.These compounds can be used alone, it is also possible to is use mixing two or more.

In the 2nd mode, in whole Component units of polymer, Component units a5 preferably comprises 1～90 mole of %, more Preferably comprise 5～80 moles of %, further preferably containing 7～60 moles of %.By the use ratio of Component units a5 is set For above-mentioned scope, it is possible to form the cured film of various excellent.

(quinone diazide B2)

2nd mode of the present invention contains quinone diazide B2.

As quinone diazide B2, it is possible to use produce the 1 of carboxylic acid, 2-quinone two Azide by irradiating of active ray Thing.

As 1,2-quinone diazide, it is possible to use phenoloid or alcohol compound (hereinafter referred to as " parent nucleus ") Condensation substance with 1,2-naphthoquinone two nitrine sulfonic acid halide.As the object lesson of these compounds, it is referred to such as Japanese Unexamined Patent Publication The record of the paragraph 0075～0078 of 2012-088459 publication, this content is included in present specification.

At phenoloid or alcohol compound (parent nucleus) and 1, in the condensation reaction of 2-naphthoquinone two nitrine sulfonic acid halide, relatively OH radix in phenoloid or alcohol compound, it is possible to use preferably with 30～85 moles of %, more preferably with 50～70 Mole 1,2-naphthoquinone two nitrine sulfonic acid halide suitable for %.Condensation reaction can be implemented by known method.

Additionally, as 1,2-quinone diazide, it is possible to suitably use and the ester bond of foregoing illustrative parent nucleus is changed to acyl The 1,2-naphthoquinone two nitrine sulfonic acid amides class of amine key, such as 2,3,4-triamido BP-1,2-naphthoquinone two nitrine-4-sulfonic acid Amide etc..Further, it is also possible to use 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] bis-phenols (1.0 moles) and the condensation substance of 1,2-naphthoquinone two nitrine-5-sulfonic acid chloride (3.0 moles), 1,1,1-tri-(p-hydroxybenzene) ethane (1.0 moles) and the condensation substance of 1,2-naphthoquinone two nitrine-5-sulfonic acid chloride (2.0 moles), 2,3,4,4 '-tetrahydroxybenzophenone The condensation substance etc. of (1.0 moles) and 1,2-naphthoquinone two nitrine-5-sulphonic acid ester (2.44 moles).

These quinones diazide B2 can be used alone or is used in combination of two or more.

The content of the quinone diazide B2 in the 2nd mode is relative to all solids composition 100 matter in resin combination Amount part is preferably 1～50 mass parts, more preferably 2～40 mass parts, more preferably 10～25 mass parts.

By the use level of quinone diazide B2 is set as above-mentioned scope, active ray is relative to becoming developer solution Aqueous alkali to irradiate part big with the difference of the dissolubility of irradiated portion, patterning performance becomes good, in addition obtained by The solvent resistance of cured film becomes good.

(cross-linking agent C2)

2nd mode of the present invention being unsatisfactory for the above-mentioned situation of condition 1 and 2, i.e. component of polymer A2 does not contains and has In the case of the polymer of crosslinkable groups, containing the cross-linking agent C2 that molecular weight is 1, less than 000.Even it addition, on Man Zuing In the case of the condition 1 or 2 stated, it is also possible to containing cross-linking agent C2.

Wherein, the cross-linking agent C1 implication used in cross-linking agent C2 and the 1st mode is identical, and preferred scope is the most identical.

(organic solvent D)

They (below, are also generally called for short by the photosensitive polymer combination described in the 1st mode of the present invention and the 2nd mode For " resin combination of the present invention ") preferably comprise organic solvent D.

As organic solvent D, it is possible to use known organic solvent, ethylene glycol monoalkyl ether class, ethylene glycol can be exemplified Dialkyl ether, ethylene glycol monoalkyl ether acetate class, propylene-glycol monoalky lether class, propylene glycol dialkyl ether, propylene glycol list Alkylether acetates class, diethylene glycol dialkyl ether class, diethylene glycol monoalkyl ether acetate class, dipropylene glycol monoalkylether Class, butanediol oxalic acid esters, dipropylene glycol dialkyl ether, dipropylene glycol monoalkylether acetate esters, alcohols, esters, ketone Class, amide-type, lactone etc..As the object lesson of these organic solvents, it is referred to Japanese Unexamined Patent Publication 2009-098616 public affairs The paragraph 0062 of report.

For preferred object lesson, propylene glycol monomethyl ether, diethylene glycol diethyl ether, diethyl can be listed Glycol ethyl-methyl ether, propylene glycol monomethyl ether, 1,3 butylene glycol diacetate esters, methoxy propanol acetate, Hexacyclonic Acid Ester, propylene-glycol diacetate, tetrahydrofurfuryl alcohol.

The boiling point of organic solvent D from the viewpoint of coating, preferably 100 DEG C～300 DEG C, more preferably 120 DEG C～ 250℃。

In the present invention, spendable organic solvent D can be used alone one or by two or more and use.It is also preferred that will boiling The different solvent of point is also used.

From be adjusted to the viscosity being suitable to coating so from the viewpoint of, containing content during organic solvent D relative to resin All solids composition 100 mass parts of compositions, preferably 100～3,000 mass parts, more preferably 200～2,000 mass Part, more preferably 250～1,000 mass parts.

As the solid component concentration of resin combination, preferably 3～50 mass %, more preferably 20～40 mass %.

(sensitizer)

In the photosensitive polymer combination described in the 1st mode of the resin combination of the present invention, the particularly present invention, In combination with light acid producing agent B1, in order to promote that it decomposes, preferably comprise sensitizer.

Sensitizer absorbing activity light or lonizing radiation and become electron excitation state.Become the sensitizer of electron excitation state Contact with light acid producing agent, produce the effects such as electron transfer, energy transfer, heating.Thus, light acid producing agent causes chemical change And decompose, and generate acid.As the example of preferred sensitizer, can list belong to following compounds and Arbitrary place of the wavelength domain of 350nm to 450nm has the compound of absorbing wavelength.

The polynuclear aromatic same clan (such as, pyrene, connection triphenylene, anthracene, 9,10-dibutoxy anthracene, 9,10-diethoxy anthracene, 3,7-dimethoxy anthracenes, 9,10-dipropoxy anthracene), ton class (such as, fluorescein, eosin, erythrosine, rhodamine B, Bangladesh Rose-red), xanthones (such as, ton ketone, thiaxanthone, dimethyl thioxanthone, diethyl thioxanthone), cyanine class (such as, sulfur Miscellaneous carbocyanine, oxa-carbocyanine), merocyanine class (such as, merocyanine, carbonyl merocyanine) if red cyanines class, oxonols class, thiazide (such as, thionine, methylene blue, toluidine blue), acridine (such as, acridine orange, chloroflavin, acriflavine), acridine ketone (example As, acridone, 10-butyl-2-chloro-acridine ketone), Anthraquinones (such as, anthraquinone), side acid in salt (such as, side acid in Salt), styrene base class, basicity styrene base class (such as, 2-{2-[4-(dimethylamino) phenyl] vinyl } benzothiazole), Coumarins (such as, 7-diethylamino-4-methylcoumarin, Hymecromone, 2,3,6,7-tetrahydrochysene-9-first Base-1H, 5H, 11H [1] .alpha.-5:6-benzopyran also [6,7,8-ij] quinolizine-11-ketone).

In these sensitizers, the preferably polynuclear aromatic same clan, acridine ketone, styrene base class, basicity styrene base class, tonkabean Element class, more preferably the polynuclear aromatic same clan.In the polynuclear aromatic same clan, most preferably anthracene derivant.

