CN1725086A - Photosensitive resin composite, spacer for display plate and display plate - Google Patents

Abstract

The present invention provides a photosensitive resin composition of a partion for display panel. The radiation sensitive composition contains [A] a copolymer of (a1) an ethylenically unsaturated carboxylic acid and/or an ethylenically unsaturated carboxylic acid anhydride, (a2) an epoxy group-containing ethylenically unsaturated compound and (a3) another ethylenically unsaturated compound, [B] a polymerizable compound having an ethylenically unsaturated bond and [C] a photopolymerization initiator comprising a compound represented by formula (1) wherein one of R<SB>1</SB>and R<SB>2</SB>is an alkyl group, an alicyclic group, an oxygen-containing heterocyclic group, a nitrogen-containing heterocyclic group, an oxygen-containing heterocyclic group or a sulfur-containing heterocyclic group; and R<SB>3</SB>-R<SB>6</SB>each represent H or an alkyl group.

Description

Photosensitive polymer combination, display panel used spacer and display board

Technical field

The present invention relates to photosensitive polymer combination, display panel used spacer and display board, in more detail, the display panel used spacer that the present invention relates to photosensitive polymer combination that the material as the spacer that is formed for display boards such as LCD panel or touch pad is fit to, forms by said composition, and the display board that possesses this spacer.

Background technology

In LCD panel, past, in order between 2 pieces of substrates, to keep certain intervals (unit interval), use has spacer particles such as the beaded glass, plastic bead of regulation particle diameter, but owing to these spacer particles freely scatter on transparent substrates such as glass substrate, so, the phenomenon that engraves on of spacer particle can take place then if having the spacer particle at image forming area, incident light is subjected to scattering, has the problem of the contrast reduction of LCD panel.

Therefore, in order to address this problem, adopt the method that forms spacer by photolithography.This method, photosensitive polymer combination is coated on the substrate, and the mask by regulation also develops behind ultraviolet exposure, forms point-like or striated spacer, because the place that can only stipulate beyond image forming area forms spacer, so can address the above problem substantially.

But actual spacer forming process for example on the substrate that uses by photolithography under the situation of formation spacer, is used the convergence exposure machine more in color filter etc.Under the situation of this convergence exposure, between mask and the substrate that has been coated with photosensitive polymer combination, certain slit is set and exposes, it is desirable on the pattern of mask itself, expose.But because above-mentioned slit is full of air or nitrogen, the light by mask open part (transparent part) is in this slotted section diffusion and launch, so there is the problem of exposing than mask pattern design size widelyer.

Therefore; in order to address this problem; the applicant is in patent document 1; by using 1; 2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oximes) is as the Photoepolymerizationinitiater initiater of photosensitive composite; even clear and definite also can form faithful reappearance mask pattern design size by the convergence exposure, and also excellent display panel used spacers such as intensity, thermotolerance.

[patent document 1] spy opens the 2001-261761 communique

And; follow the maximization of LCD panel, control module slit more correctly is if the cohesive of diaphragm that is formed by photosensitive resin composition for isolator and substrate is insufficient; the spacer that forms can slide from substrate, and the result is the holding unit slit correctly.On LCD panel, carry out the high apertureization of image, the area in the black background zone that the result can the configuration isolation thing also reduces gradually.Therefore, even, require spacer to have the higher transparency in order to make spacer enter the tone that to a certain degree image-region does not damage image yet.

But, comprise what Japanese document 1 was put down in writing, the existing photosensitive polymer combination that uses during spacer forms, still not enough with the cohesive and the transparent aspect of substrate, the photosensitive polymer combination that possesses these characteristics is simultaneously developed in strong expectation.

In addition, in recent years,, developed the maximization of female glass substrate from the large tracts of landization of liquid crystal indicator and the aspects such as raising of throughput rate.Existing substrate dimension (about 680 * 880mm) is because substrate dimension is also little than mask size, so can be by disposable Exposure mode reply.

But large-sized substrate (for example about 1500 * 1800mm) is made the mask size identical with this substrate dimension possibility hardly, is difficult to by disposable Exposure mode reply.

Therefore as the corresponding Exposure mode of large-sized substrate, advocate the substep Exposure mode.But, according to the substep Exposure mode, multiexposure, multiple exposure on a slice substrate, at that time, situation produces the position and closes, required time of branch moved further.The substep Exposure mode is compared with disposable Exposure mode, the danger that has throughput to reduce.Disposable Exposure mode allows at 300mJ/cm ²About the exposure light sensitivity, and the substep Exposure mode requires the exposure light sensitivity at 150mJ/cm ²Or below.But, in the existing material, at 150mJ/cm ²Or following exposure is difficult to obtain enough spacer shape and thickness.

