CN103076716B - Resin combination, photosensitive polymer combination, pad and display device - Google Patents

Abstract

The present invention provides resin combination, the photosensitive polymer combination containing the resin combination, the pad formed by the photosensitive polymer combination and the display device for possessing the pad of the increase of the molecular weight for the copolymer (A1) that can suppress to make unsaturated carboxylic acid (a1) be polymerized with the unsaturated compound (a2) containing epoxy radicals.Comprising at least making the alkali soluble resin (A) of copolymer (A1) that unsaturated carboxylic acid (a1) and unsaturated compound (a2) containing epoxy radicals be polymerized, the resin combination of the solvent (S) containing propylene glycol monomethyl ether, the compound for coordinating following formula (1) to evaluate.

Description

Resin combination, photosensitive polymer combination, pad and display device

Technical field

Photosensitive polymer combination the present invention relates to resin combination, containing the resin combination, use the resin group The pad (サ of ス ペ mono-) of compound formation and the display device for possessing the pad.

Background technology

The photonasty at least making alkali soluble resin, photopolymerization monomer and Photoepolymerizationinitiater initiater dissolve in a solvent Resin combination, is used in a variety of applications where.For the photosensitive polymer combination, because alkali soluble resin is molten well Solution, is readily obtained the photosensitive polymer combination for the film that can form expectation thickness, vapo(u)rability is excellent, the toxicity to human body is few Deng therefore, propylene glycol monomethyl ether (following, be also recited as " PGMEA ") is widely used as solvent.It is photosensitive as this The concrete example of the purposes of property resin combination, for example, the pad that can be enumerated in display device forms purposes.

In display device, due to various purposes, the space for being used to form defined height between two plate bases is utilized Pad.For example, in liquid crystal panel, due to using the structure for clamping liquid crystal material with transparent substrates such as two sheet glass substrates, Therefore, in order to filling liquid crystal material, it is necessary to form pad between two plate bases.

In the past, in order to form pad, using the method that the microballon particle for forming pad is spread in the entire surface of substrate.But It is, it is difficult to padded by this method with the formation of high positional precision, microballon is also adhered in pixel display portion, therefore, with figure The problem of contrast and display image quality of picture are reduced.

On the other hand, it is following method by the method for photosensitive polymer combination formation pad：Sense is coated with substrate Photosensitive resin composition, after defined mask is exposed, is developed, and forms the pad of point-like etc..Therefore, according to this Method, only defined part beyond pixel display portion can form pad, can manufacture can degree of being contrasted and The display device of the excellent image of image quality.

As can be with suitably used photosensitive polymer combination in this method, it is proposed that following photosensitive resin composition Thing, using at least by selected from least one of ethylenically unsaturated carboxylic acids and ethylenically unsaturated carboxylic acids acid anhydride and the alkene containing epoxy radicals Ethylenically unsaturated compounds carry out the copolymer of copolymerization as alkali soluble resin (with reference to patent document 1).

Patent document 1：Japanese Unexamined Patent Publication 2006-184841 publications

The content of the invention

But, in photosensitive polymer combination, as alkali soluble resin, using will at least be selected from ethylenically unsaturated carboxylic acids And at least one of ethylenically unsaturated carboxylic acids acid anhydride carries out being total to for copolymerization with the alefinically unsaturated compounds containing epoxy radicals Polymers, as solvent, using the solvent containing PGMEA, in this case, by the autoreactivity of alkali soluble resin, alkali can The molecular weight of soluble resin easily increases, therewith, the problem of developability with photosensitive polymer combination is reduced.

The present invention be in view of such conventional situation and carry out, even if its object is to there is provided using containing PGMEA Solvent, can also suppress to make unsaturated carboxylic acid (a1) and being total to that the unsaturated compound (a2) containing epoxy radicals is polymerized The resin combination of the increase of the molecular weight of polymers (A1), the photosensitive polymer combination containing the resin combination, by the sense The pad of photosensitive resin composition formation and the display device for possessing the pad.

In-depth study has been repeated in order to solve above-mentioned problem in the present inventor.As a result find, by comprising containing At least make the alkali for the copolymer (A1) that unsaturated carboxylic acid (a1) and the unsaturated compound (a2) containing epoxy radicals be polymerized Coordinate the compound of specific structure in the resin combination of soluble resin (A) and solvent (S) containing PGMEA, obtain energy Enough suppress the resin combination of the increase of the molecular weight of alkali soluble resin, photoresist group is prepared using the resin combination Compound, thereby, it is possible to solve above-mentioned problem, so as to complete the present invention.Specifically, the present invention provides as follows.

The 1st aspect of the present invention is a kind of resin combination, wherein, contain alkali soluble resin (A), following formula (1) table The compound and solvent (S) shown,

Above-mentioned alkali soluble resin (A) is contained：At least make unsaturated carboxylic acid (a1) and the unsaturated compound containing epoxy radicals (a2) copolymer (A1) being polymerized,

Above-mentioned solvent (S) contains propylene glycol monomethyl ether,

(in formula, R¹And R²Separately represent hydrogen atom or organic group.But, R¹And R²At least one table Show organic group.R¹And R²Cyclic structure, R can be bonded together to form¹And R²Heteroatomic key can also be included.R³Represent singly-bound Or organic group.R⁴And R⁵Separately represent hydrogen atom, halogen atom, hydroxyl, sulfydryl, thioether group, silicyl, silane Alcohol radical, nitro, nitroso, sulfino, sulfo group, sulfonic group, phosphino-, phosphinyl, phosphono, phosphonate group or organic group.R⁶、R⁷、 R⁸And R⁹Separately represent hydrogen atom, halogen atom, hydroxyl, sulfydryl, thioether group, silicyl, silanol group, nitro, Asia Nitro, sulfino, sulfo group, sulfonic group, phosphino-, phosphinyl, phosphono, phosphonate group, amino, ammonium or organic group.But, R⁶ And R⁷It is not hydroxyl.R⁶、R⁷、R⁸And R⁹In more than two can bond together to form cyclic structure, R⁶、R⁷、R⁸And R⁹Also may be used To include heteroatomic key.R¹⁰Represent hydrogen atom or organic group).

The 2nd aspect of the present invention is a kind of photosensitive polymer combination, wherein, the resin combination containing first method, Photopolymerization monomer (B) and Photoepolymerizationinitiater initiater (C).

The 3rd aspect of the present invention is the pad formed by the photosensitive polymer combination of second method.

The 4th aspect of the present invention is the display device for the pad for possessing Third Way.

Invention effect

Even if in accordance with the invention it is possible to provide using the solvent containing PGMEA, can also suppress to make unsaturated carboxylic acid (a1) The resin combination of the increase of the molecular weight for the copolymer (A1) being polymerized with the unsaturated compound (a2) containing epoxy radicals Thing, the photosensitive polymer combination containing the resin combination, the pad formed by the photosensitive polymer combination and possess The display device of the pad.

Embodiment

Resin combination

The present invention resin combination, at least containing alkali soluble resin (A), above-mentioned formula (1) represent compound and Solvent (S), alkali soluble resin (A), which contains, at least makes unsaturated carboxylic acid (a1) enter with the unsaturated compound (a2) containing epoxy radicals The copolymer (A1) that row is polymerized, solvent (S) contains propylene glycol monomethyl ether (PGMEA).The resin group of the present invention Compound, the increase of the molecular weight due to suppressing the alkali soluble resin (A) during keeping, it is therefore preferable that for aftermentioned photonasty tree The preparation of oil/fat composition.Hereinafter, illustrated for each composition contained in the resin combination of the present invention.

<Alkali soluble resin (A)>

Alkali soluble resin refers to following resin, passes through the mass % of resin concentration 20 resin solution (solvent：Propane diols list Methylether acetate), the TMAH in 2.38 mass % at the resin film of 1 μm of thickness, 23 DEG C is formed on substrate (TMAH) when being impregnated 1 minute in the aqueous solution, more than 0.01 μm of thickness is dissolved.

It is to be used for the resin of photosensitive polymer combination all the time as alkali soluble resin (A), as long as containing extremely Make the resin for the copolymer (A1) that unsaturated carboxylic acid (a1) and the unsaturated compound (a2) containing epoxy radicals be polymerized less, It is not particularly limited.The copolymer (A1) included in the alkali soluble resin (A), in the case where forming PGMEA solution, leads to Autoreactivity molecular weight is crossed easily to increase.But, resin combination of the invention includes the compound that aftermentioned formula (1) is represented, because This, suppresses the increase of the molecular weight of copolymer (A1).In addition, by containing the copolymer A 1, being readily obtained breakdown strength and right The excellent pad of the adaptation of substrate.

As unsaturated carboxylic acid (a1), it can enumerate：The monocarboxylic acids such as (methyl) acrylic acid, crotonic acid；Maleic acid, rich horse The dicarboxylic acids such as acid, citraconic acid, mesaconic acid, itaconic acid；Acid anhydrides of these dicarboxylic acids etc..In these, from copolyreaction, resulting Resin alkali-solubility, the viewpoint such as easiness that obtains is set out, and is preferably (methyl) acrylic acid and maleic anhydride.These are not Saturated carboxylic acid (a1) can be used alone or can also be applied in combination two or more.