The content of sensitizer 100 mass parts relative to light acid producing agent B1 or quinone diazide B2 are preferably 0～1, 000 mass parts, more preferably 10～500 mass parts, more preferably 50～200 mass parts.

Additionally, sensitizer can be used alone one, it is also possible to by two or more and use.

(alkali compounds)

The resin combination of the present invention can also contain alkali compounds.

As alkali compounds, can chemically amplify in the alkali compounds used in solidification compound and arbitrarily select Use.Such as aliphatic amine, aromatic amine, hetero ring type amine, quaternary ammonium hydroxide, the quaternary ammonium salt etc. of carboxylic acid can be listed.As Their object lesson, can list the chemical combination described in paragraph 0204～0207 of Japanese Unexamined Patent Publication 2011-221494 publication Thing.

Specifically, as aliphatic amine, such as Trimethylamine, diethylamide, triethylamine, diη-propyl can be listed Amine, three n-pro-pyl amine, two n-pentyl amine, three n-pentyl amine, diethanolamine, triethanolamine, dicyclohexylamine, dicyclohexylmethyl Amine etc..

As aromatic amine, such as aniline, benzyl amine, DMA, diphenylamine etc. can be listed.

As hetero ring type amine, such as pyridine, 2-picoline, 4-picoline, 2-ethylpyridine, 4-ethyl can be listed Pyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl 4-phenyl pyridine, 4-dimethylaminopyridine, imidazoles, benzimidazole, 4-methylimidazole, 2-Phenylbenzimidazole, 2,4,5-triphenylimidazolyl, nicotine, nicotinic acid, nicotiamide, quinoline, 8-hydroxyquinoline, Pyrazine, pyrazoles, pyridazine, purine, pyrrolidine, piperidines, piperazine, morpholine, 4-methyl morpholine, N-cyclohexyl-N '-[2-(4-morpholine Base) ethyl] thiourea, 1,5-diazabicylo [4.3.0]-5-nonene, 1,8-diazabicylo [5.3.0]-7-endecatylene, fourth Alkane-1,2,3,4-tetrabasic carboxylic acid four (1,2,2,6,6-pentamethyl-4-piperidyl) etc..

As quaternary ammonium hydroxide, such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, the positive fourth of hydroxide four can be listed Base ammonium, hydroxide four n-hexyl ammonium etc..

As the quaternary ammonium salt of carboxylic acid, such as acetic acid tetramethyl-ammonium, benzoic acid tetramethyl-ammonium, acetic acid tetra-n-butyl can be listed Ammonium, benzoic acid tetra-n-butyl ammonium etc..

In them, preferably hetero ring type amine, particularly preferred N-cyclohexyl-N '-[2-(4-morpholinyl) ethyl] thiourea.

Alkali compounds can be used alone one, it is also possible to by two or more and use.

Additionally, containing content during alkali compounds relative to all solids composition 100 mass parts in resin combination It is preferably 0.001～3 mass parts, more preferably 0.05～0.5 mass parts.

(surfactant)

The resin combination of the present invention can also contain surfactant.

As surfactant, it is possible to use any one in anion system, cation system, nonionic system or both sexes, but Preferably surfactant is nonionic system surfactant.As surfactant, preferably nonionic system surfactant, more Preferably fluorine system surfactant.

As the surfactant that can use in the 1st mode, the Megafac such as commercially available product can be listed F142D、Megafac F172、Megafac F173、Megafac F176、Megafac F177、Megafac F183、 Megafac F479、Megafac F482、Megafac F554、Megafac F780、Megafac F781、Megafac F781-F、Megafac R30、Megafac R08、Megafac F-472SF、Megafac BL20、Megafac R-61、 Megafac R-90 (Dainippon Ink Chemicals's system), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431, Novec FC-4430 (Sumitomo 3M Limited system), AsahiGuard AG7105,7000, 950、7600、Surflon S-112、Surflon S-113、Surflon S-131、Surflon S-141、Surflon S- 145、Surflon S-382、Surflon SC-101、Surflon SC-102、Surflon SC-103、Surflon SC- 104, Surflon SC-105, Surflon SC-106 (Asahi Glass Co., Ltd's system), EFTOP EF351, EFTOP 352, EFTOP 801, EFTOP 802 (Mitsubishi Materials Electronic Chemicals Co., Ltd. system), Ftergent 250 (Neos Corporation system).Additionally, in addition to the foregoing, KP (SHIN-ETSU HANTOTAI's chemical industry can also be listed Co., Ltd.'s system), POLYFLOW (Kyoeisha Chemical Co., Ltd.'s system), EFTOP (Mitsubishi Materials Electronic Chemicals Co., Ltd. system), Megafac (Dainippon Ink Chemicals's system), Fluorad (Sumitomo 3M Limited system), AsahiGuard, Surflon (Asahi Glass Co., Ltd's system), each series such as PolyFox (OMNOVA system).

Additionally, as surfactant, the change described in Japanese Unexamined Patent Publication 2014-238438 publication paragraph 0151～0155 Compound can also list as preferred example.

It is preferably relative to 100 mass parts in all solids composition of resin combination containing content during surfactant 0.001～5.0 mass parts, more preferably 0.01～2.0 mass parts.

Surfactant can only comprise one, it is also possible to comprises two or more.When comprising two or more, preferably it closes Metering reaches above-mentioned scope.

(closely sealed modifying agent)

The resin combination of the present invention can also contain closely sealed modifying agent.

As closely sealed modifying agent, alkoxysilane compound containing trialkylsilyl group in molecular structure etc. can be listed.

Alkoxysilane compound containing trialkylsilyl group in molecular structure preferably becomes the inorganic matter such as silication such as silicon, silicon oxide, silicon nitride of base material and closes The compound that the adaptation of the metals such as thing, gold, copper, molybdenum, titanium, aluminum and dielectric film improves.

As the object lesson of closely sealed modifying agent, such as gamma-amino propyl trimethoxy silicane, gamma-amino can be listed Propyl-triethoxysilicane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl group triethoxysilane, γ-glycidoxypropyl dimethoxysilane, γ-methacryloyloxypropyl methyl diethoxy silane, γ-first Base acryloxypropyl triethoxysilane, γ-r-chloropropyl trimethoxyl silane, γ mercaptopropyitrimethoxy silane, β- (3,4-epoxycyclohexyl) ethyl trimethoxy silane, vinyltrimethoxy silane etc..In them, preferably γ-epoxy the third oxygen Base propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, more preferably γ-glycidoxypropyl group Trimethoxy silane.They can be used alone one or are used in combination of two or more.

The content of closely sealed modifying agent relative to all solids composition 100 mass parts of resin combination be preferably 0.001～ 15 mass parts, more preferably 0.005～10 mass parts.Closely sealed modifying agent can only use one, it is possible to use two or more. When using two or more, preferably total amount reaches above-mentioned scope.

(antioxidant)

The resin combination of the present invention can also contain antioxidant.

As antioxidant, known antioxidant can be contained.By adding antioxidant, have and be prevented from solidification The coloring of film, maybe can reduce the thickness caused by decomposition reduce, the excellent such advantage of heat resistant transparent in addition.

As such antioxidant, can list such as phosphorous antioxidant, amide-type, hydrazides class, hindered amine system resist Oxidant, sulfur system antioxidant, phenol system antioxidant, Vitamin C acids, zinc sulfate, saccharide, nitrite, sulphite, sulfur Thiosulfate, hydroxy amine derivatives etc..In them, from the viewpoint of the coloring of cured film, thickness reduce, particularly preferred phenol system Antioxidant, amide system antioxidant, hydrazides system antioxidant, sulfur system antioxidant, most preferably phenol system antioxidant.They can To be used alone one, it is also possible to by two or more mixing.