In addition, about the shape of spacer, the controlled required value more and more strictness in recent years of thickness, follow since the shape that method changes when forming spacer, Thickness Variation, composition solution through the time change, the stability that relates to shape, thickness stays research topic.

Summary of the invention

Problem of the present invention, providing can faithful reappearance mask design size into forming under high sensitive, and with the cohesive excellence of substrate, at 150mJ/cm ²Or following exposure also can obtain enough spacer shape and thickness, intensity, thermotolerance etc. are also excellent, in addition, the photosensitive polymer combination of the display panel used spacer of the stability of the controlled process of the shape of spacer, thickness, elapsed time excellent in stability.

According to the present invention, above-mentioned problem, the firstth, realize by photosensitive polymer combination (hereinafter referred to as " photosensitive polymer combination (1) "), it is characterized in that said composition contains:

[A] be ethene unsaturated carboxylic acid and/or ethene unsaturated carboxylic acid anhydrides and (a2) contain the ethene unsaturated compound of epoxy radicals and (a3) multipolymer of other ethene unsaturated compound (a1),

[B] has the polymerizable compound of ethene unsaturated link, and

The Photoepolymerizationinitiater initiater that [C] is made of the represented compound of following formula (1)

[in the formula (1), R ₁, R ₂Be respectively the functional group of sulfur heterocyclic ring base of oxygen-containing heterocycle, the carbon number 4～20 of nitrogen heterocycle, the carbon number 4～20 of oxygen-containing heterocycle, the carbon number 4～20 of alicyclic group (ア リ サ イ Network リ Star Network) (except the above-mentioned naphthenic base), the carbon number 4～20 of naphthenic base, phenyl (but, can by at least one or above replacement of alkoxy, phenyl and the halogen atom of the alkyl of carbon number 1～6, carbon number 1～6), the carbon number 7～20 of the alkyl that is selected from hydrogen atom, carbon number 1～20, carbon number 3～8.But, R ₁, R ₂In any one be the oxygen-containing heterocycle of the alkyl of carbon number 13～20, the alicyclic group of carbon number 7～20 (except the above-mentioned naphthenic base), carbon number 4～20, the nitrogen heterocycle of carbon number 4～20, the oxygen-containing heterocycle of carbon number 4～20, the sulfur heterocyclic ring base of carbon number 4～20.R ₃The alkyl of the straight chain shape of expression hydrogen atom or carbon number 1～12, a chain or ring-type, R ₄, R ₅And R ₆The alkyl of the straight chain shape of expression hydrogen atom or carbon number 1～6, a chain or ring-type.]

According to the present invention, above-mentioned problem, the secondth, realize by the display panel used spacer that forms by photosensitive polymer combination (1).

According to the present invention, above-mentioned problem, the 3rd is to realize by the display board with above-mentioned display panel used spacer.

Description of drawings

Fig. 1 is the figure that illustrates the pattern cross sectional shape.

Embodiment

Below the present invention is described in detail.

Photosensitive polymer combination (1)

-multipolymer [A]-

[A] composition in the photosensitive polymer combination (1), be by (a1) ethene unsaturated carboxylic acid and/or ethene unsaturated carboxylic acid anhydrides and (a2) contain the ethene unsaturated compound of epoxy radicals and (a3) multipolymer of other ethene unsaturated compound (hereinafter referred to as " multipolymer [A] ") constitute.

In each composition that constitutes multipolymer [A], as (a1) ethene unsaturated carboxylic acid and/or ethene unsaturated carboxylic acid anhydrides (following it is generically and collectively referred to as " unsaturated carboxylic acid class monomer (a1) "), can enumerate for example monocarboxylic acid classes such as acrylic acid, methacrylic acid, crotonic acid, 2-methyl ethanol acyloxy ethyl succinic acid, 2-methyl ethanol acyloxy ethyl hexahydrophthalic acid; Omega-dicarboxylic acids such as maleic acid, fumaric acid, pyrocitric acid, mesaconic acid, itaconic acid; The anhydrides of above-mentioned dicarboxylic acid etc.

In these unsaturated carboxylic acid class monomers (a1), the dissolubility and the acquisition of aqueous alkali are easy to viewpoint, preferred acrylic acid, methacrylic acid, maleic anhydride etc. from copolyreaction, gained multipolymer.

In photosensitive polymer combination (1), unsaturated carboxylic acid class monomer (a1) can separately or mix two kinds or above use.