Component units from unsaturated carboxylic acid (a1) ratio shared in copolymer (A1), preferably 20 mass % with On, more preferably 20~30 mass %.Copolymer (A1), within the range containing the Component units from unsaturated carboxylic acid (a1) In the case of, using resin combination, easily prepare the excellent photosensitive polymer combination of developability.

As the preferred compound of the unsaturated compound (a2) containing epoxy radicals, it can enumerate：The epoxy radicals containing ester ring type Unsaturated compound and the unsaturated compound containing epoxy radicals without ester ring type group, more preferably epoxy containing ester ring type The unsaturated compound of base.

Hereinafter, for the unsaturationization of the preferred unsaturated compound (a2) containing epoxy radicals, the i.e. epoxy radicals containing ester ring type Compound is illustrated.As the unsaturated compound of the epoxy radicals containing ester ring type, as long as the unsaturation with ester ring type epoxy radicals Compound, is not particularly limited.It can be monocyclic to constitute the ester ring type group of ester ring type epoxy radicals, or polycyclic.Make For monocyclic ester ring type group, it can enumerate：Cyclopenta, cyclohexyl etc..In addition, being used as polycyclic ester ring type group, Ke Yilie Lift：Norborny, isobornyl, three cyclononyls, tricyclodecyl, tetracyclododecyl group etc..These epoxy radicals containing ester ring type are not Saturated compounds can be used alone or can also be applied in combination two or more.

Specifically, as the unsaturated compound of the epoxy radicals containing ester ring type, for example, it can enumerate：Following formula (a2-1)~ (a2-16) compound represented.In these, in order that the developability of the photosensitive polymer combination prepared using resin combination Appropriateness, the compound that preferably following formula (a2-1)~(a2-6) is represented, more preferably following formula (a2-1)~(a2-4) is represented Compound.

In above-mentioned formula, R¹¹Represent hydrogen atom or methyl, R¹²The sturated aliphatic hydrocarbon base of the divalent of carbon number 1~6 is represented, R¹³The alkyl of the divalent of carbon number 1~10 is represented, n represents 0~10 integer.It is used as R¹², preferably straight-chain or branched Alkylidene, such as methylene, ethylidene, propylidene, butylidene, ethylethylene residue, pentylidene, hexylidene.It is used as R¹³, for example Preferably methylene, ethylidene, propylidene, butylidene, ethylethylene residue, pentylidene, hexylidene, phenylene, cyclohexylene ,- CH₂-Ph-CH₂- (Ph represents phenylene).

Then, illustrated for the unsaturated compound containing epoxy radicals without ester ring type group.As without The unsaturated compound containing epoxy radicals of ester ring type group, can be enumerated：Glycidyl (methyl) acrylate, the contracting of 2- methyl Water glyceryl (methyl) acrylate, 3,4- epoxy radicals butyl (methyl) acrylate, 6,7- epoxy radicals heptyl (methyl) propylene Acid esters etc. (methyl) acrylic acid epoxy base alkyl esters；α-ethylacrylate ethylene oxidic ester, α-n-propyl acrylic acid shrink sweet Grease, α-n-butyl acryloyloxy ethyl acid glycidyl ester, α-ethylacrylate 6, the alpha-alkyl acrylic acid epoxy base such as 7- epoxy radicals heptyl esters Alkyl esters etc..In these, the viewpoint, preferably glycidyl such as intensity of resin after copolyreaction, solidification (methyl) acrylate, 2- methylglycidyls (methyl) acrylate and 6,7- epoxy radicals heptyl (methyl) acrylic acid Ester.These unsaturated compounds containing epoxy radicals without ester ring type group can be used alone or can also be applied in combination It is two or more.

In addition, the Component units for carrying out the unsaturated compound (a2) of self-contained epoxy radicals ratio shared in copolymer (A1) Example, particularly preferably preferably more than 30 mass %, more preferably more than 35 mass %, 35~80 mass %.Copolymer (A1) In the case of Component units within the range containing the unsaturated compound (a2) for carrying out self-contained epoxy radicals, resin combination is used Thing, the photosensitive polymer combination of breakdown strength and the pad excellent with the adaptation of substrate can be formed by easily preparing.In addition, The ratio of the unsaturated compound of in the unsaturated compound (a2) containing the epoxy radicals, epoxy radicals containing ester ring type, preferably 50 More than quality %, more preferably more than 80 mass %, particularly preferably 100 mass %.

Copolymer (A1) can be and above-mentioned unsaturated carboxylic acid (a1) and the above-mentioned unsaturated compound containing epoxy radicals (a2) unsaturated compound (a3) of the group containing ester ring type without epoxy radicals is made to be polymerized together.

As the unsaturated compound (a3) of the group containing ester ring type, as long as the unsaturated chemical combination with ester ring type group Thing, is not particularly limited.Ester ring type group can be monocyclic, or polycyclic., can be with as monocyclic ester ring type group Enumerate cyclopenta, cyclohexyl etc..In addition, as polycyclic ester ring type group, can enumerate：Adamantyl, norborny, different ice Chip base, three cyclononyls, tricyclodecyl, tetracyclododecyl group etc..The unsaturated compound (a3) of these groups containing ester ring type can be with It is used alone or can also be applied in combination two or more.

Specifically, as the unsaturated compound (a3) of the group containing ester ring type, for example, following formula (a3-1) can be enumerated The compound that~(a3-7) is represented.In these, in order that the development of the photosensitive polymer combination prepared using resin combination Property appropriateness, the compound that preferably following formula (a3-3)~(a3-8) is represented, more preferably following formula (a3-3), (a3-4) is represented Compound.

In above-mentioned formula, R²¹Represent hydrogen atom or methyl, R²²Represent that the aliphatic of the divalent of singly-bound or carbon number 1~6 is satisfied And alkyl, R²³Represent the alkyl of hydrogen atom or carbon number 1~5.It is used as R^22,The preferably Asia of singly-bound, straight-chain or branched Alkyl, such as methylene, ethylidene, propylidene, butylidene, ethylethylene residue, pentylidene, hexylidene.It is used as R²³, for example preferably For methyl, ethyl.

The Component units of unsaturated compound (a3) from the above-mentioned group containing ester ring type are shared in copolymer (A1) Ratio, preferably 1~50 mass %, more preferably 10~50 mass %, particularly preferably 15~45 mass %.

In addition, copolymer (A1) can also be the copolymer for making other compounds other than the above further be polymerized. As other such compounds, can enumerate (methyl) esters of acrylic acid, (methyl) acrylic amide, allyl compound, Vinyl ethers, vinyl ester, phenylethylene etc..These compounds can be used alone or can also be applied in combination two kinds More than.

As (methyl) esters of acrylic acid, it can enumerate：Methyl (methyl) acrylate, ethyl (methyl) acrylate, The straight-chains such as propyl group (methyl) acrylate, amyl group (methyl) acrylate, t-octyl (methyl) acrylate or branched Alkyl (methyl) acrylate；Chloroethyl (methyl) acrylate, 2,2- dimethyl hydroxyls propyl group (methyl) acrylate, 2- hydroxyls Base ethyl (methyl) acrylate, trimethylolpropane list (methyl) acrylate, benzyl (methyl) acrylate, furfuryl group (first Base) acrylate etc..

As (methyl) acrylic amide, it can enumerate：(methyl) acrylamide, N- alkyl (methyl) acrylamide, N- Aryl (methyl) acrylamide, N, N- dialkyl group (methyl) acrylamide, N, N- aryl (methyl) acrylamide, N- methyl-N- Phenyl (methyl) acrylamide, N- hydroxyethyl-N- methyl (methyl) acrylamide etc..

As allyl compound, allyl acetate, allyl hexanoate, allyl octanoate, dodecylic acid alkene can be enumerated The alkene such as propyl ester, hexadecanoic acid allyl ester, stearic allyl propionate, allyl benzoate, acetoacetate allyl ester, allyl lactate Propyl ester class；Allyloxyethanol etc..

As vinyl ethers, it can enumerate：Hexyl vinyl ethers, octyl vinyl ether, decave, ethyl hexyl Base vinyl ethers, methoxy-ethylvinyl ether, ethoxy ethyl vinyl ether, chloroethyl vinyl ether, 1- methyl -2,2- bis- Methyl-propyl vinyl ethers, 2- ethylbutyl vinyl ethers, hydroxyethyl vinyl ether, diethylene glycol vinyl ethers, dimethyl Amino-ethyl vinyl ethers, diethylamino ethyl vinyl ether, Butylaminoethyl vinyl ethers, benzyl vinyl ether, four The alkyl vinyl ethers such as tetrahydrofurfuryl vinyl ethers；Vinyl phenyl ether, vinyltoluene base ether, vinyl chloride phenyl ether, ethene Ethenyl aromatic yl ethers such as base -2,4- dichlorophenyl ether, vinyl naphthyl ether, vinyl anthryl ether etc..

As vinyl ester, it can enumerate：Vinyl butyrate, vinyl iso-butyl acid esters, vinyl trimethyl acetic acid Ester, vinyl diethacetic acid ester, vinyl valerate, vinyl capronate, vinyl chloroacetate ester, vinyl dichloroacetic acid Ester, ethenylmethoxy acetic acid esters, vinyl butoxy acetic acid ester, vinyl benzene yl acetate, vinylacetyl yl acetate, Vinyl lactate, vinyl-beta-phenyl butyrate, vinyl benzoate, vinyl salicylate, chlorobenzoic acid vinyl acetate, four Chlorobenzoic acid vinyl acetate, naphthoic acid vinyl acetate etc..