As object lesson, can list described in the paragraph 0026～0031 of Japanese Unexamined Patent Publication 2005-29515 publication Compound, these contents are included in present specification.

As the commercially available product of phenol system antioxidant, can list such as Adekastab AO-15, Adekastab AO-18, Adekastab AO-20、Adekastab AO-23、Adekastab AO-30、Adekastab AO-37、Adekastab AO- 40、Adekastab AO-50、Adekastab AO-51、Adekastab AO-60、Adekastab AO-70、Adekastab AO-80、Adekastab AO-330、Adekastab AO-412S、Adekastab AO-503、Adekastab A-611、 Adekastab A-612、Adekastab A-613、Adekastab PEP-4C、Adekastab PEP-8、Adekastab PEP-8W、Adekastab PEP-24G、Adekastab PEP-36、Adekastab PEP-36Z、Adekastab HP-10、 Adekastab 2112、Adekastab 260、Adekastab 522A、Adekastab 1178、Adekastab 1500、 Adekastab C、Adekastab 135A、Adekastab 3010、Adekastab TPP、Adekastab CDA-1、 Adekastab CDA-6, Adekastab ZS-27, Adekastab ZS-90, Adekastab ZS-91 (more than, Co., Ltd. ADEKA system), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irganox MD1024, Irganox 1035FF、Irganox1035、Irganox 1098、Irganox 1330、Irganox 1520L、Irganox 3114、 Irganox1726, Irgafos 168, Irgamod 295 (BASF system), Tinuvin 405 (BASF system) etc..Wherein it is possible to it is suitable When use Adekastab AO-60, Adekastab AO-80, Irganox 1726, Irganox 1035, Irganox 1098, Tinuvin 405。

It is preferably relative to all solids composition 100 mass parts of resinous compositions containing content during antioxidant 0.1～10 mass %, more preferably 0.2～5 mass %, particularly preferably 0.5～4 mass %.By being set as this scope, can Obtain the sufficient transparency of formed film, and sensitivity when pattern is formed also becomes good.

(other composition)

The resin combination of the present invention is in addition to mentioned component, it is also possible to add UV absorbent, gold as required Belong to passivator or acid proliferation generator, development accelerant, plasticizer, hot radical producing agent, thermal acid generator, thickening agent and organic Or the known additive such as inorganic antisettling agent.Additionally, as these compounds, it is also possible to see, for example Japanese Unexamined Patent Publication The paragraph 0201～0224 of 2012-88459 publication, the record of Japanese Unexamined Patent Publication 2014-238438 publication, these contents are received Enter in present specification.

Additionally, as other additive, it is possible to use the paragraph 0120～0121 of Japanese Unexamined Patent Publication 2012-8223 publication Described in hot radical producing agent, nitrogen-containing compound described in International Publication the 2011/136074th and thermal acid generator, These contents are included in present specification.

(modulator approach of photosensitive polymer combination)

Each composition can with the ratio of regulation and be mixed by the resin combination of the present invention by arbitrary method, stirs molten Solve and modulate.For example, it is also possible to after each composition being dissolved in the most in advance solution being made by solvent, by them with the ratio of regulation Mix and modulate the photosensitive polymer combination of the present invention.The composition solution modulated as above can also use such as hole Footpath is to use after the filter of 0.2 μm etc. filters.

[manufacture method of cured film]

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

(1) operation (painting process) resin combination of the present invention containing organic solvent D being applied on substrate；

(2) from the resin combination of coating, remove the operation (solvent removal step) of organic solvent D；

(3) operation (the exposure work that the resin combination eliminating organic solvent D is exposed by activity lonizing radiation Sequence)；

(4) exposed resin combination is carried out by developer solution the operation (developing procedure) developed；

(5) developed resin combination is carried out heat cure and obtain the operation (post-bake process) of cured film.

Each operation is illustrated by next coming in order.

In the operation of (1), preferably the resin combination of the present invention is coated make on substrate bag solvent-laden wet Profit film.

Before the operation carrying out (1), it is also possible to carry out the washing such as neutralizing treatment or plasma washing relative to substrate.This Outward, it is also possible to substrate surface is processed with hexamethyldisiloxane etc. relative to the substrate after washing.As with hexamethyl The method that substrate surface is processed by disilazane, is not particularly limited, but can list and such as substrate is exposed to pregnancy Method etc. in base disilazane steam.

As substrate, inorganic substrate, resin substrate can be listed, employ the composite of resin material and inorganic material Substrate etc..

As inorganic substrate, such as glass substrate, quartz base plate, silicon substrate, silicon nitride board and at these can be listed On substrate, evaporation has the composite base plate of molybdenum, titanium, aluminum, copper etc..

As resin substrate, can list by polybutylene terephthalate (PBT), polyethylene terephthalate, poly-naphthalene Naphthalate, PBN, polystyrene, Merlon, polysulfones, polyether sulfone, polyarylate, pi-allyl Diglycol carbonates, polyamide, polyimides, polyamidoimide, Polyetherimide, polybenzoxazole, polyphenylene sulfide, polycyclic alkene Fluororesin, liquid crystal polymer, acrylic resin, epoxy resin, the silicone trees such as hydrocarbon, norbornene resin, polychlorotrifluoroethylene Fat, ionomer resin, cyanate ester resin, crosslinking dimethyl ester, cyclic polyolefin, aromatic ether, maleimide-alkene, The substrate that the synthetic resin such as cellulose, episulfide compounds is constituted.

These substrates can also form such as thin film transistor (TFT) (thin film according to the form of end article Transistor:TFT) multilayer laminate constructions as element.

Resin combination coating process on substrate is not particularly limited, it is possible to use such as slot coated method, spraying The methods such as method, rolling method, method of spin coating, cast coating method, slit and circumgyration.

In the case of slot coated method, preferably the relative moving speed of substrate Yu slit die is set as 50～ 120mm/sec。

Moistening thickness when being coated with by resin combination is not particularly limited, and can enter with the thickness corresponding with purposes Row coating.Such as it is preferably 0.5～10 μm.

Before can also being coated with the resin combination of the present invention on substrate, application is such as Japanese Unexamined Patent Publication 2009-145395 The pre-wet method of what is called as described in publication.

In the operation of (2), the above-mentioned moistening film formed from coating resin compositions, by decompression (vacuum) And/or heating etc., solvent is removed and on substrate, forms desciccator diaphragm.The heating condition of solvent removal step be preferably 70～ At 130 DEG C about 30～300 seconds.When temperature and time is above-mentioned scope, there is the pattern when carrying out the operation of (4) described later Adaptation better and also can reduce the tendency of residue further.

In the operation of (3), the substrate being provided with desciccator diaphragm is irradiated the active ray of the pattern of regulation.In this operation In, in exposure portion, generating the acidic group such as carboxyl or phenolic hydroxyl group, exposure portion dissolubility in developer solution improves.

That is, comprise containing have acidic group by acid decomposability radical protection group Component units component of polymer and In the mode of light acid producing agent, by the irradiation of active ray, light acid producing agent decomposes and produces acid.And then, by produce The catalytic action of acid, the sour decomposability group comprised in desciccator diaphragm is hydrolyzed, and generates carboxyl or phenolic hydroxyl group.

Additionally, in the mode comprising quinone diazide, by the irradiation of active ray, quinone diazide generate Carboxyl.