In multipolymer [A], by the containing ratio of unsaturated carboxylic acid class monomer (a1) repeat units derived, be preferably 5～50 weight %, more preferably 10～40 weight % are preferably 15～30 weight % especially.At this moment, if then there is the tendency that the dissolubility of aqueous alkali is reduced in the containing ratio less than 5 weight % of unsaturated carboxylic acid class monomer (a1) repeat units derived, on the other hand,, then probably the dissolubility of aqueous alkali is become excessive if surpass 40 weight %.

In addition, the ethene unsaturated compound (hereinafter referred to as " containing epoxy radicals monomer (a2) ") that contains epoxy radicals as (a2), can enumerate for example glycidyl acrylate, acrylic acid 2-methyl ethylene oxidic ester, acrylic acid 3,4-epoxy butyl ester, acrylic acid 6,7-epoxy heptyl ester, acrylic acid 3, acrylic acid epoxy alkyl esters such as 4-epoxy cyclohexyl; Glycidyl methacrylate, methacrylic acid 2-methyl ethylene oxidic ester, methacrylic acid 3,4-epoxy butyl ester, methacrylic acid 6,7-epoxy heptyl ester, methacrylic acid 3, methacrylic acid epoxy alkyl ester classes such as 4-epoxy cyclohexyl; α-Yi Jibingxisuan ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, α-Yi Jibingxisuan 6, alpha-alkyl acrylic acid epoxy alkyl esters such as 7-epoxy heptyl ester; Neighbour-vinyl benzyl glycidol ether ,-the vinyl benzyl glycidol ether, right-diglycidyl ethers such as vinyl benzyl glycidol ether.

These contain in the monomer (a2) of epoxy radicals, viewpoint from copolyreaction and spacer intensity, preferable methyl glycidyl acrylate, methacrylic acid 2-methyl ethylene oxidic ester, methacrylic acid 6,7-epoxy butyl ester, neighbour-vinyl benzyl glycidol ether, between-the vinyl benzyl glycidol ether, right-vinyl benzyl glycidol ether etc.

In photosensitive polymer combination (1), the monomer (a2) that contains epoxy radicals can separately or mix two kinds or above use.

In multipolymer [A], by the containing ratio of the monomer that contains epoxy radicals (a2) repeat units derived, be preferably 10～70 weight %, more preferably 20～60 weight % are preferably 30～50 weight % especially.At this moment, contain epoxy radicals monomer (a2) if the containing ratio deficiency of repeat units derived 10 weight %, then the intensity of gained spacer has the tendency of reduction, on the other hand, if surpass 70 weight %, then the storage stability of gained multipolymer has the tendency of reduction.

And, as (a3) other ethene unsaturated compound (below, abbreviate " other monomer (a3) " as), can enumerate for example alkyl-acrylates such as methyl acrylate, isopropyl acrylate; Alkyl methacrylates such as methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, the secondary butyl ester of methacrylic acid, metering system tert-butyl acrylate; Cyclohexyl acrylate, acrylic acid 2-methyl cyclohexane ester, acrylic acid three ring [5.2.1.0 ^2,6] decane-8-base, acrylic acid 2-(three ring [5.2.1.0 ^2,6] decane-8-base oxygen) acrylate cyclic ester classes such as ethyl ester, isobornyl acrylate; Cyclohexyl methacrylate, methacrylic acid 2-methyl cyclohexane ester, methacrylic acid three ring [5.2.1.0 ^2,6] decane-8-base, methacrylic acid 2-(three ring [5.2.1.0 ^2,6] decane-8-base oxygen) methacrylic acid alicyclic esters classes such as ethyl ester, isobornyl methacrylate; Acrylic acid such as phenyl acrylate, benzyl acrylate aryl ester or aralkyl ester class; Aryl methacrylate such as phenyl methacrylate, benzyl methacrylate or aralkyl ester class; Dicarboxylic acid dialkyl esters classes such as diethyl maleate, DEF, diethyl itaconate; Methacrylic acid hydroxyl alkyl esters such as 2-hydroxyethyl methacrylate, methacrylic acid 2-hydroxy propyl ester; Tetrahydrofurfuryl methacrylate, tetrahydrofuran base methacrylate, THP trtrahydropyranyl-2-methyl acrylate etc. contain unsaturated assorted five or six membered ring methyl acrylic ester of an oxygen atom; Styrene, α-Jia Jibenyixi ,-methyl styrene, p-methylstyrene, to vinyl aromatic compounds such as methoxy styrenes; Remove 1,3-butadiene, isoprene, 2, outside 3-dimethyl-1,3-butadiene equiconjugate dienes compound, also have vinyl cyanide, methacrylonitrile, acrylamide, Methacrylamide, vinyl chloride, vinylidene chloride, vinyl acetate etc.