As phenylethylene, it can enumerate：Styrene；Methyl styrene, dimethyl styrene, trimethyl styrene, second Base styrene, diethyl, isopropyl styrene, butylstyrene, hexyl styrene, cyclohexylstyrenes, decyl benzene Ethene, benzylstyrene, 1-chloro-4-methyl-benzene, trifluoromethyl styrene, ethoxyl methyl styrene, acetoxy-methyl benzene second The ring-alkylated styrenes such as alkene；The alkoxy benzene second such as methoxy styrene, 4- methoxyl group -3- methyl styrenes, dimethoxy styrene Alkene；Chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachloro styrene, pentachloro- styrene, bromstyrol, Dowspray 9, The halogen such as the bromo- 4- trifluoromethyl styrenes of iodobenzene ethene, fluorobenzene ethene, trifluorostyrene, 2-, the fluoro- 3- trifluoromethyl styrenes of 4- For styrene etc..

Weight average molecular weight (the Mw of copolymer (A1)：The measure converted by the styrene of gel permeation chromatography (GPC) Value.It is identical in this specification), preferably 2000~200000, more preferably 5000~30000.By being set as above range, With the flat of the developability after being readily available the film formation energy of the photosensitive polymer combination prepared using resin combination, exposing The tendency of weighing apparatus.

In addition, as alkali soluble resin (A), the resin containing following copolymer can also be preferably used, wherein, it is described Copolymer is：Copolymer (A2), it at least has：Come from above-mentioned unsaturated carboxylic acid (a1) Component units and with it is rear State the Component units at the position that photopolymerization monomer (B) can polymerize；Or copolymer (A3), it at least has：Come from above-mentioned The Component units of unsaturated carboxylic acid (a1), the Component units for coming from the above-mentioned unsaturated compound (a2) containing epoxy radicals and tool There are the Component units at the position that can polymerize with aftermentioned photopolymerization monomer (B).Alkali soluble resin (A) contains copolymer (A2) or in the case of (A3), it is possible to increase the adaptation to substrate of photosensitive polymer combination, photosensitive polymer combination Solidification after breakdown strength.

Copolymer (A2) and copolymer (A3), can be by making to be used as the record of other compounds on copolymer (A1) (methyl) esters of acrylic acid, (methyl) acrylic amide, allyl compound, vinyl ethers, vinyl ester, styrene The copolymer of the further copolymerization such as class.

Component units with the position that can polymerize with photopolymerization monomer (B), be preferably as with optical polymerism list The position that body (B) can polymerize includes the Component units at the position with olefinic unsaturated group.With such Component units Copolymer, on copolymer (A2), one of the carboxyl included in homopolymer that can be by making above-mentioned unsaturated carboxylic acid (a1) The epoxy radicals with being included in the above-mentioned unsaturated compound containing epoxy radicals is divided to be reacted to prepare.In addition, copolymer (A3) can With by making with the Component units for coming from above-mentioned unsaturated carboxylic acid (a1) and coming from the above-mentioned unsaturationization containing epoxy radicals A part for epoxy radicals in the copolymer of the Component units of compound (a2), with unsaturated carboxylic acid (a1) reacted to prepare.

The weight average molecular weight of copolymer (A2) and copolymer (A3), preferably 2000~50000, more preferably 5000~ 30000.By being set as above range, with the film for being readily available the photosensitive polymer combination prepared using resin combination The tendency of the balance of the developability formed after, exposing.

It should be noted that as alkali soluble resin (A), except the resin selected from copolymer (A1) and (A3) with Outside, other known alkali soluble resins can also be included.But, the resin selected from copolymer (A1) and (A3) is in alkali Shared ratio is preferably more than 80 mass % in soluble resin (A), more preferably more than 90 mass %, most preferably 100 Quality %.

In addition, the content of the alkali soluble resin (A) in resin combination is not particularly limited.Typically, resin combination The content of alkali soluble resin (A) in thing, preferably 5~60 mass %, more preferably 10~30 mass %.Now, easily Prepare the resin combination that viscosity is low, be easily processed.

<The compound that formula (1) is represented>

The resin combination of the present invention contains the compound of following formula (1) expression.By making to include above-mentioned alkali-soluble tree Contain the compound in the resin combination of fat (A) and solvent (C) containing PGMEA, alkali soluble resin (A) can be suppressed Molecular weight.

In above-mentioned formula (1), R¹And R²Separately represent hydrogen atom or organic group, but R¹And R²At least one Individual expression organic group.

It is used as R¹And R²In organic group, can enumerate：Alkyl, alkenyl, cycloalkyl, cycloalkenyl group, aryl, aralkyl Deng.The organic group, can also include the key or substituent beyond the alkyl such as hetero atom in the organic group.In addition, this has Machine group can be any one in straight-chain, branched, ring-type.The organic group is usually 1 valency, but is forming ring-type knot In situation of structure etc., organic group more than divalent can be obtained.

R¹And R²Cyclic structure can be bonded together to form, heteroatomic bonding can also be further included.It is used as ring-type knot Structure, can enumerate Heterocyclylalkyl, heteroaryl etc., or condensed ring.

It is used as R¹And R²Organic group in alkyl beyond key, as long as do not damage the present invention effect, then without spy Do not limit, can enumerate：Contain the heteroatomic key such as oxygen atom, nitrogen-atoms, silicon atom.As concrete example, it can enumerate：Ether Key, thioether bond, carbonyl bond, thiocarbonyl group key, ester bond, amido link, amino-formate bond, imido key (- N=C (- R)-,-C (= NR)-：R represents hydrogen atom or organic group), carbonic acid ester bond, sulphonyl key, sulfenyl key, azo bond etc..

From the viewpoint of heat resistance, R is used as¹And R²Organic group in alkyl beyond key, preferably ehter bond, Thioether bond, carbonyl bond, thiocarbonyl group key, ester bond, amido link, amino-formate bond, imido key (- N=C (- R)-,-C (=NR)-：R Represent the organic group of hydrogen atom or 1 valency), carbonic acid ester bond, sulphonyl key, sulfenyl key.

It is used as R¹And R²Organic group in alkyl beyond substituent, as long as do not damage the present invention effect, then do not have It is particularly limited to, can enumerates：Halogen atom, hydroxyl, sulfydryl, thioether group, cyano group, isocyano group, cyanic acid ester group, NCO, It is thiocyanic acid ester group, different thiocyanic acid ester group, silicyl, silanol group, alkoxy, alkoxy carbonyl, carbamyl, thio Carbamyl, nitro, nitroso, carboxyl, carboxylic acid ester groups, acyl group, acyloxy, sulfino, sulfo group, sulfonic group, phosphino-, phosphinyl (ホ ス Off イ ニ Le base), phosphono (ホ ス ホ ノ yls), phosphonate group (ホ ス ホ Na ト yls), oxyimino, alkylether radicals, Alkenyl ether, alkyl sulfide ether, alkenyl thioether group, aryl ether, aryl thioethers base, amino (- NH₂、-NHR、-NRR’：R and R ' separately represents alkyl) etc..The hydrogen atom included in above-mentioned substituent, can be replaced by alkyl.In addition, above-mentioned substitution The alkyl included in base can be any one in straight-chain, branched and ring-type.

It is used as R¹And R²Organic group in alkyl beyond substituent, preferably halogen atom, hydroxyl, sulfydryl, thioether Base, cyano group, isocyano group, cyanic acid ester group, NCO, thiocyanate groups, isothiocyanate group, silicyl, silanol group, Alkoxy, alkoxy carbonyl, carbamyl, sulphur carbamyl, nitro, nitroso, carboxyl, carboxylic acid ester groups, acyl group, acyloxy, Sulfino, sulfo group, sulfonic group, phosphino-, phosphinyl, phosphono, phosphonate group, oxyimino, alkylether radicals, alkenyl ether, alkane Base thioether group, alkenyl thioether group, aryl ether, aryl thioethers base.

More than, it is used as R¹And R², preferably at least one alkyl or the virtue of carbon number 1~12 for carbon number 1~12 Base or the Heterocyclylalkyl or heteroaryl for bonding together and being formed carbon number 2~20.As Heterocyclylalkyl, piperazine can be enumerated Piperidinyl, morpholinyl etc., as heteroaryl, can enumerate imidazole radicals, pyrazolyl etc..

In above-mentioned formula (1), R³Represent singly-bound or organic group.

It is used as R³In organic group, can enumerate from alkyl, alkenyl, cycloalkyl, cycloalkenyl group, aryl, aralkyl etc. Remove the group after 1 hydrogen atom.The organic group, can also include substituent in the organic group., can as substituent To enumerate R¹And R²The substituent of middle illustration.In addition, the organic group can be any one in straight-chain, branched.

More than, it is used as R³, it is preferably from the aryl of the alkyl or carbon number 1~12 of singly-bound or carbon number 1~12 Remove the group after 1 hydrogen atom.