Light source as active ray, it is possible to use low pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, chemical lamp, luminescence two Pole pipe (LED) light source, excimer laser generator etc., preferably use i ray (365nm), h ray (405nm), g ray (436nm) etc. there is the active ray of the wavelength that wavelength is more than 300nm and below 450nm.Additionally, can also lead to as required Cross light splitting wave filter as long wavelength cutoff wave filter, short wavelength's cut-off filter, band filter to adjust irradiation light.Expose Light quantity is preferably 1～500mJ/cm²。

As exposure device, it is possible to use mirror surface projection alignment exposer, stepper, scanning device, close induction type, contact, The exposure machine of the various modes such as microlens array, lens scan device, laser explosure.In addition it is also possible to carry out employing so-called The exposure of super resolution technology.As super resolution technology, can list and carry out the multiple-exposure of multiexposure, multiple exposure or use phase shift The method of mask, annular illumination method etc..By using these super resolution technologies can form the pattern of more fine, thus excellent Choosing.

In the operation of (4), use developer solution that resin combination is developed.Development easily it is dissolved in by having The exposure portion region of the acidic group in liquid removes, and forms eurymeric image.

In the developer solution used in developing procedure, preferably comprise the aqueous solution of alkali compounds.As alkali compounds, The alkali metal hydroxides such as such as Lithium hydrate, sodium hydroxide, potassium hydroxide can be used；Sodium carbonate, potassium carbonate, cesium carbonate Deng alkali carbonate class；The alkali metal hydrogencarbonate class such as sodium bicarbonate, potassium bicarbonate；Tetramethyl ammonium hydroxide, hydroxide four The tetraalkylammonium hydroxide classes such as ethyl ammonium, tetrapropylammonium hydroxide, tetrabutylammonium, diethyldimethylammonhydroxide hydroxide: The hydroxides such as choline (hydroxy alkyl) trialkyl ammonium class；The silicates such as sodium silicate, sodium metasilicate；Ethamine, propylamine, diethylamine, The alkyl amines such as triethylamine；The alcamines such as dimethylethanolamine, triethanolamine；1,8-diazabicylo-[5.4.0]-7-11 The ester ring type amines such as carbene, 1,5-diazabicylo-[4.3.0]-5-nonene.

In them, preferably sodium hydroxide, potassium hydroxide, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, hydroxide 4 third Base ammonium, tetrabutylammonium, choline (hydroxide-2-hydroxyethyl trimethyl ammonium).

In addition it is also possible to by the aqueous solution of above-mentioned bases add the water-miscible organic solvent such as proper amount of methanol or ethanol or Surfactant and the aqueous solution that obtains use as developer solution.

The pH of developer solution is preferably 10.0～14.0.

Developing time is preferably 30～500 seconds, additionally, the method for development can be puddle method (sheathed immersion method), spray Any one in pouring method, infusion process etc..

After development, it is also possible to carry out drip washing operation.In drip washing operation, by the substrate pure water after development etc. is clear Wash, carry out the removing of accompanying developer solution, the removing of development residue.ELUTION METHOD can use known method.Can enumerate Go out such as spray drip washing or dipping drip washing etc..

In the operation of (5), by being heated by obtained eurymeric image, acid decomposability group thermal decomposition is made to give birth to Become the acidic group such as carboxyl or phenolic hydroxyl group, cross-link with crosslinkable groups, cross-linking agent etc., thus can form cured film.This heating is excellent Choosing uses the heater such as hot plate or baking oven to carry out.Heating-up temperature is preferably 200 DEG C～350 DEG C, more preferably 250 DEG C～ 350℃.If heat time heating time is then preferably 5～90 minutes on hot plate, if baking oven is then preferably 30～120 minutes.By adding Heat carries out cyclization or cross-linking reaction such that it is able to form the cured film that thermostability, hardness etc. are more excellent.Additionally, carry out During heat treated, it is also possible to improve the transparency further by carrying out in a nitrogen atmosphere.

Before rear baking, it is also possible to carry out after bake roasting (roasting procedure in the middle of adding) after toasting at a lower temperature. During underway baking, after preferably heating 1～60 minute at 90～150 DEG C, under the high temperature more than 200 DEG C, carry out after bake Roasting.In addition it is also possible to be divided into the multistage in three stages more than to heat centre baking, rear baking.By arranging so Toast in the middle of, toast afterwards, the tip angle of pattern can be adjusted.These heating can use hot plate, baking oven, infrared heater Deng known heating means.

Furthermore it is possible to before rear baking, to formed figuratum substrate by active ray carry out exposing again comprehensively (after Exposure) after, toast after carrying out, thus produce acid from the light acid producing agent being present in unexposed portion, as promoting crosslinking work The catalyst function of sequence, such that it is able to promote the curing reaction of film.As preferably exposing when including post-exposure operation Amount, preferably 100～3,000mJ/cm², particularly preferably 100～500mJ/cm²。

The cured film obtained by the resin combination of the present invention can also use as dry-etching resist.To pass through Post-bake process carries out the cured film obtained by heat cure when using as dry-etching resist, as etch processes, permissible Carry out being ashed, plasma etching, the dry-etching such as ozone etching process.

Additionally, the manufacture method of the cured film of the present invention is after above-mentioned post-bake process, from making obtained cured film From the viewpoint of alignment films function, it is preferable to carry out light orientation process.

Light orientation process, in addition to the light using wavelength to be below 313nm, is not particularly limited, but uses the purple of polarization Outside line is preferred in terms of orientation obtaining uniformly.In the case of Gai, the method for the ultraviolet irradiating polarization be not particularly limited. It addition, as polarized light, be not particularly limited, such as rectilinearly polarized light, circularly polarized light, elliptically polarized light etc. can be listed, its In, preferably rectilinearly polarized light.

As long as additionally, substantially obtain polarized light, it is also possible to the light of no polarization is certain from the normal slope of thin film Angle is irradiated.In other words, it is also possible to from the oblique irradiation non-polarized light on cured film surface.So-called " oblique illumination ", only If tilted the direction of polar angle θ (0 < θ < 90 °) relative to cured film normal to a surface direction, then it is not particularly limited, permissible Suitably select according to purpose, but θ is preferably 20～80 °.

As the light source of the light used, such as xenon lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, metal halide can be listed Thing lamp etc..

Relative to the ultraviolet obtained by such light source, by using interferometric filter or colored filter etc., permissible Limit the wave-length coverage irradiated.Additionally, relative to the light from these light sources, by using polarizing filter or ahrens prism, Rectilinearly polarized light can be obtained.

[cured film]

The cured film of the present invention is the cured film obtained by the resin composition of the above-mentioned present invention.Additionally, this The cured film that the cured film of invention obtains preferably by the forming method of the cured film of the above-mentioned present invention.

The cured film of the present invention suitably can use as interlayer dielectric and protecting film, particularly as layer insulation When film uses, by implementing light orientation process in advance, cured film also has the function as alignment films, so to liquid crystal described later The purposes of display device is useful.

[liquid crystal indicator]

The liquid crystal indicator of the present invention has the cured film of the present invention.

As the liquid crystal indicator of the present invention, as long as using the layer insulation that the resin combination using the present invention is formed Film is not particularly limited, and goes for taking the known liquid crystal indicator of various structure.Additionally, due to use this The interlayer dielectric that bright resin combination is formed can double as alignment films, it is possible to makes from known liquid crystal indicator Remove the structure of alignment films.