In these other monomers (a3), from copolyreaction and gained multipolymer deliquescent viewpoint to aqueous alkali, preferred acrylic acid 2-methyl cyclohexane ester, metering system tert-butyl acrylate, methacrylic acid three ring [5.2.1.0 ^2,6] decane-8-base, styrene, p-methoxystyrene, tetrahydrofurfuryl methacrylate, 1,3-butadiene etc.

In photosensitive polymer combination (1), other monomer (a3) can separately or mix 2 kinds or above use.

In multipolymer [A], the containing ratio of other monomer (a3) repeat units derived is preferably 10～70 weight %, more preferably 20～50 weight %, preferred especially 30～50 weight %.At this moment, other monomer (a3) if the containing ratio deficiency of repeat units derived 10 weight %, the storage stability of gained multipolymer has the tendency of reduction, on the other hand, if surpass 70 weight %, the gained multipolymer has the tendency of reduction to the dissolubility of aqueous alkali.

Multipolymer [A] has carboxyl and/or acid anhydride and epoxy radicals, the dissolubility that aqueous alkali is had appropriateness, do not use special hardening agent even do not unite simultaneously, also can easily solidify by heating, the photosensitive polymer combination (1) that contains this multipolymer, residual and the demoulding that or not when developing can easily form the spacer of predetermined pattern.

Multipolymer [A] can be by for example making unsaturated carboxylic acid class monomer (a1), contain the monomer (a2) of epoxy radicals and other monomer (a3) in appropriate solvent, polymerization in the presence of radical polymerization initiator and making.

As the solvent that uses in the above-mentioned polymerization, can enumerate for example alcohols such as methyl alcohol, ethanol, n-propanol, isopropyl alcohol; Ethers such as tetrahydrofuran, diox; Ethylene glycol monoalkyl ether classes such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether; Ethylene glycol monoalkyl ether acetate classes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol propyl ether acetic acid esters, ethylene glycol mono-n-butyl ether acetic acid esters;

Ethylene glycol monoalkyl ether propionic acid esters such as glycol monoethyl ether propionic ester, ethylene glycol monoethyl ether propionic ester, ethylene glycol propyl ether propionic ester, ethylene glycol mono-n-butyl ether propionic ester;

Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, TC, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether; Propylene-glycol monoalky lether classes such as propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list n-propyl ether, propylene glycol list n-butyl ether;

Propylene-glycol monoalky lether acetate esters such as propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, propylene glycol list n-propyl ether acetic acid esters, propylene glycol list n-butyl ether acetic acid esters;

Propylene-glycol monoalky lether propionic acid esters such as propylene glycol monomethyl ether propionic ester, propylene glycol list ethylether propionic ester, propylene glycol list n-propyl ether propionic ester, propylene glycol list n-butyl ether propionic ester;

Toluene, dimethylbenzene etc. are aromatic hydrocarbon based;

Ketones such as MEK, 2 pentanone, propione, cyclohexanone, 4-hydroxy-4-methyl-2 pentanone;

2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxypropionic acid n-propyl, the positive butyl ester of 2-methoxypropionic acid, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-ethoxy-propionic acid n-propyl, the positive butyl ester of 2-ethoxy-propionic acid, 2-positive propoxy methyl propionate, 2-positive propoxy ethyl propionate, 2-positive propoxy propionic acid n-propyl, 2-positive propoxy n-butyl propionate, 2-n-butoxy methyl propionate, 2-n-butoxy ethyl propionate, 2-n-butoxy propionic acid n-propyl, 2-n-butoxy n-butyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-methoxypropionic acid n-propyl, the positive butyl ester of 3-methoxypropionic acid, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-ethoxy-propionic acid n-propyl, the positive butyl ester of 3-ethoxy-propionic acid, 3-positive propoxy methyl propionate, 3-positive propoxy ethyl propionate, 3-positive propoxy propionic acid n-propyl, 3-positive propoxy n-butyl propionate, 3-n-butoxy methyl propionate, 3-n-butoxy ethyl propionate, 3-n-butoxy propionic acid n-propyl, alkoxypropan acid alkyl ester class or methyl acetates such as 3-n-butoxy n-butyl propionate, ethyl acetate, n-propyl acetate, n-butyl acetate, hydroxy methyl acetate, hydroxyl ethyl acetate, the glycolic acid n-propyl, the positive butyl ester of glycolic acid, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, the 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-hydracrylic acid n-propyl, the positive butyl ester of 3-hydracrylic acid, 2-hydroxy-3-methyl methyl butyrate, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid n-propyl, the positive butyl ester of methoxyacetic acid, ethoxy acetate, ethoxy ethyl acetate, the ethoxyacetic acid n-propyl, the positive butyl ester of ethoxyacetic acid, the positive propoxy methyl acetate, positive propoxy ethyl acetate, the positive propoxy n-propyl acetate, the positive propoxy n-butyl acetate, the n-butoxy methyl acetate, n-butoxy ethyl acetate, the n-butoxy n-propyl acetate, other ester class such as n-butoxy n-butyl acetate etc.