In above-mentioned formula (1), R⁴And R⁵Separately represent hydrogen atom, halogen atom, hydroxyl, sulfydryl, thioether group, first silicon Alkyl, silanol group, nitro, nitroso, sulfino, sulfo group, sulfonic group, phosphino-, phosphinyl, phosphono, phosphonate group or organic Group.

It is used as R⁴And R⁵In organic group, R can be enumerated¹And R²The group of middle illustration.The organic group, with R¹With And R²Situation it is same, key and substituent beyond the alkyl such as hetero atom in the organic group can also be included.In addition, this is organic Group can be any one in straight-chain, branched, ring-type.

More than, it is used as R⁴And R⁵, separately preferably hydrogen atom, the alkyl of carbon number 1~10, carbon number 4 ~13 cycloalkyl, the cycloalkenyl group of carbon number 4~13, the aryloxyalkyl group of carbon number 7~16, the virtue of carbon number 7~20 Alkyl, the alkyl of carbon number 2~11 with cyano group, the alkyl of carbon number 1~10 with hydroxyl, carbon number 1~ 10 alkoxy, the amide groups of carbon number 2~11, the alkylthio group of carbon number 1~10, the acyl group of carbon number 1~10, carbon Ester group (- the COOR ,-OCOR of atomicity 2~11：R represents alkyl), the aryl of carbon number 6~20, electron donating property group and/ Or the benzyl of the aryl of the carbon number 6~20 of electron-withdrawing substituent group, electron donating property group and/or electron-withdrawing substituent group Base, cyano group, methylsulfany.More preferably R⁴And R⁵The two is hydrogen atom or R⁴For methyl, R⁵For hydrogen atom.

In above-mentioned formula (1), R⁶、R⁷、R⁸And R⁹Separately represent hydrogen atom, halogen atom, hydroxyl, sulfydryl, thioether Base, silicyl, silanol group, nitro, nitroso, sulfino, sulfo group, sulfonic group, phosphino-, phosphinyl, phosphono, phosphonic acids Base, amino, ammonium or organic group.

It is used as R⁶、R⁷、R⁸And R⁹In organic group, R can be enumerated¹And R²The organic group of middle illustration.This is organic Group and R¹And R²Situation it is same, the key and substituent beyond the alkyl such as hetero atom can also be included in the organic group. In addition, the organic group can be any one in straight-chain, branched, ring-type.

It should be noted that in above-mentioned formula (1), R⁶And R⁷It is not hydroxyl.

R⁶、R⁷、R⁸And R⁹More than two can bond together to form cyclic structure, heteroatomic key can also be included.As Cyclic structure, can enumerate Heterocyclylalkyl, heteroaryl etc., or condensed ring.For example, to R⁶、R⁷、R⁸And R⁹For, they In more than two bonding and can be formed will be bonded with R⁶、R⁷、R⁸And R⁹Phenyl ring the shared naphthalene of atom, anthracene, phenanthrene, indenes Deng condensed ring.

More than, it is used as R⁶、R⁷、R⁸And R⁹, separately preferably hydrogen atom, the alkyl of carbon number 1~10, carbon The cycloalkyl of atomicity 4~13, the cycloalkenyl group of carbon number 4~13, the aryloxyalkyl group of carbon number 7~16, carbon number 7~ Alkyl, the carbon atom of 20 aralkyl, the alkyl of carbon number 2~11 with cyano group, carbon number 1~10 with hydroxyl Alkoxy, the amide groups of carbon number 2~11, the alkylthio group of carbon number 1~10, the acyl of carbon number 1~10 of number 1~10 Base, the ester group of carbon number 2~11, the aryl of carbon number 6~20, electron donating property group and/or electron-withdrawing substituent group The aryl of carbon number 6~20, the benzyl of electron donating property group and/or electron-withdrawing substituent group, cyano group, methylsulfany, Nitro.

In addition, for R⁶、R⁷、R⁸And R⁹For, more than two bondings in them will be bonded with so as to be formed R⁶、R⁷、R⁸And R⁹Shared naphthalene, anthracene, phenanthrene, the indenes of atom of phenyl ring etc. condensed ring.

More preferably R⁶、R⁷、R⁸And R⁹All hydrogen atoms, or R⁶、R⁷、R⁸And R⁹Any one be nitro, its excess-three Individual is hydrogen atom.

In above-mentioned formula (1), R¹⁰Represent hydrogen atom or organic group.

It is used as R¹⁰In organic group, R can be enumerated¹And R²The organic group of middle illustration.The organic group and R¹And R²Situation it is same, the key and substituent beyond the alkyl such as hetero atom can also be included in the organic group.In addition, this is organic Group can be any one in straight-chain, branched, ring-type.

The compound that above-mentioned formula (1) represents, because the contraposition in phenyl ring has-OR¹⁰Base, therefore, dissolving in a solvent Property is good.

More than, it is used as R¹⁰, the preferably alkyl of hydrogen atom or carbon number 1~12, more preferably methyl.

In the compound that above-mentioned formula (1) represents, as particularly preferred concrete example, the chemical combination that following formula is represented can be enumerated Thing.

The synthetic method for the compound that above-mentioned formula (1) represents is not particularly limited, can be according to described in aftermentioned embodiment Method synthesis.

The content for the compound that above-mentioned formula (1) in resin combination is represented, is not hindering the scope of the purpose of the present invention Inside it is not particularly limited.The content for the compound that above-mentioned formula (1) represents, is typically relative to the mass of alkali soluble resin (A) 100 Part, preferably 0.01~10 mass parts, more preferably 0.01~5 mass parts.

<Solvent (S)>

Resin combination, contains the solvent containing propylene glycol monomethyl ether (PGMEA) as solvent (S).

The content of PGMEA in solvent (S), is not particularly limited, preferably in the range of the purpose of the present invention is not hindered For more than 50 mass %, particularly preferably more preferably more than 70 mass %, 100 mass %.PGMEA's in solvent (S) contains In the case of measuring as more than 50 mass %, easily cause the increase of the molecular weight of alkali soluble resin (A), it is therefore, of the invention Effect is notable.

In the case that solvent (S) is containing other organic solvents beyond PGMEA, other organic solvents are not hindering this It is not particularly limited in the range of the purpose of invention.As other organic solvents beyond PGMEA, specifically, it can enumerate Ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol list n-propyl ether, ethylene glycol list n-butyl ether, diethylene glycol list first Base ether, TC, diethylene glycol list n-propyl ether, diethylene glycol list n-butyl ether, triethylene glycol monomethyl ether, Triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl, propane diols list n-propyl ether, propane diols Dan Zhengding Base ether, DPGME, dihydroxypropane single-ethyl ether, DPG list n-propyl ether, DPG list n-butyl ether, (poly-) alkylene glycol monoalkyl ethers such as tripropylene glycol monomethyl ether, tripropylene glycol list ethylether；Ethylene glycol single methyl ether acetic acid Ester, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, TC acetic acid esters, propane diols Single monoethyl ether acetate etc. (poly-) alkylene glycol monoalkyl ether acetate class；Methyl ethyl ketone, cyclohexanone, 2-HEPTANONE, 3- heptanone Deng ketone；The lactic acid alkyl ester classes such as 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester；2- hydroxy-2-methyls ethyl propionate, 3- first Epoxide methyl propionate, 3- methoxypropionates, 3- ethoxypropanoates, 3- ethoxyl ethyl propionates, ethoxyacetic acid second Ester, hydroxyl ethyl acetate, 2- hydroxy-3-methyls methyl butyrate, 3- methoxybutyls acetic acid esters, 3- methyl -3- methoxybutyls Acetic acid esters, 3- methyl -3- methoxybutyls propionic ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, second The sour n-pentyl ester of sour isobutyl ester, Ant, isoamyl acetate, n-butyl propionate, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, butyric acid N-butyl, methyl pyruvate, ethyl pyruvate, pyruvic acid n-propyl, methyl acetoacetate, ethyl, 2- oxygen Other esters such as base ethyl butyrate；Toluene, dimethylbenzene etc. are aromatic hydrocarbon；1-METHYLPYRROLIDONE, DMF, Amide-types such as N, N- dimethylacetamide base acid amides etc..In these, preferably alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl Ether acetic acid esters, lactic acid alkyl ester class, more preferably alkylene glycol monoalkyl ether acetate class.These solvent can individually make With or can also be applied in combination two or more.

The content of solvent (S) in resin combination is not particularly limited, it is considered to use the photosensitive of resin combination preparation The composition of property resin combination is suitably determined.

<The manufacture method of resin combination>

The resin combination of the present invention, can be by the way that above-mentioned each composition be stirred with three roller mills, ball mill, sand mill etc. The machine of mixing is mixed (scattered, mixing), is filtered to prepare with filters such as 5 μm of molecular filters as needed.

《Photosensitive polymer combination》

Photosensitive polymer combination, it is also poly- containing photopolymerization monomer (B) and light in addition to above-mentioned resin combination Close initiator (C).Hereinafter, illustrated for each composition included in photosensitive polymer combination.

<Alkali soluble resin (A)>

The resin that can be used as alkali soluble resin (A), on resin combination, as described above.

Content of the alkali soluble resin (A) in photosensitive polymer combination, relative to photosensitive polymer combination Solid constituent, preferably 40~85 mass %, more preferably 45~75 mass %.By being set as above range, with easy Obtain the tendency of the balance of developability.