Such as, as the object lesson of the thin film transistor (TFT) (TFT) that the liquid crystal indicator of the present invention is possessed, can enumerate Go out non-crystalline silicon-TFT, low temperature polycrystalline silicon-TFT, oxide semiconductor TFT etc..The cured film of the present invention is excellent due to electrical characteristics, institute It is preferably used can combine with these TFT.

Additionally, the liquid crystal drive mode can taked as the liquid crystal indicator of the present invention, TN (Twisted can be listed Nematic) mode, VA (Vertical Alignment) mode, IPS (In-Plane-Switching) mode, FFS (Fringe Field Switching) mode, OCB (Optically Compensated Bend) mode etc..

In panel is constituted, can also make in the liquid crystal indicator of COA (Color Filteron Allay) mode By the cured film of the present invention, such as, can be used as organic insulating film (115) or the Japan of Japanese Unexamined Patent Publication 2005-284291 publication The organic insulating film (212) of JP 2005-346054 publication.

Additionally, the cured film of the resin combination of the present invention and the present invention is not limited to such use, may be used for each Plant in purposes.Such as, in addition to interlayer dielectric, it is also possible to be appropriately used for the protecting film of color filter or for by liquid crystal The thickness of the liquid crystal layer in showing device keep constant distance piece or be arranged in solid-state imager on color filter micro- Mirror etc..

For the details of liquid crystal indicator, it is referred to Japanese Unexamined Patent Publication 2007-328210 publication and Japan is special Opening the record of 2014-238438 publication, this content is included in this specification.

Embodiment

Below based on embodiment, the present invention is described in detail further.Material shown in below example, make Consumption, ratio, process content, process step etc. without departing from the purport of the present invention, then can suitably change.Therefore, this Bright scope should be by the limited explanation of embodiment described below.It addition, unless otherwise specified, then " part ", " % " is quality criteria.

(there is the synthesis of the Component units (monomer a-1) of light orientation group)

By trans-4-hydroxy-methyl cinnamate (Tokyo HuaCheng Industry Co., Ltd's system, 12.5g, 0.07mol) and triethyl group Amine (Wako Pure Chemical Industries, Ltd.'s system, 7.79g, 0.07mol) is dissolved in oxolane (following, to be abbreviated as " THF ") 100mL In, after being cooled to 0 DEG C, it is slowly added dropwise methacrylic chloride (Tokyo HuaCheng Industry Co., Ltd's system, 7.33g, 0.07mol).

Then, add water 500g relative to the reaction system of nebulousurine, filter after stirring 1 hour, obtain 14g and there is cinnamic acid Ester group is as the monomer a-1 of light orientation group.Structure is confirmed by NMR (nuclear magnetic resonance).

(there is the synthesis of the Component units (monomer a-2) of light orientation group)

Ferulic acid ethyl ester (Tokyo HuaCheng Industry Co., Ltd's system, 22.2g, 0.1mol) is dissolved In dimethyl acetylamide 150mL, add potassium carbonate (Wako Pure Chemical Industries, Ltd.'s system, 30g, 0.22mol), by temperature Rise to 90 DEG C.

Then, dropping 4-methaform (Wako Pure Chemical Industries, Ltd.'s system, 21.6g, 0.2mol), stir 3 hours.

Afterwards, reaction solution is injected in water 1L, after being neutralized with 2NHCl, extracts with ethyl acetate 700mL Take, clean with saturated aqueous common salt and concentrate.

Then, carry out point taking by silica gel column chromatography, obtain 23g midbody compound.

Make this midbody compound 15g (0.05mol) and triethylamine (Wako Pure Chemical Industries, Ltd.'s system, 5.6g, 0.056mol) it is dissolved in THF100mL, is cooled to 0 DEG C.

Then, dropping methacrylic chloride (Tokyo HuaCheng Industry Co., Ltd's system, 5.8g, 0.056mol), stir 3 hours After, reaction solution is injected in water 500g, to concentrate after ethyl acetate extraction.

Then, divided by silica gel column chromatography and take, obtain 20g and there is interval base cinnamate as light orientation group Monomer a-2.

(there is the synthesis of the Component units (monomer a-3) of light orientation group)

Hydroquinone (Wako Pure Chemical Industries, Ltd.'s system, 63.8g, 0.58mol) is made to be dissolved into dimethyl acetylamide 500mL In, add potassium carbonate (Wako Pure Chemical Industries, Ltd.'s system, 40g, 0.29mol), temperature is risen to 90 DEG C.

Then, dropping methacrylic acid 4-neoprene ester (Wako Pure Chemical Industries, Ltd.'s system, 25.6g, 0.145mol), stir Mix 3 hours.

Afterwards, reaction solution is injected in water 1L, with in 2NHCl and after, with ethyl acetate 700mL extract, with saturated Saline solution cleans and concentrates.Coarse crystallization is taken out, is divided by silica gel column chromatography and take, obtain 18g midbody compound.

Make this midbody compound 18g and triethylamine (Wako Pure Chemical Industries, Ltd.'s system, 7.79g, 0.07mol) molten Solution, in THF100mL, is cooled to 0 DEG C.

Then, dropping cinnamoyl chloride (Tokyo HuaCheng Industry Co., Ltd's system, 13.1g, 0.07mol), after stirring 3 hours, Reaction solution is poured in water 500g, to concentrate after ethyl acetate extraction.

Then, divided by silica gel column chromatography and take, obtain 22g and there is the chalcone derivative base monomer a-as light orientation group 3。

(there is the synthesis of the Component units (monomer a-4) of light orientation group)

With Macromolecules 2004, Vol.37, #7, the most similarly operate, synthesized and there is azo group conduct The monomer a-4 of light orientation group.

(there is the synthesis of the Component units (monomer a-5) of light orientation group)

With Jounal of Polymer Science, Part A:Polymer Chemistry, 2010, Vol.48, #19, 4323 similarly operate, and have synthesized the monomer a-5 having coumarin base as light orientation group.

(acidic group is by the synthesis of the Component units (monomer e-1) of acid decomposability radical protection)

Methacrylic acid (Wako Pure Chemical Industries, Ltd.'s system, 86g, 1mol) is cooled to 15 DEG C, adds camphorsulfonic acid (Tokyo HuaCheng Industry Co., Ltd's system, 4.6g, 0.02mol).

Then, drip in reaction solution 2-dihydrofuran (Kawaken Fine Chemicals Co., Ltd. system, 71g, 1mol, 1.0 equivalents).

After one hour of the stirring, add saturated sodium bicarbonate (500mL), extract with ethyl acetate (500mL).

Then, dried with magnesium sulfate, after insoluble matter is filtered below 40 DEG C concentrating under reduced pressure, further by by residue Yellow oil carry out decompression distillation, as monomer e-1, obtaining 125g boiling point (bp.) is 54～56 DEG C/3.5mmHg fraction Methacrylic acid tetrahydrochysene-2H-furan-2-ester as colorless oil (yield is 80%).

(acidic group is by the synthesis of the Component units (monomer e-2) of acid decomposability radical protection)

Then, in reaction solution drip ethyl vinyl ether (Tokyo HuaCheng Industry Co., Ltd's system, 74g, 1mol, 1.0 Equivalent).

After stirring 1 hour, add saturated sodium bicarbonate (500mL), extract with ethyl acetate (500mL).

Then, dried with magnesium sulfate, after insoluble matter is filtered below 40 DEG C concentrating under reduced pressure, further by by residue Yellow oil carry out decompression distillation, as monomer e-2, obtaining 125g boiling point (bp.) is 50～52 DEG C/3.5mmHg fraction Ethoxyethyl methacrylates as colorless oil (yield is 78%).