In these solvents, preferred diethylene glycol alkyl ether, propylene-glycol monoalky lether acetate esters, alkoxypropan acid alkyl ester class etc.

Above-mentioned solvent, can be separately or 2 kinds or above mixing use.

In addition, the radical polymerization initiator as using in the above-mentioned polymerization is not particularly limited, for example can enumerate 2,2 '-azoisobutyronitrile, 2,2 '-azo two-(2, the 4-methyl pentane nitrile), 2,2 '-azo two-(4-methoxyl-2, the 4-methyl pentane nitrile), 4,4 '-azo two (4-cyanopentanoic acid), dimethyl 2,2 '-azo two (2 Methylpropionic acid ester), 2,2 '-azo two azo-compounds such as (4-methoxyl-2,4-methyl pentane nitriles); Benzoyl peroxide, lauroyl superoxide, tert-butyl hydroperoxide pivalate, 1, organic peroxides such as two (tert-butyl hydroperoxide) cyclohexanes of 1-; Hydrogen peroxide etc.In addition, use as radical polymerization initiator under the situation of superoxide, use can be united in they and reductive agent, as the oxidation-reduction type initiating agent.

These radical polymerization initiators can separately or mix 2 kinds or above use.

The multipolymer that obtains like this [A], the preparation for radiation sensitive resin composition is perhaps separated in the preparation that solution directly can be supplied radiation sensitive resin composition from solution.

The weight average molecular weight that is converted into polystyrene that multipolymer [A] is measured by gel permeation chromatography (GPC) (below be called " Mw ") is generally 2,000～100,000, is preferably 5,000～50,000.At this moment, if Mw less than 2,000, reductions such as the development of gained diaphragm, residual film ratio, perhaps pattern form, thermotolerance etc. can be impaired, and on the other hand, if surpass 100,000, sharpness reduces, and pattern form may be impaired.

-polymerizable compound [B]-

[B] composition in the photosensitive polymer combination (1) is polymerizable compound with ethene unsaturated link (below be called " polymerizable compound [B] ").

As polymerizable compound [B], be not particularly limited, good from polymerism, the viewpoint that the intensity of gained spacer improves is set out, be preferably simple function, 2 officials can or 3 officials can or above (methyl) esters of acrylic acid.

As above-mentioned simple function (methyl) esters of acrylic acid, can enumerate for example 2-hydroxyethylmethacry,ate, 2-hydroxyethyl methacrylate, the diethylene glycol monoethyl ether acrylate, the diethylene glycol monoethyl ether methacrylate, iso-bornyl acrylate, the isobornyl methacrylate, 3-methoxyl butylacrylic acid ester, 3-methoxyl butyl methyl acrylate, 2-acryloxy ethyl-2-hydroxypropyl phthalic ester, 2-methacryloxyethyl-2-hydroxypropyl phthalic ester etc., perhaps as commercially available product, can enumerate for example ア ロ ニ Star Network ス M-101, same M-111, same M-114 (East Asia synthetic (strain) system); KAYARAD TC-110S, same TC-120S (Japanese chemical drug (strain)); PVC ス コ-ト 158, same 2311 (Osaka organic chemistry industry (strain) systems) etc.

In addition, as above-mentioned 2 officials energy (methyl) esters of acrylic acid, can enumerate for example glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, the diethylene glycol dimethylacrylate, tetraethylene glycol diacrylate, the TEG dimethylacrylate, 1, the 6-hexanediyl ester, 1, the 6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethylacrylate, two phenoxetol fluorenes diacrylates, two phenoxetol fluorenes dimethylacrylates etc., as commercially available product, can enumerate for example ア ロ ニ Star Network ス M-210 in addition, same M-240, same M-6200 (East Asia synthetic (strain) system), KAYARAD HDDA, same HX-220, same R-604 (Japanese chemical drug (strain) system), PVC ス コ-ト 260, with 312, same 335HP (Osaka organic chemistry industry (strain) system) etc.