<The compound that formula (1) is represented>

The compound that above-mentioned formula (1) represents, it is as described above on resin combination.It is above-mentioned in photosensitive polymer combination The content for the compound that formula (1) is represented, it is same with the content in resin combination.The content for the compound that above-mentioned formula (1) represents, It is typically relative to the mass parts of alkali soluble resin (A) 100, more preferably preferably 0.01~10 mass parts, 0.01~5 mass Part.The compound that above-mentioned formula (1) represents, when preparing photosensitive polymer combination using above-mentioned resin combination, can be added.

<Photopolymerization monomer (B)>

As the present invention photosensitive polymer combination in contain photopolymerization monomer (B) (hereinafter also referred to as " and (B) into Point ") it is preferable to use the monomer with olefinic unsaturated group.There is simple function in monomer with the olefinic unsaturated group Monomer and polyfunctional monomer.

As monofunctional monomer, it can enumerate：(methyl) acrylamide, methylol (methyl) acrylamide, methoxy methyl Base (methyl) acrylamide, ethoxyl methyl (methyl) acrylamide, butoxymethyl (methyl) acrylamide, butoxy methoxy Ylmethyl (methyl) acrylamide, N- methylols (methyl) acrylamide, N- hydroxymethyls (methyl) acrylamide, (methyl) third Olefin(e) acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2- acryloyls Amine -2- methyl propane sulfonic acids, tert-butyl acrylamide sulfonate, methyl (methyl) acrylate, ethyl (methyl) acrylate, fourth Base (methyl) acrylate, 2- ethylhexyls (methyl) acrylate, cyclohexyl (methyl) acrylate, 2- hydroxyethyl (first Base) acrylate, 2- hydroxypropyls (methyl) acrylate, 2- hydroxybutyls (methyl) acrylate, 2- phenoxy group -2- hydroxyls Propyl group (methyl) acrylate, 2- (methyl) acryloxy -2- hydroxypropyl phthalates, glycerine list (methyl) propylene Acid esters, tetrahydrofurfuryl (methyl) acrylate, dimethylamino (methyl) acrylate, glycidyl (methyl) acrylic acid Ester, 2,2,2- trifluoroethyls (methyl) acrylate, 2,2,3,3- tetra- fluoropropyl (methyl) acrylate, phthalic acid derive Half (methyl) acrylate of thing etc..These monofunctional monomers can be used alone or can also be applied in combination two or more.

On the other hand, as polyfunctional monomer, it can enumerate：Ethylene glycol two (methyl) acrylate, (first of diethylene glycol two Base) acrylate, tetraethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, polypropylene glycol two (methyl) Acrylate, butanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6- hexylene glycols two (methyl) third Olefin(e) acid ester, trimethylolpropane tris (methyl) acrylate, glycerine two (methyl) acrylate, pentaerythritol triacrylate, Tetramethylol methane tetraacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate, pentaerythrite two (methyl) Acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) Double (4- (methyl) the acryloxy diethoxy phenyl) third of acrylate, dipentaerythritol six (methyl) acrylate, 2,2- Alkane, 2,2- double (4- (methyl) acryloxypolyethoxyphenyl) propane, 2- hydroxyls -3- (methyl) acryloxypropyls (methyl) acrylate, ethylene glycol diglycidyl base ether two (methyl) acrylate, diethylene glycol diglycidyl glyceryl ether two (methyl) acrylate, phthalic acid 2-glycidyl base ester two (methyl) acrylate, glycerol tri-acrylate, glycerine gather Poly- (methyl) acrylate of glycidyl ether, carbamate (methyl) acrylate (that is, toluene di-isocyanate(TDI)), front three Reactant, the methylene with 2- hydroxyethyls (methyl) acrylate such as base hexylidene diisocyanate and hexylidene diisocyanate Double (methyl) acrylamides of base, (methyl) acrylamide methylene ether, the contracting of polyalcohol and N- methylols (methyl) acrylamide The polyfunctional monomers such as compound, three propylene formaldehyde etc..These polyfunctional monomers can be used alone or can also be applied in combination two More than kind.

In these monomers with olefinic unsaturated group, from raising photosensitive polymer combination to the closely sealed of substrate From the viewpoint of breakdown strength after property, the solidification of photosensitive polymer combination, polyfunctional monomers more than preferably 3 functions, Polyfunctional monomers more than more preferably 6 functions.

(B) content of composition, relative to the solid constituent of photosensitive polymer combination, preferably 5~50 mass % are more excellent Elect 10~40 mass % as.By being set as above range, with being readily available sensitivity, developability, the balance of resolving power Tendency.

<Photoepolymerizationinitiater initiater (C)>

As the present invention photosensitive polymer combination in contain Photoepolymerizationinitiater initiater (C) (hereinafter also referred to as " and (C) into Point "), it is not particularly limited, known Photoepolymerizationinitiater initiater can be used.

As Photoepolymerizationinitiater initiater, specifically, it can enumerate：1- hydroxycyclohexylphenylketones, 2- hydroxy-2-methyls- 1- phenyl-propane -1- ketone, 1- [4- (2- hydroxyl-oxethyls) phenyl] -2- hydroxy-2-methyl -1- propane -1- ketone, 1- (4- isopropyls Base phenyl) -2- hydroxy-2-methyl propane -1- ketone, 1- (4- dodecylphenyls) -2- hydroxy-2-methyl propane -1- ketone, 2,2- Dimethoxy -1,2- diphenylethane -1- ketone, double (4- dimethylaminophenyls) ketone, 2- methyl isophthalic acids-[4- (methyl sulphur) benzene Base] -2- morpholino propane -1- ketone, 2- benzyl -2- dimethylaminos -1- (4- morphlinophenyls)-butane -1- ketone, ethyl ketone, 1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases], 1- (O- acetyl group oxime), 1,2- octanediones, 1- [4- (benzene Base sulphur) -, 2- (O- benzoyl oximes)], TMDPO, 4- -4 '-methyl of benzoyl Dimethyl sulfide, 4- dimethylaminobenzoic acids, 4- dimethylaminobenzoic acids methyl esters, EDMAB, 4- dimethylaminobenzoic acids butyl ester, 4- dimethylamino -2- ethylhexyl Benzoic acids, 4- dimethylamino -2- isoamyl benzenes Formic acid, benzyl-'beta '-methoxy ethyl acetals, benzyl dimethyl ketal, 1- phenyl -1,2- pentanediones -2- (O- ethyoxyl carbonyls Base) oxime, o- benzoyls methyl benzoate, 2,4- diethyl thioxanthones, CTX, 2,4- dimethyl thioxanthones, 1- be chloro- 4- butoxy thioxanthones, thioxanthene, 2- diurils ton, 2,4- diethyl thioxanthene, 2- methyl thioxanthene, 2- isopropylthioxanthones, 2- ethyl anthracenes Quinone, prestox anthraquinone, 1,2- benzos anthraquinone, 2,3- diphenyl anthraquinone, azodiisobutyronitrile, benzoyl peroxide, isopropyl Base benzene peroxide, 2-mercaptobenzimidazole, 2- mercaptobenzoxazoles, 2-mercaptobenzothiazole, 2- (Chloro-O-Phenyl) -4,5- bis- (m-methoxyphenyl)-imidazole dimer, benzophenone, 2- chlorobenzophenones, p, p '-bis- dimethylamino benzophenones, 4, 4 '-bis- diethylamino benzophenone, 4,4 '-dichloro benzophenone, 3,3- dimethyl -4- methoxy benzophenones, benzyl, benzene Acyloin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, Benzoin butyl ether, acetophenone, 2,2- diethoxy acetophenones, to dimethyl acetophenone, to dimethylamino benzylacetone, dichloro-benzenes Ethyl ketone, trichloroacetophenone, p-tert.-butyl acetophenone, to dimethylamino benzoylformaldoxime, to tert-butyl group trichloroacetophenone, to the tert-butyl group Dichloroacetophenone, α, the chloro- 4- metaphenoxy acetophenones of α-one, thioxanthones, 2- methyl thioxanthones, ITX, dibenzo Cycloheptanone, amyl group -4- dimethyl aminobenzoates, 9- phenylacridines, 1,7- pairs-(9- acridinyls) heptane, 1,5- pairs-(9- Acridinyl) pentane, 1,3- be double-(9- acridinyls) propane, to methoxyl group triazine, 2,4,6- tri- (trichloromethyl)-s- triazines, 2- first Double (the trichloromethyl)-s- triazines of base -4,6-, double (the trichloromethyl)-s- of 2- [2- (5- methylfuran -2- bases) vinyl] -4,6- Double (the trichloromethyl)-s- triazines of triazine, 2- [2- (furans -2- bases) vinyl (エ テ ニ Le)] -4,6-, 2- [2- (4- diethyl Amino-2-methyl phenyl) vinyl] -4,6- pairs of (trichloromethyl)-s- triazines, 2- [2- (3,4- Dimethoxyphenyl) ethene Base] -4,6- pairs of (trichloromethyl)-s- triazines, double (the trichloromethyl)-s- triazines of 2- (4- methoxyphenyls) -4,6-, 2- (4- second Epoxide styryl) -4,6- couples of (trichloromethyl)-s- triazines, double (the trichloromethyl)-s- of 2- (4- n-butoxyphenyls) -4,6- Triazine, 2,4- pairs-trichloromethyl -6- (the bromo- 4- methoxyl groups of 3-) phenyl-s- triazines, 2,4- pairs-trichloromethyl -6- (the bromo- 4- of 2- Methoxyl group) phenyl-s- triazines, 2,4- be double-trichloromethyl -6- (the bromo- 4- methoxyl groups of 3-) styryl phenyl-s- triazines, 2,4- Double-trichloromethyl -6- (the bromo- 4- methoxyl groups of 2-) styryl phenyl-s- triazines etc..It is especially excellent in terms of sensitivity in these Choosing uses the Photoepolymerizationinitiater initiater of oxime system.These Photoepolymerizationinitiater initiaters can be used alone or can also be applied in combination two kinds with On.