(there is the synthesis of the polymer (P1) of Component units s1)

Diethylene glycol methyl ethyl ether (following, to be abbreviated as " HS-EDM ") 22g, under stream of nitrogen gas, is heated to 70 DEG C also Stirring.With the monomer a-1 (11.1g, 45mol%) of dropping synthesis in 2 hours, methacrylic acid hexafluoro isopropyl ester (below, brief note For " HFIP ") (Tokyo HuaCheng Industry Co., Ltd's system, 3.5g, 15mol%), methacrylic acid (following, to be abbreviated as " MAA ") (Wako Pure Chemical Industries, Ltd.'s system, 1.7g, 20mol%), glycidyl methacrylate (following, to be abbreviated as " GMA ") (Wako Pure Chemical Industries, Ltd.'s system, 2.8g, 20mol%), radical polymerization initiator (V-65 and Wako Pure Chemical Industries strain formula Commercial firm's system) 497mg (2mol%) and the mixed solution of PGMEA (30g).After completion of dropwise addition, by reacting at 70 DEG C further 4 hours, obtain the PGMEA solution (solid component concentration: 27%) with the polymer P 1 of Component units s1.

(there is the synthesis of the polymer (P2～P15) of Component units s1)

In addition to the kind of monomer, initiator and solvent is changed according to following 1st table, by with polymer P 1 Same method, synthetic polymer P2～P15.It addition, the numerical value described in hurdle of each monomer component of following 1st table is relative The usage amount (mol%) of each monomer in the total amount of monomer component.Additionally, the numerical value described in the hurdle of polymerization initiator is for setting The total amount of monomer component is mol% during 100mol%.Additionally, the abbreviation used in embodiment is as described below.

HFIP: methacrylic acid hexafluoro isopropyl ester (Tokyo HuaCheng Industry Co., Ltd's system)

6FM: trifluoroethyl methacrylate (Osaka Organic Chemical Industry Co., Ltd.'s system)

KBM-503:3-methacryloxypropyl trimethoxy silane (Shin-Etsu Chemial Co., Ltd's system)

C18MA: methacrylic acid octadecane ester (Tokyo HuaCheng Industry Co., Ltd's system)

MAA: methacrylic acid (Wako Pure Chemical Industries, Ltd.'s system)

MMA: methyl methacrylate (Wako Pure Chemical Industries, Ltd.'s system)

St: styrene (Wako Pure Chemical Industries, Ltd.'s system)

AA: acrylic acid (Wako Pure Chemical Industries, Ltd.'s system)

GMA: glycidyl methacrylate (Tokyo HuaCheng Industry Co., Ltd's system)

(Osaka Organic Chemical Industry strain formula meeting of OXE-30: methacrylic acid (3-Ethyloxetane-3-base) methyl ester Society's system)

DCPM: methacrylic acid bicyclo-pentyl ester (FANCRYL FA-513M, Hitachi Chemical Co., Ltd.'s system)

NBMA:N-butoxy methyl acrylamide (Mitsubishi Rayon Co., Ltd. system)

V-601: radical polymerization initiator (Wako Pure Chemical Industries, Ltd.'s system)

V-65: radical polymerization initiator (Wako Pure Chemical Industries, Ltd.'s system)

PGMEA: MPEG 2-methoxy-propane-1,3-diol. acetas (Daicel Corporation system)

HS-EDM: diethylene glycol methyl ethyl ether (Toho Chemical Industry Co., Ltd.'s system)

Table 1

(synthesis of other light orientation polymer)

By the side as specific copolymer P1 described in [0084] paragraph (synthesis example 1) of WO2010/150748 Method, obtains polymer 16.

By with the light orientation described in [0161] paragraph of Japanese Unexamined Patent Publication 2013-177561 publication (modulation example 1) The method that polymer (A-1) is same, synthetic polymer P17.

(there is the modulation of the polymer of other Component units)

< comprise and there is acidic group by the Component units a1 of the group of acid decomposability radical protection and there is the structure of crosslinkable groups Become the synthesis of the polymer A-1 of unit a2 >

By HS-EDM (82 parts) under stream of nitrogen gas, it is heated to 90 DEG C and stirs.

Then, dripped, with 2 hours, the methacrylic acid tetrahydrochysene-2H-furan-2-ester (43 parts synthesized as monomer e-1 (being equivalent to the 40.5mol% in whole monomer component)), (48 parts (are equivalent in whole monomer component OXE-30 37.5mol%)), MAA (6 parts (being equivalent to the 9.5mol% in whole monomer component)), hydroxy ethyl methacrylate (with Wako Pure Chemical Industries Co., Ltd. system, 11 parts (being equivalent to the 12.5mol% in whole monomer component)), radical polymerization initiator V-601 (4.3 parts) and the mixed solution of PGMEA (82 parts), by further at 90 DEG C react 2 hours, obtain polymer A- The solution (solid component concentration: 40%) of 1.

It addition, the weight average molecular weight measured by gel permeation chromatography (GPC) of obtained polymer A-1 is 15, 000。

By PGMEA (238g) under stream of nitrogen gas, it is heated to 90 DEG C and stirs.

Then, dripped, with 2 hours, the methacrylic acid tetrahydrochysene-2H-furan-2-ester (240g synthesized as monomer e-1 (being equivalent to the 61.1mol% in whole monomer component)), (50.4g (is equivalent in whole monomer component MAA 17.6mol%)), MMA (27.9g (being equivalent to the 21.3mol% in whole monomer component)), radical polymerization initiator V-601 (14.7g) and the mixed solution of PGMEA (238g), react 2 hours at 90 DEG C further, by adding PGMEA after the cooling period (42g) solution (solid component concentration: 38%) of polymer A-2, is obtained.

Obtained by the weight average molecular weight measured by gel permeation chromatography (GPC) of polymer A-2 be 15,000.

By HS-EDM (145g) under stream of nitrogen gas, it is heated to 70 DEG C and stirs.

Then, with 2 hours droppings GMA (144.7g (67.9mol%)), MAA (16.7g (12.9mol%)), St (28.1g (18.0mol%)), DCPM (3.87g (1.17mol%), radical polymerization initiator V-65 (20.8g (5.6mol% amount of monomer Conversion)) and the mixed solution of HS-EDM (145g).

After completion of dropwise addition, by reacting 4 hours at 70 DEG C, (solid constituent is dense to obtain the PGMEA solution of polymer A-3 Degree: 35%).

After carrying out nitrogen displacement in flask, put into 459.0g and be dissolved with 2, the diethylene glycol of 2 '-azobis isobutyronitrile 9.0g Dimethyl ether solution.

Then, after putting into St (22.5g), MAA (45.0g), DCPM (67.5g) and GMA (90.0g), start lentamente to stir Mix.

Then, making the temperature of solution rise to 80 DEG C, after this temperature being kept 5 hours, at 90 DEG C, heating makes to gather for 1 hour Conjunction terminates.

Afterwards, it is added drop-wise in substantial amounts of water make reactant solidify by reaction generation solution.After this coagulum is washed then molten Solution, in THF (200g), makes it solidify with substantial amounts of water again.

The operation of this re-dissolved and solidification is added up to after carrying out 3 times, obtained coagulum is carried out at 60 DEG C 48 little Time drying under reduced pressure, obtain polymer A-4.Afterwards, reach the mode of 25 weight % according to solid component concentration and use diethylene glycol Make polymer A-4 solution.

By HS-EDM (11g) under stream of nitrogen gas, it is heated to 70 DEG C and stirs.