And, as above-mentioned 3 officials can or above (methyl) esters of acrylic acid, can enumerate for example trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylate, dipentaerythritol five acrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylate, three (2-acryloxy ethyl) phosphate, three (2-methacryloxyethyl) phosphate etc.

Especially, 9 officials can or above (methyl) acrylate, can enumerate to make and have alkylidene straight chain and alicyclic structure, contain the compound of 2 or above isocyanate group and molecule contain 1 or above hydroxyl 3 officials can, 4 officials can and 5 officials can the reaction of (methyl) acrylate compounds and the urethane acrylate compound that gets.

As above-mentioned commercially available product, for example can enumerate ア ロ ニ Star Network ス M-309, same M-400, same M-405, same M-450, same M-7100, same M-8030, same M-8060, same TO-1450 (East Asia synthetic (strain) system), KAYARAD TMPTA, same DPHA, same DPCA-20, same DPCA-30, same DPCA-60, same DPCA-120 (Japanese chemical drug (strain) system), PVC ス コ-ト 295, with 300, with 360, same GPT, same 3PA, 400 (Osaka organic chemistry industry (strain) systems) etc. together.9 officials can or the commercially available product of above multifunctional urethane acrylate, as an example, for example can enumerate ニ ユ Off ロ Application テ イ ア R-1150 (more than, the first industrial pharmacy (strain) system), KAYARAD DPHA-40H (more than, Japanese chemical drug (strain) system) etc.

These simple functions, 2 officials can or 3 officials can or above (methyl) esters of acrylic acid in, more preferably 3 officials can or above (methyl) esters of acrylic acid, preferred especially trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, pentaerythrite five acrylate and pentaerythrite six acrylate.

Above-mentioned simple function, 2 officials can or 3 officials can or above (methyl) esters of acrylic acid, 2 kinds or above use alone or in combination.

In photosensitive polymer combination (1), the use amount of polymerizable compound [B] with respect to 100 weight portion multipolymers [A], is preferably 50～140 weight portions, more preferably 60～120 weight portions.At this moment, if use amount less than 50 weight portions of polymerizable compound [B] probably can produce the incompleteness of developing during development, on the other hand, and if surpass 140 weight portions, the tendency that exists gained spacer hardness to reduce.

-Photoepolymerizationinitiater initiater [C]-

[C] composition in photosensitive polymer combination (1) is made of O-acyl group oxime type Photoepolymerizationinitiater initiater, compound shown in the preferred especially above-mentioned formula (1) (below be called " Photoepolymerizationinitiater initiater [C] ").

The said Photoepolymerizationinitiater initiater of the present invention is meant the composition that can make the active seed of polymerizable compound [B] beginning polymerization by exposures such as visible light, ultraviolet ray, far ultraviolet, electron beam, X ray, generation.

In " Photoepolymerizationinitiater initiater [C] " shown in the above-mentioned formula (1), R ₁, R ₂Be respectively and be selected from hydrogen atom, the alkyl of carbon number 1～20, the naphthenic base of carbon number 3～8, phenyl (but can be by the alkyl of carbon number 1～6, the alkoxy of carbon number 1～6, phenyl, and at least one or above replacement of halogen atom), the alicyclic group of carbon number 7～20 (ア リ サ イ Network リ Star Network) (except the above-mentioned naphthenic base), the oxygen-containing heterocycle of carbon number 4～20, the nitrogen heterocycle of carbon number 4～20, the oxygen-containing heterocycle of carbon number 4～20, the functional group of the sulfur heterocyclic ring base of carbon number 4～20.But R ₁, R ₂In any one, be the oxygen-containing heterocycle of the alkyl of carbon number 13～20, the alicyclic group of carbon number 7～20 (except the above-mentioned naphthenic base), carbon number 4～20, the nitrogen heterocycle of carbon number 4～20, the oxygen-containing heterocycle of carbon number 4～20, the sulfur heterocyclic ring base of carbon number 4～20.R ₃The alkyl of the straight chain shape of expression hydrogen atom or carbon number 1～12, a chain or ring-type, R ₄, R ₅And R ₆The alkyl of the straight chain shape of expression hydrogen atom or carbon number 1～6, a chain or ring-type.

As the alicyclic group (except the above-mentioned naphthenic base) of above-mentioned carbon number 7～20, can enumerate for example bicyclic alkyl, tricyclic alkyl, spiro cycloalkyl group, Fourth Ring alkyl, contain the terpenes skeleton group, contain the group of adamantyl skeleton etc.