(C) content of composition, relative to the solid constituent of photosensitive polymer combination, preferably 0.5~30 mass %, more Preferably 1~20 mass %.By being set as above range, sufficient heat resistance, chemical-resistant can be obtained, in addition, making Film formation can be improved, bad so as to suppress solidification.

Furthermore it is possible to combine light-initiated auxiliary agent in (C) composition.As light-initiated auxiliary agent, it can enumerate：Three ethanol Amine, methyl diethanolamine, triisopropanolamine, 4- dimethylaminobenzoic acids methyl esters, EDMAB, 4- bis- Methylaminobenzoate isopentyl ester, 4- dimethylaminobenzoic acid 2- ethylhexyls, benzoic acid 2- dimethylamino ethyl esters, N, N- Dimethyl-p-toluidine, 4,4 '-bis- (dimethylamino) benzophenone, 9,10- dimethoxys anthracene, 2- ethyl -9,10- dimethoxies Base anthracene, 9,10- diethoxies anthracene, 2- ethyl -9,10- diethoxy anthracenes etc..These light-initiated auxiliary agents can be used alone or It can also be applied in combination two or more.

<Colouring agent (D)>

The photosensitive polymer combination of the present invention, as needed, can include colouring agent (D).Particularly in photonasty tree In the case that oil/fat composition contains opacifier as colouring agent, the formation for being preferred for black pad is used.Padded by black, energy Enough light leak (Guang order け suppressed from the liner part in display device), so as to manufacture can display contrast it is high preferred Image display device.

The colouring agent (D) contained in photosensitive polymer combination as the present invention, is not particularly limited, for example, in face Color indexes (C.I.；The Society of Dyers and Colourists companies issue) in be categorized into pigment (Pigment) Compound, specifically, preferably use the compound with color index (C.I.) numbering as described below.

As the example for the yellow uitramarine that can be suitably used, it can enumerate：C.I. (following, " the C.I. face of pigment yellow 1 Material is yellow " equally, only record numbering), 3,11,12,13,14,15,16,17,20,24,31,53,55,60,61,65,71,73, 74、81、83、86、93、95、97、98、99、100、101、104、106、108、109、110、113、114、116、117、119、 120、125、126、127、128、129、137、138、139、147、148、150、151、152、153、154、155、156、166、 167th, 168,175,180 and 185.

As the example for the orange pigment that can be suitably used, it can enumerate：C.I. (following, " the C.I. face of pigment orange 1 Material orange " equally, only record numbering), 5,13,14,16,17,24,34,36,38,40,43,46,49,51,55,59,61,63, 64th, 71 and 73.

As the example for the violet pigment that can be suitably used, it can enumerate：C.I. pigment violet 1 (following, " C.I. face Material is purple " equally, only record numbering), 19,23,29,30,32,36,37,38,39,40 and 50.

As the example for the red pigment that can be suitably used, it can enumerate：C.I. (following, " the C.I. face of paratonere 1 Material it is red " equally, only record numbering) 2,3,4,5,6,7,8,9,10,11,12,14,15,16,17,18,19,21,22,23,30, 31、32、37、38、40、41、42、48:1、48:2、48:3、48:4、49:1、49:2、50:1、52:1、53:1、57、57:1、57: 2、58:2、58:4、60:1、63:1、63:2、64:1、81:1、83、88、90:1、97、101、102、104、105、106、108、 112、113、114、122、123、144、146、149、150、151、155、166、168、170、171、172、174、175、176、 177、178、179、180、185、187、188、190、192、193、194、202、206、207、208、209、215、216、217、 220th, 223,224,226,227,228,240,242,243,245,254,255,264 and 265.

The example conduct for the blue pigment that can be suitably used, can be enumerated：C.I. pigment blue 1 (following, " C.I. face Material is blue " equally, only record numbering), 2,15,15:3、15:4、15:6th, 16,22,60,64 and 66.

As can be suitably used, it is above-mentioned outside form and aspect pigment example, can enumerate：C.I. pigment Green 7, C.I. the viridine green such as pigment green 36, C.I. naphthol greens 37, C.I. pigment browns 23, C.I. pigment brown 25s, C.I. pigment browns 26, C.I. the black pigment such as the dark brown pigment such as pigment brown 28, C.I. pigment blacks 1, C.I. pigment blacks 7.

In addition, in the case of using colouring agent as opacifier, as opacifier, preferably using black pigment.As black Color pigment, can be enumerated：Carbon black, titanium are black, the metal oxide of copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver etc., combined oxidation No matter thing, metal sulfide, metal sulfate or metal carbonate etc., organic matter, the various pigment of inorganic matter.In these, preferably Use the carbon black with high light-proofness.

As carbon black, channel carbon black, furnace black, thermal black, lampblack etc. can be used known to carbon black, preferably use screening The excellent channel carbon black of photosensitiveness.Alternatively, it is also possible to use resin-coating carbon black.

In addition, the tone in order to adjust carbon black, as auxiliary pigment, can be properly added above-mentioned organic pigment.

In order that above-mentioned colouring agent is uniformly dispersed in photosensitive polymer combination, it can also use and further disperse Agent.As such dispersant, polyethyleneimine amine, carbamate resins class, the high score of crylic acid resin are preferably used Sub- dispersant.Especially as colouring agent, in the case of using carbon black color, crylic acid resin is preferably used as dispersant Dispersant.

In addition, inorganic pigment and organic pigment can each be used alone or it is two or more be used in combination, and use in the case of, phase For the mass parts of total amount 100 of inorganic pigment and organic pigment, organic pigment is used preferably in the range of 10~80 mass parts, More preferably used in the range of 20~40 mass parts.

The usage amount of colouring agent in photosensitive polymer combination, can be fitted in the range of the purpose of the present invention is not hindered Work as selection, typically, relative to total 100 mass parts of the solid constituent of photosensitive polymer combination, preferably 5~70 mass Part, more preferably 25~60 mass parts.By being set as above range, the pad of desired shape is easily formed.

In the case of especially with photosensitive polymer combination formation black pad, the envelope preferably padded with black is every 1 μm of OD values reach that more than 0.5 mode adjusts the amount of the opacifier in photosensitive polymer combination.Envelope in black pad Every 1 μm of OD values then easily suppress the light leak from the liner part of display device well if more than 0.5, so as to Sufficiently displayed contrast.

It is preferred that colouring agent is formed after the dispersion liquid disperseed with appropriate concentration using dispersant, it is added to photonasty tree In oil/fat composition.

<Solvent (S)>

The solvent (S) contained as photosensitive polymer combination, can use and can be used in above-mentioned resin combination Solvent (S) organic solvent of the same race.When preparing photosensitive polymer combination, in order that photosensitive polymer combination reach it is desired Solid component concentration, can add solvent (S) or concentrated resin composition.In the case of concentrated resin composition, preferably exist Decompression is lower to be distilled off solvent (S) at low temperature as far as possible.Resin combination is as photosensitive polymer combination comprising an adequate amount of In the case of solvent (S), relative to resin combination, without new additional solvent (S).

The content of (S) composition in photosensitive polymer combination, is not particularly limited, with what can be coated with substrate etc. Concentration, suitably set according to coating film thickness.The viscosity of photosensitive polymer combination is preferably 5~500cp, more preferably 10~ 50cp, more preferably 20~30cp.In addition, solid component concentration is preferably 5~100 mass %, more preferably 20~50 Quality %.

<Other compositions>

In photosensitive polymer combination, as needed, it can be improved containing light absorber, surfactant, adaptation The additives such as agent, defoamer are forbidden in agent, thermal polymerization.All additives can use known additive.Inhaled as light Receive agent, 1,5- dihydroxy naphthlenes, alpha-Naphthol etc. can be enumerated, as surfactant, can enumerate anionic species, cationic, The compound of nonionic class etc., as adaptation enhancer, can enumerate known silane coupler, prohibit as thermal polymerization Only agent, can enumerate quinhydrones, Hydroquinone monoethylether etc., as defoamer, can enumerate organic silicon, fluoride compound etc..

<The preparation method of photosensitive polymer combination>

Photosensitive polymer combination, can enter above-mentioned each composition with mixers such as three roller mills, ball mill, sand mills Row mixing (scattered, mixing), filtered as needed with the filter of 5 μm of molecular filters (ソ Block ラ Application Off イ Le タ less) etc. come Prepare.