Then, with dropping MAA (4.3g (50.0mol%)), MMA (5.0g (50.0mol%)), radical polymerization in 2 hours Initiator V-601 (0.497g (conversion of 2mol% amount of monomer)) and the mixed solution of HS-EDM (11g).

After completion of dropwise addition, by 90 DEG C react 2 hours, obtain polymer A-5 solution (solid component concentration: 30%).

By HS-EDM (91g) under stream of nitrogen gas, it is heated to 70 DEG C and stirs.

Then, with 2 hours droppings OXE-30 (75g (67.9mol%)), MAA (6.7g (12.9mol%)), St (11.3g (18.0mol%)), DCPM (((change 4.5g for 1.5g (1.17mol%), radical polymerization initiator V-65 by 3.0mol% amount of monomer Calculate)) and the mixed solution of HS-EDM (91g).

After completion of dropwise addition, by 70 DEG C react 4 hours, obtain polymer A-6 solution (solid component concentration: 30%).

By being orientated with the non-light described in [0165] paragraph of Japanese Unexamined Patent Publication 2013-177561 publication (modulation example 5) The method that property polymer (E-1) is same, has synthesized non-smooth orientation polymer A-7.

(cross-linking agent)

As cross-linking agent, use cross-linking agent shown below.

<C-1>

As the cross-linking agent C-1 that molecular weight is 1, less than 000, use multi-functional epoxy compound (EX-321L, Nagase Chemtex Corporation system).

<HMM>

HMMM (HMM, Tokyo HuaCheng Industry Co., Ltd's system)

(acid producing agent)

As acid producing agent (light acid producing agent and thermal acid generator), synthesize or use acid producing agent shown below.

Beta naphthal (10g), chlorobenzene (30mL) aaerosol solution in add aluminum chloride (10.6g), 2-chlorpromazine chloride (10.1g), mixed liquor is heated to 40 DEG C and reacts 2 hours.Under ice-cold, reactant liquor drips 4NHCl aqueous solution (60mL), Add ethyl acetate (50mL) and carry out separatory.Potassium carbonate (19.2g) is added in organic layer, after reacting 1 hour at 40 DEG C, Add 2NHCl aqueous solution (60mL) separatory, after organic layer is concentrated, crystallization is starched with Di Iso Propyl Ether (10mL) again Change, filter and be dried and obtain ketonic compound (6.5g).

Obtained ketonic compound (3.0g), methanol (30mL) aaerosol solution in add acetic acid (7.3g), 50 matter Amount % aqueous hydroxylamine (8.0g), is heated to reflux.After letting cool, add water (50mL), the crystallization separated out is filtered.Cold first After alcohol washing, it is dried and obtains oxime compound (2.4g).

Obtained oxime compound (1.8g) is made to be dissolved in acetone (20mL), ice-cold lower interpolation triethylamine (1.5g), Paratoluensulfonyl chloride (2.4g), is warming up to room temperature and reacts 1 hour.Water (50mL), the crystallization that will separate out is added in reactant liquor After filtration, carry out repulped with methanol (20mL), filter and be dried and obtain B-1 (2.3g).

It addition, B-1¹H-NMR spectrum (300MHz, CDCl₃) it is 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)。

Make 1-amino-beta naphthal hydrochlorate 4.0g be suspended in N-Methyl pyrrolidone 16g, add sodium bicarbonate 3.4g After, drip 4,4-dimethyl-3-oxopentanoic 4.9g, heat 2 hours at 120 DEG C in a nitrogen atmosphere.After letting cool, instead Answer and mixed liquor adds water, ethyl acetate separatory, organic facies is dried with magnesium sulfate, filter, concentrate and obtain thick B-2A.Will Thick B-2A, by silica gel column chromatography purification, obtains 1.7g intermediate B-2A.

B-2A (1.7g) is mixed with xylol (6mL), adds p-methyl benzenesulfonic acid monohydrate 0.23g and at 140 DEG C Lower heating 2 hours.After letting cool, reaction mixture adds water, ethyl acetate separatory, organic facies is dried with magnesium sulfate After, filter, concentrate and obtain thick B-2B.

THF (2mL) is mixed with thick B-2B total amount, ice-cold lower dropping 2M hydrochloric acid/THF solution 6.0mL, then drip nitrous Isoamyl valerate (0.84g), is warming up to room temperature (25 DEG C) and stirs 2 hours afterwards.Water, acetic acid is added in obtained reactant mixture Ethyl ester separatory, after being washed with water by organic layer, be dried with magnesium sulfate, filters, and concentrates and obtains the thick B-2C of intermediate.

Thick for intermediate B-2C total amount is mixed with acetone (10mL), ice-cold lower interpolation triethylamine (1.2g), to toluene After sulfonic acid chloride (1.4g), it is warming up to room temperature and stirs 1 hour.Water, ethyl acetate is added also in obtained reaction mixture Separatory, organic facies is dried with magnesium sulfate, filter, concentrate and obtain thick B-2.By thick B-2 with cold methanol repulped after, mistake Filter, is dried and obtains B-2 (1.2g).

It addition, B-2¹H-NMR spectrum (300MHz, CDCl₃) it is δ=8.5-8.4 (m, 1H), 8.0-7.9 (m, 4H), 7.7-7.6 (m, 2H), 7.6-7.5 (m, 1H), 7.4 (d.2H), 2.4 (s, 3H), 1.4 (s, 9H).

<B-3>

Use commercially available acid producing agent (PAG-103, BASF system).

Synthesize according to the method described in the paragraph 0128 of WO2011/087011 publication.

[chemical formula 33]

Commercially available triarylsulfonium salt (GSID-26-1, BASF system)

[chemical formula 34]

<TAS-200>

Quinone diazide (TAS-200, Toyo Synthetic Industry Co., Ltd.'s system)

<PTSA>

As thermal acid generator, use p-methyl benzenesulfonic acid monohydrate (PTSA, Tokyo HuaCheng Industry Co., Ltd's system).

(other composition)

As alkali compounds, use the compound of following structure.

[chemical formula 35]

<F-554>

As surfactant, use (F-554, Dainippon Ink Chemicals's system) Han perfluoroalkyl nonionic surfactant.

<KBM-403>

As closely sealed modifying agent, use γ-glycidoxypropyltrime,hoxysilane (KBM-403, SHIN-ETSU HANTOTAI's chemical industry Co., Ltd.'s system).

(embodiment 1～74 and comparative example 1～4)

Each composition shown in following 2nd table is dissolved in solvent (PGMEA) mixing to solid component concentration and reaches 18 Quality %, filters with the politef filter that bore is 0.2 μm, obtains the photonasty of each embodiment and comparative example Resin combination.It addition, the addition in table represent each composition with the addition of solid component meter, unit is mass parts.

Table 2

Table 3

(patterning is evaluated)

By glass substrate (EAGLE XG, 0.7mm are thick (Corning Incorporated system)) in hexamethyldisiloxane (HMDS) under steam expose 30 seconds, after each photosensitive polymer combination of spin application, prebake conditions on 90 DEG C/120 seconds hot plates and Make solvent volatilize, form the photosensitive polymer combination layer that thickness is 3.0 μm.

Then, obtained photosensitive polymer combination layer is used the MPA5500CF (high-pressure mercury of Canon Co., Ltd Lamp), the mask via regulation is exposed.

And then, by the photosensitive polymer combination layer after exposure, with alkaline developer, (tetramethyl ammonium hydroxide of 0.4% is water-soluble Liquid) carry out 23 DEG C/60 seconds development after, with ultra-pure water drip washing 20 seconds.By when making the hole exploring of 10 μm by these operations Good i x ray exposure x amount (Eopt) is as sensitivity.It is worth the lowest, then gets over low light exposure opening, it may be said that for high sensitivity.Evaluate base Standard is following.It addition, be scope no problem in practicality during A～C, D is judged as problematic.Show the result in following 3rd table In.