Nitrogen heterocycle as carbon number 4～20, the oxygen-containing heterocycle of carbon number 4～20, the sulfur heterocyclic ring base of carbon number 4～20 can be enumerated for example thia penta cyclic group (チ オ ラ ニ Le), azepine azepines (ア ゼ ピ ニ Le), dihydro azepine azepines, two oxa-s, penta cyclic group, triazinyl Evil thiazolyl (オ キ サ チ ア ニ Le), thiazolyl oxadiazole base, the dioxy indanyl, ジ ヒ ア Na Off レ ニ Le, furyl, thienyl, pyrrole radicals oxazolyl isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, the furazan base, pyranose, pyridazinyl, pyrimidine radicals, pyrazinyl, pyrrolinyl, morpholinyl, piperazinyl, the quinine base, indyl, isoindolyl, benzofuranyl, benzothienyl, indolinyl (イ Application De リ ジ ニ Le), Chromanyl, quinolyl, isoquinolyl, プ リ ニ Le, quinazolyl, the cinnolines base, phthalazinyl, pteridine radicals, carbazyl, acridinyl, phenanthridinyl, the thioxanthene base, phenazinyl, fen thiophene base phenoxthine base Fen Evil base, thianthrene group etc.

As R in the formula (1) ₃The alkyl of straight chain shape, chain or ring-type of carbon number 1～12, can enumerate for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, cyclopentyl, cyclohexyl etc.

In addition, as R ₄, R ₅And R ₆Straight chain shape, the chain or the cyclic alkyl of carbon number 1～6, can enumerate for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl etc.

As the instantiation of compound [C], can enumerate:

1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-two suberyl methane-1-ketoxime-O-acetic acid esters,

1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-two suberyl-1-ketoxime-O-acetic acid esters,

1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-adamantyl methane-1-ketoxime-O-benzoic ether,

1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-adamantyl methane-1-ketoxime-O-acetic acid esters,

1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-tetrahydrofuran methylmethane-1-ketoxime-O-benzoic ether,

1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-tetrahydrofuran methylmethane-1-ketoxime-O-acetic acid esters,

1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-thienyl methane-1-ketoxime-O-benzoic ether,

1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-thienyl methane-1-ketoxime-O-acetic acid esters,

1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-morphan base (モ ロ Off オ ニ Le) methane-1-ketoxime-O-benzoic ether,

1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-the same oxime of morphan methylmethane-1--O-acetic acid esters,

1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-two cyclobutane-carboxylic acid esters,

1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-tristane carboxylate,

1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-adamantanecarboxylic acid ester etc.,

Can use 2 kinds or above these Photoepolymerizationinitiater initiaters [C] simultaneously.

Also can unite the O-acyl group oxime type Photoepolymerizationinitiater initiater (hereinafter referred to as " Photoepolymerizationinitiater initiater [C-2] ") of use except that above-mentioned formula (1) as Photoepolymerizationinitiater initiater [C].

Instantiation as these Photoepolymerizationinitiater initiaters [C-2]; for example can enumerate 1; 2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oximes), 1; 2-diacetyl-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oximes), 1; 2-diacetyl-1-[4-(thiophenyl) phenyl]-2-(O-acetyl group oxime), 1; 2-octadione-1-[4-(methyl mercapto) phenyl]-2-(O-benzoyl oximes), 1,2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-(4-methyl benzoyl oxime)) etc.Wherein, preferred especially 1,2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oximes).

By using these Photoepolymerizationinitiater initiaters [C], even at 150mJ/cm ²Or also can obtain having light sensitivity, fusible spacer under the following exposure.

The use amount of the Photoepolymerizationinitiater initiater [C] in the photosensitive polymer combination (1) with respect to 100 weight portion polymerizable compounds [B], is preferably 5～30 weight portions, more preferably 5～20 weight portions.At this moment, use amount less than 5 weight portions of Photoepolymerizationinitiater initiater [C], residual film ratio has the tendency of reduction during development, and on the other hand, if surpass 30 weight portions, unexposed portion has the tendency of reduction during development to the dissolubility of alkaline-based developer.

In addition, in the photosensitive polymer combination (1), can unite with Photoepolymerizationinitiater initiater [C] and use at least a other Photoepolymerizationinitiater initiater.