It should be noted that from the molecular weight of alkali soluble resin (A) can be made to go out in terms of compared with being kept under low state Hair, photosensitive polymer combination is preferably triggered by adding photopolymerization monomer (B), photopolymerization in above-mentioned resin combination After agent (C) and other compositions as needed, solvent (S) regulation is prepared to desired amount.

On the other hand, photosensitive polymer combination, can also be by the way that alkali soluble resin (A), above-mentioned formula (1) be represented After compound, photopolymerization monomer (B), Photoepolymerizationinitiater initiater (C) and other compositions as needed are mixed, using molten Agent (S) adjusts the solid component concentration of photosensitive polymer combination to desired scope to prepare.Now, alkali soluble resin (A) molecular weight, may also be slightly increased before photosensitive polymer combination is prepared, but from above-mentioned formula (1) expression of cooperation Compound etc. is examined in terms of preparing the increase for the molecular weight that can suppress alkali soluble resin (A) after photosensitive polymer combination Consider, be preferred.

《Pad and display device》

The pad of the present invention is in addition to using above-mentioned photosensitive polymer combination, with using photosensitive polymer combination shape Into conventional pad it is same.In addition, the display device of the present invention is formed except possessing by above-mentioned photosensitive polymer combination Pad outside, it is same with conventional display device.As the specific example of display device, can enumerate liquid crystal display device, Display device of organic EL modes etc..Hereinafter, the forming method only for pad is illustrated.

It is not particularly limited, can be used from all the time using the method for above-mentioned photosensitive polymer combination formation pad Display device pad forming method in suitably select.As the forming method of preferred pad, it can be listed below Method, wherein, including：Painting process, above-mentioned photosensitive polymer combination is coated with substrate, forms photo-sensitive resin； Exposure process, photo-sensitive resin is exposed according to the figure of the pad of regulation；And developing procedure, will be photosensitive after exposure Property resin bed developed, formed pad figure.

First, in painting process, on the substrate that should form pad, using roll coater, invert coating machine, scrape rod coating Machine etc. contacts the non-contact type apparatus for coating such as transfer printing type apparatus for coating and spinning machine (rotary apparatus for coating), curtain curtain coater, The photosensitive polymer combination of the present invention is coated with, as needed, solvent is removed by drying, forms photo-sensitive resin.

Then, the substrate that photo-sensitive resin is formed on surface is used for exposure process.In exposure process, across minus Mask, to photo-sensitive resin irradiation ultraviolet radiation, PRK isoreactivity energy-ray, by photo-sensitive resin according to the rules Pad visuals be exposed.High-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, xenon lamp, carbon arc lamp can be used in exposure Etc. the light source for sending ultraviolet.Light exposure is different according to the composition of photosensitive polymer combination, such as preferably from about 50~ 600mJ/cm²

In developing procedure, the photo-sensitive resin after exposure is developed with developer solution, thus, pad is formed.Development Method is not particularly limited, and can use infusion process, spray-on process etc..As the specific example of developer solution, monoethanol can be enumerated The developer solution or sodium hydroxide of the organics such as amine, diethanol amine, triethanolamine, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salt etc. The aqueous solution.The present invention photosensitive polymer combination, the increase of the molecular weight due to inhibiting alkali soluble resin and show The developability of appropriateness, therefore, it is possible to appropriate development.

In addition, as needed, being calcined, being heating and curing after implementing to the pad after development.The temperature being calcined afterwards is preferred For 150~250 DEG C.

Embodiment

Hereinafter, the present invention is given the account in greater detail by embodiment, but the present invention is not limited to these reality Apply example.

In embodiment and comparative example, the compound represented as above-mentioned formula (1), using following compounds 1~7, as The comparative compound of the compound represented relative to above-mentioned formula (1), uses following comparative compounds 1~6.Compound described below 1~7 synthetic method.It should be noted that in embodiment and comparative example, the compound and ratio that above-mentioned formula (1) is represented It is also referred to as " addition compound " compared with compound.

[synthetic method of compound 1]

3- (4- methoxyphenyls) acryloyl chloride 5.90g (30mmol) are dissolved in the ether of 50ml drying, three are added Ethylamine 4.59ml (equivalent proportion 1.1), diethylamide 2.41ml (equivalent proportion 1.1), are stirred 1 hour at room temperature.With water 50ml, satisfy And NaHCO₃After the aqueous solution 50ml and 1N hydrochloric acid are cleaned, dried, concentrated under reduced pressure with magnesium sulfate.With hexane-ethylacetate As developing solvent, using silica gel as support carrier, refined by column chromatography, obtain corresponding compound 1 (4.65g, 20mmol).The yield of acryloyl chloride benchmark is 67%.

[synthetic method of compound 2]

3- (2- nitro -4- methoxyphenyls) acryloyl chloride 7.25g (30mmol) is dissolved in the ether of 50ml drying, Triethylamine 4.59ml (equivalent proportion 1.1), imidazoles 2.25ml (equivalent proportion 1.1) are added, is stirred 1 hour at room temperature.With water 50ml, Saturation NaHCO₃After the aqueous solution 50ml and 1N hydrochloric acid are cleaned, dried, concentrated under reduced pressure with magnesium sulfate.With hexane-acetic acid second Ester, using silica gel as support carrier, is refined by column chromatography as developing solvent, obtains corresponding compound 2 (4.08g, 15mmol).The yield of acryloyl chloride benchmark is 50%.

[synthetic method of compound 3]

3- (3- nitro -4- methoxyphenyls) acryloyl chloride 7.25g (30mmol) is dissolved in the ether of 50ml drying, Triethylamine 4.59ml (equivalent proportion 1.1), imidazoles 2.25ml (equivalent proportion 1.1) are added, is stirred 1 hour at room temperature.With water 50ml, Saturation NaHCO₃After the aqueous solution 50ml and 1N hydrochloric acid are cleaned, dried, concentrated under reduced pressure with magnesium sulfate.With hexane-acetic acid second Ester, using silica gel as support carrier, is refined by column chromatography as developing solvent, obtains corresponding compound 3 (4.08g, 15mmol).The yield of acryloyl chloride benchmark is 50%.

[synthetic method of compound 4]

By 2- methyl -3- (2- nitro -4- methoxyphenyls) acryloyl chloride 7.67g (30mmol) 50ml drying ether Middle dissolving, adds triethylamine 4.59ml (equivalent proportion 1.1), imidazoles 2.25ml (equivalent proportion 1.1), stirs 1 hour at room temperature.With Water 50ml, saturation NaHCO₃After the aqueous solution 50ml and 1N hydrochloric acid are cleaned, dried, concentrated under reduced pressure with magnesium sulfate.With hexane- Ethyl acetate, using silica gel as support carrier, is refined by column chromatography as developing solvent, obtains corresponding compound 4 (4.29g, 15mmol).The yield of acryloyl chloride benchmark is 50%.

[synthetic method of compound 5]

3- (4- methoxyphenyls) acryloyl chloride 5.90g (30mmol) are dissolved in the ether of 50ml drying, three are added Ethylamine 4.59ml (equivalent proportion 1.1), imidazoles 2.25ml (equivalent proportion 1.1), are stirred 1 hour at room temperature.With water 50ml, saturation NaHCO₃After the aqueous solution 50ml and 1N hydrochloric acid are cleaned, dried, concentrated under reduced pressure with magnesium sulfate.Made with hexane-ethylacetate For developing solvent, using silica gel as support carrier, refined by column chromatography, obtain corresponding compound 5 (3.41g, 15mmol).The yield of acryloyl chloride benchmark is 50%.

[synthetic method of compound 6]

3- (2- nitro -4- methoxyphenyls) acryloyl chloride 7.25g (30mmol) is dissolved in the ether of 50ml drying, Triethylamine 4.59ml (equivalent proportion 1.1), diethylamide 2.41ml (equivalent proportion 1.1) are added, is stirred 1 hour at room temperature.Use water 50ml, saturation NaHCO₃After the aqueous solution 50ml and 1N hydrochloric acid are cleaned, dried, concentrated under reduced pressure with magnesium sulfate.With hexane-second Acetoacetic ester, using silica gel as support carrier, is refined by column chromatography as developing solvent, obtains corresponding compound 6 (5.55g, 20mmol).The yield of acryloyl chloride benchmark is 67%.

[synthetic method of compound 7]

3- (3- nitro -4- methoxyphenyls) acryloyl chloride 7.25g (30mmol) is dissolved in the ether of 50ml drying, Triethylamine 4.59ml (equivalent proportion 1.1), diethylamide 2.41ml (equivalent proportion 1.1) are added, is stirred 1 hour at room temperature.Use water 50ml, saturation NaHCO₃After the aqueous solution 50ml and 1N hydrochloric acid are cleaned, dried, concentrated under reduced pressure with magnesium sulfate.With hexane-second Acetoacetic ester, using silica gel as support carrier, is refined by column chromatography as developing solvent, obtains corresponding compound 7 (5.55g, 20mmol).The yield of acryloyl chloride benchmark is 67%.

[embodiment 1~14 and comparative example 1~6]

The alkali soluble resin (A) and addition compound of the species described in table 1 and amount is dissolved in PGMEA, make The standby mass % of resin concentration 30 resin combination.Using resulting resin combination, according to following methods, molecular weight is carried out It is increased to evaluate.

It should be noted that in table 1, each abbreviation is expressed as follows respectively, the numerical value in bracket is use level (quality Part).