A: less than 150mJ/cm²

B:150mJ/cm²Less than 300mJ/cm²

C:300mJ/cm²Less than 600mJ/cm²

D: not opening

Expose on the glass substrate of 30 seconds under hexamethyldisiloxane (HMDS) steam, spin application each photonasty tree After oil/fat composition, carried out prebake conditions at 90 DEG C/120 seconds on hot plate and make solvent volatilize, form the photonasty tree that thickness is 3.0 μm Oil/fat composition layer.

Then, ultrahigh pressure mercury lamp is used to reach 300mJ/cm according to accumulative irradiation dose²(energy intensity: 20mW/cm², i penetrates Line) mode be exposed, this substrate is utilized baking oven carry out 230 DEG C/30 minutes heating after, further with baking oven 230 Heat 2 hours at DEG C, obtain cured film.

Spectrophotometer (U-3000: Hitachi Co., Ltd's system) is used to measure this cured film with wavelength 400nm Absorbance.Unit represents with %.Being scope no problem in practicality during A～C, D is judged as problematic.Show the result in following In 3rd table.

More than A:95%

B: less than 95% and be more than 90%

C: less than 90% and be more than 80%

D: less than 80%

(orientation is evaluated)

It is coated with each photosensitive polymer combination relative to substrate by spin-coating method, the hot plate of 80 DEG C carries out 1 minute in advance After drying, burn till in the cleaning oven of 240 DEG C 60 minutes, form the cured film that thickness is 3 μm.

Then, being formed by sputtering and dry-etching at central part can be to the comb teeth-shaped of the 1cm × 1cm of external connection ITO (Indium Tin Oxide) transparency electrode (In Plane Switching (IPS) type).

Afterwards, relative to above-mentioned substrate, use ultraviolet polarized light exposure device (HC-2150PUFM, LAN TECHNICAL SERVICE CO., LTD. system), carry out light orientation process by deflection light.

Then, the encapsulant of epoxy resin is used to make the liquid crystal cells that cell gap is 3 μm.

The horizontal alignment liquid-crystal composition MLC-2055 of Merck is injected in liquid crystal cells, inlet is solid with UV After the sealing compound of the property changed seals, make on the two sides of liquid crystal cells differently-oriented directivity as one man paste polarization plates, made liquid crystal display Element.

As evaluation, to liquid crystal display cells 20 times of multiplying powers confirmations with micropolariscope on lamp box (white light source) The orientation of liquid crystal cell, and evaluate its situation.Metewand is following.Show the result in following 3rd table.

A: no problem

B: have deep or light in black display

C: have orientation defect, see bright spot

D: not orientation, entirely without being blocked

Additionally, record the sensitivity after being orientated.Metewand is following.It is worth the lowest, then more completes to take with low light exposure To, it may be said that orientation sensitivity is the highest.Show the result in following 3rd table.

A: less than 300mJ/cm²

B:300mJ/cm²Less than 500mJ/cm²

C:500mJ/cm²Less than 1500mJ/cm²

D:1500mJ/cm²Above

(humidity resistance)

Then, the square wave to this liquid crystal display cells applying ± 5V, 30Hz, confirm the 1cm × 1cm with transparency electrode The appearance (ON/OFF) that is blocked of part.Make 10 elements, place them into accelerating aging test machine (Pressure Cooker test) in (temperature 60 C/relative humidity 90%, LH-113 Constant Temperature and Humidity Chambers, ESPEC CORP. system) and confirm 24 The appearance of the driving after hour.Metewand is following.Show the result in following 3rd table.

A: be not changed in

The 20% of B: element changes

The 50% of C: element changes

D: do not drive

Table 4

Table 5

Known by the result shown in the 1st table～the 3rd table, when there is no to coordinate the polymer with Component units s1, i.e. Make to inject liquid-crystal composition, orientation and orientation sensitivity also inequality (comparative example 1 and 2) after implementing light orientation process.

In addition know, when having coordinated the polymer of other light orientation without Component units s1, patterning performance Difference (comparative example 3 and 4).

On the other hand, know at least one met in above-mentioned condition 1～3 and coordinated and have Component units s1's In any one in the 1st mode and the 2nd mode of the photosensitive polymer combination of polymer, orientation and orientation sensitivity all become Well, become and double as the interlayer dielectric (embodiment 1～53 (the 1st mode) and embodiment 54～74 (the 2nd mode)) of alignment films.

Claims

1. a photosensitive polymer combination, it is containing component of polymer A1 and the photosensitive resin composition of light acid producing agent B1 Thing, described component of polymer A1 contains and comprises the polymerization having acidic group by the Component units a1 of the group of acid decomposability radical protection Thing A1-1,

Described photosensitive polymer combination meets at least one in following 1～3:

1: described polymer A 1-1 comprises the Component units a2 with crosslinkable groups further,

2: as described component of polymer A1, contain the polymer comprising the Component units a2 with crosslinkable groups further A1-2,

Further, at least one during described photosensitive polymer combination meets following 4 and 5:

4: described polymer A 1-1 or described polymer A 1-2 comprise the Component units shown in following s1,

5: as described component of polymer A1, contain polymer A 1-3 comprising the Component units shown in following s1 further,

S1: have in the group selecting free fluorine substituted hydrocarbon radical, siloxane backbone and alkyl that carbon number is 10～30 to form extremely Lack the Component units of a kind of part-structure and there is the Component units of light orientation group.

Photosensitive polymer combination the most according to claim 1, wherein, described acidic group is by the base of acid decomposability radical protection Group is the acidic group protected group of form with acetal.

3. a photosensitive polymer combination, it is the photoresist group containing component of polymer A2 Two azide of quinone B2 Compound, described component of polymer A2 contains polymer A 2-1 comprising the Component units a3 with acidic group,

1: described polymer A 2-1 comprises the Component units a2 with crosslinkable groups further,

2: as described component of polymer A2, contain the polymer comprising the Component units a2 with crosslinkable groups further A2-2,

4: described polymer A 2-1 or described polymer A 2-2 comprise the Component units shown in following s1,

5: as described component of polymer A2, contain polymer A 2-3 comprising the Component units shown in following s1 further,

4. according to 1 described photosensitive polymer combination wantonly in claims 1 to 3, wherein, described smooth orientation group is logical Cross photodimerizationization reaction and give the group of orientation.

5. according to 1 described photosensitive polymer combination wantonly in claims 1 to 3, wherein, described smooth orientation group is meat Cinnamic acid ester group or chalcone derivative base.

6., according to 1 described photosensitive polymer combination wantonly in claims 1 to 3, wherein, described crosslinkable groups is epoxy Base or oxetanyl.

7., according to 1 described photosensitive polymer combination wantonly in claims 1 to 3, wherein, there is the structure shown in described s1 The content becoming the polymer of unit is 0.1～20 mass % relative to all solids composition of compositions.

8. according to 1 described photosensitive polymer combination wantonly in claims 1 to 3, wherein, containing organic solvent D.

9. a manufacture method for cured film, it includes following operation:

The operation that photosensitive polymer combination described in claim 8 is applied on substrate；

10. a cured film, it is to make consolidating of wantonly 1 described photosensitive polymer combination solidification in claim 1～8 Change film.

11. 1 kinds of liquid crystal indicators, it has the cured film described in claim 10.