(alkali soluble resin (A))

As alkali soluble resin, the resin for including the unit for coming from following monomers with following mass ratioes is used.

A-1：Methacrylic acid: three ring [5.2.1.0^2,6] decane -8- methyl acrylates: 3,4- epoxy-cyclohexanes - 1- methyl methacrylate=30: 45: 35

A-2：Methacrylic acid: three ring [5.2.1.0^2,6] decane -8- methyl acrylates: 3,4- epoxy-cyclohexanes - 1- methyl methacrylate=30: 25: 55

A-3：Methacrylic acid: three ring [5.2.1.0^2,6] decane -8- methyl acrylates: 3,4- epoxy-cyclohexanes - 1- methyl methacrylates: epoxy dicyclopentenyl acrylate=30: 45: 35: 35

A-4：Methacrylic acid: three ring [5.2.1.0^2,6] decane -8- methyl acrylates: 3,4- epoxy-cyclohexanes - 1- methyl methacrylates: epoxy dicyclopentenyl acrylate=30: 25: 55: 55

A-5：Methacrylic acid: three ring [5.2.1.0^2,6] decane -8- methyl acrylates: 3,4- epoxy-cyclohexanes - 1- methyl methacrylates: 2- (3,4- epoxy-cyclohexane -1- bases) -6- methacryloxies heptanesulfonic acid=30: 45: 35∶35

A-6：Methacrylic acid: three ring [5.2.1.0^2,6] decane -8- methyl acrylates: 3,4- epoxy-cyclohexanes - 1- methyl methacrylates: 2- (3,4- epoxy-cyclohexane -1- bases) -6- methacryloxies heptanesulfonic acid=30: 25: 55∶55

A-7：Methacrylic acid: three ring [5.2.1.0^2,6] decane -8- methyl acrylates: 3,4- epoxy-cyclohexanes - 1- methyl methacrylates: glycidyl methacrylate=30: 45: 35: 35

A-8：Methacrylic acid: three ring [5.2.1.0^2,6] decane -8- methyl acrylates: 3,4- epoxy-cyclohexanes - 1- methyl methacrylates: glycidyl methacrylate=30: 25: 55: 55

[molecular weight is increased to be evaluated]

To embodiment 1~14 immediately after preparation and the resin combination of comparative example 1~6, pass through gel permeation chromatography Determine the weight average molecular weight (Mw of the alkali soluble resin included in each resin combination¹).Then, by embodiment 1~14 and The resin combination of comparative example 1~6 is in thermostat, stand after 168 hours (1 week) at 25 DEG C, passes through gel permeation chromatography Determine the weight average molecular weight (Mw of the alkali soluble resin included in each resin combination²).Use Mw¹And Mw², pass through following formula meter Calculate molecular weight increment rate.The molecular weight increment rate of each resin combination is shown in table 1.

<Molecular weight increment rate calculates formula>

Molecular weight increment rate (%)=Mw²/Mw¹×100

Based on the molecular weight increment rate calculated, according to following benchmark, the increased degree of molecular weight is judged.It will sentence Determine result and be shown in table 1.

○：Molecular weight increment rate is less than 120%.

×：Molecular weight increment rate is more than 120%.

Table 1

It can be seen from table 1, in the resin combination of the embodiment 1~14 of the compound represented containing above-mentioned formula (1), molecule Amount increment rate is controlled below 120%.On the other hand, the ratio containing structure as the compounds represented with above-mentioned formula (1) In resin combination compared with the comparative example 1~6 of compound, molecular weight increment rate reaches more than 125%.Can by these results Know, by easily carrying out including in resin combination without the compound that above-mentioned formula (1) represents is added, then in resin combination , the copolymer i.e. alkali soluble resin at least making unsaturated carboxylic acid and the unsaturated compound containing epoxy radicals are polymerized Molecular weight increase.

[embodiment 15~28 and comparative example 7~12]

Using at the resin combination and 25 DEG C immediately after preparation obtained by embodiment 1~14 and comparative example 1~6 Resin combination after preserving 168 hours, prepares the photosensitive polymer combination of embodiment 15~28 and comparative example 7~12. Specifically, in the species described in the alkali soluble resin (A) containing the amount described in table 2 and the table 2 of addition compound In resin combination, after the photopolymerization monomer (B) and Photoepolymerizationinitiater initiater (C) that add species and amount described in table 2, lead to PGMEA regulation solid component concentrations are crossed, the mass % of solid component concentration 15 photosensitive polymer combination is prepared.Using resulting Photosensitive polymer combination, according to following methods, carry out the evaluation of the developability of photosensitive polymer combination.

It should be noted that in table 2, each abbreviation is expressed as follows respectively, the numerical value in bracket is use level (quality Part).

(photopolymerization monomer (B))

DPHA：Dipentaerythritol acrylate (Nippon Kayaku K. K's system)

(Photoepolymerizationinitiater initiater (C))

OXE01：1,2- octanedione, 1- [4- (phenyl sulphur)-, 2- (O- benzoyl oximes)] (BASF AG's system “IRGACURE OXE01”)

[developability evaluation]

On glass substrate (the ニ Application グ company systems of U one, Eagle-XG), with spin coater be coated with the various embodiments described above and After the photosensitive polymer combination prepared in comparative example, at 80 DEG C dry 5 minutes, obtain 3.0~5.0 μm thickness it is photosensitive Property resin bed.Then, for the photo-sensitive resin, across the mask irradiation ultraviolet radiation for the dot pattern for being formed with 5~10 μm.Connect , by carrying out spray development in 23 DEG C of the mass % of concentration 0.04 potassium hydroxide aqueous solution is heated to, form point-like Figure.In addition, time (the BP being completely dissolved by measuring until unexposed portion：Breakaway poing), evaluate developability.Developability is commented Valency, after to the photosensitive polymer combination obtained using resin combination immediately after preparation and being preserved 168 hours at 25 DEG C of use The obtained photosensitive polymer combination of resin combination carry out.Show the result in table 2.

Table 2

It can be seen from table 2, add in the resin combination of the embodiment 1~14 of the compound represented containing above-mentioned formula (1) Enter the photosensitive polymer combination of after photopolymerization monomer (B) and Photoepolymerizationinitiater initiater (C), embodiment 15~28, on making The photosensitive polymer combination that is obtained with resin combination immediately after preparation and use the resin combination after preserving 168 hours Obtained photosensitive polymer combination, BP difference is 0~5 second, and the two developing time there's almost no difference.

On the other hand understand, the ratio of the comparative compound of structure as the compounds represented with above-mentioned formula (1) are added Compared with comparative example 7~12 obtained from adding photopolymerization monomer (B) and Photoepolymerizationinitiater initiater (C) in the resin combination of example 1~6 Photosensitive polymer combination, on the photosensitive polymer combination obtained using resin combination immediately after preparation and use The photosensitive polymer combination that resin combination after preserving 168 hours is obtained, BP difference is more than 10 seconds, if do not used Resin combination immediately after preparation prepares photosensitive polymer combination, then developing time significantly postpones.

Claims (6)

1. a kind of resin combination, it is characterised in that the compound that is represented containing alkali soluble resin (A), following formula (1) and Solvent (S),

The alkali soluble resin (A) is contained：At least make unsaturated carboxylic acid (a1) and the unsaturated compound (a2) containing epoxy radicals The copolymer (A1) being polymerized,

The unsaturated compound (a2) containing epoxy radicals includes the unsaturated compound of the epoxy radicals containing ester ring type,

The solvent (S) contains propylene glycol monomethyl ether,

In formula, R¹And R²Separately represent hydrogen atom or organic group, still, R¹And R²At least one expression it is organic Group, R¹And R²Cyclic structure can be bonded together to form, heteroatomic key can also be included；R³Represent singly-bound；R⁴And R⁵Respectively Independently represent hydrogen atom, halogen atom, hydroxyl, sulfydryl, thioether group, silicyl, silanol group, nitro, nitroso, sub- sulphur Base, sulfo group, sulfonic group, phosphino-, phosphinyl, phosphono, phosphonate group or organic group；R⁶、R⁷、R⁸And R⁹Independently earth's surface Show hydrogen atom, halogen atom, hydroxyl, sulfydryl, thioether group, silicyl, silanol group, nitro, nitroso, sulfino, sulfo group, sulphur Acidic group, phosphino-, phosphinyl, phosphono, phosphonate group, amino, ammonium or organic group, still, R⁶And R⁷It is not hydroxyl, R⁶、 R⁷、R⁸And R⁹In more than two can bond together to form cyclic structure, heteroatomic key can also be included；R¹⁰Represent hydrogen atom Or organic group.

2. resin combination according to claim 1, wherein, coming from the copolymer (A1) is described containing epoxy radicals Unsaturated compound (a2) unit ratio be more than 30 mass %.

3. resin combination according to claim 1 or 2, wherein, come from the insatiable hunger in the copolymer (A1) Ratio with the unit of carboxylic acid (a1) is more than 20 mass %.

4. a kind of photosensitive polymer combination, wherein, contain the resin combination described in claim 1, photopolymerization monomer (B) With Photoepolymerizationinitiater initiater (C).

5. one kind pad, it is formed as the photosensitive polymer combination described in claim 4.

6. a kind of display device, it possesses the pad described in claim 5.