As above-mentioned other Photoepolymerizationinitiater initiater, can enumerate for example bisglyoxaline compounds, benzoin compounds, acetophenone compounds, benzophenone compound, α-cyclohexadione compounds, multinuclear benzoquinone compound, Oxoxanthone, phosphine compound, compound in triazine class etc.Wherein, preferred acetophenone compounds (hereinafter referred to as " (D) composition "), bisglyoxaline compounds (hereinafter referred to as " (E) composition ").

(D) composition: acetophenone compounds

In addition, as above-mentioned acetophenone compounds, can enumerate for example alpha-hydroxy ketones, alpha-amido ketone compounds, the compound beyond them.

Instantiation as above-mentioned alpha-hydroxy ketones, can enumerate 1-phenyl-2-hydroxy-2-methyl propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 1-hydroxycyclohexylphenylketone etc., instantiation as above-mentioned alpha-amido ketone compounds, can enumerate the single morpholinyl propane of 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2--1-ketone, 2-benzyl-2-dimethylamino-1-(the single morpholinyl phenyl of 4-)-butanone-1 etc., instantiation as the compound beyond them, for example can enumerate 2, the 2-dimethoxy-acetophenone, 2, the 2-diethoxy acetophenone, 2,2-dimethoxy-2-phenyl acetophenone etc.

These acetophenone compounds, 2 kinds or above use alone or in combination.

By using these acetophenone compounds, can make light sensitivity, spacer shape and compression strenght better.

(E) composition: bisglyoxaline compounds

As the instantiation of above-mentioned bisglyoxaline compounds, can enumerate 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline,

2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline,

2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline,

2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline,

2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline,

2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline,

2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline,

2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc.

In the above-mentioned bisglyoxaline compounds, preferred 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc., preferred especially 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline.

Above-mentioned bisglyoxaline compounds, 2 kinds or above use alone or in combination.

By using these bisglyoxaline compounds, can make light sensitivity, sharpness and cohesive better.

In addition, in order to make the united imidazole enhanced sensitivity, can use aliphatics with dialkyl amido or aromatic series compounds (below be called " sensitizer [E-2] ").

As the instantiation of above-mentioned sensitizer [E-2], can enumerate for example N methyldiethanol amine, 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, right-the dimethylaminobenzoic acid ethyl ester, right-dimethylaminobenzoic acid isopentyl ester etc.In these sensitizers, preferred 4,4 '-two (diethylamino) benzophenone.

These sensitizers [E-2], can use simultaneously 2 kinds or more than.

The use amount of sensitizer [E-2], with respect to 100 weight portions [A], preferably with 0.1～50 weight portion, more preferably the ratio of 1～20 weight portion contains.

The amount of compound [E-2] under the situation of less than 0.1 weight portion, exists gained spacer film belly and the bad tendency of pattern form takes place, and in addition, if surpass 50 weight portions, then can have the bad tendency of pattern form equally.

Use under the situation of united imidazole, and, can use sulfur alcohol compound (below be called " sulfur alcohol compound [E-3] ") as the hydrogen supplying compound.United imidazole can be by having the benzophenone compound enhanced sensitivity of dialkyl amido, and the united imidazole fracture produces imidazole radical.At this moment, do not find high free radical polymerization energy of initiation, becoming back taper, to be not suitable for the situation of shape like that in the majority.This problem can relax by adding sulfur alcohol compound [E-3] in the system that coexists at united imidazole and the benzophenone compound with dialkyl amido.Owing in imidazole radical, supply with from the mercaptan compound to the hydroperoxyl radical, produce neutral imidazoles and have the high sulphur free radical compounds of polymerization energy of initiation.Therefore become the shape of the positive taper that is more suitable for from back taper.

The usage ratio of above-mentioned sulfur alcohol compound [E-3], with respect to 100 weight portion compounds [C], preferably with 0.1～50 weight portion, more preferably the ratio with 1～20 weight portion contains.There is film belly or the bad tendency of pattern form that the gained spacer takes place in the amount of sulfur alcohol compound [E-3] under the situation of less than 0.1 weight portion, in addition, if surpass 50 weight portions, similarly exist the bad tendency of pattern form takes place.

As its instantiation, can enumerate the single mercaptan of aliphatics such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-sulfydryl-5-methoxyl benzo thiazole, 2-sulfydryl-aromatic mercaptans such as 5-methoxyl benzo imidazoles, 3-mercaptopropionic acid, 3-mercapto-propionate, 3-mercaptopropionic acid ethyl ester, 3-mercaptopropionic acid monooctyl ester.As 2 officials can or above aliphatics mercaptan, can enumerate 3,6-dioxy-1, hot two mercaptan of 8-, pentaerythrite four (mercaptoacetate), pentaerythrite four (3-mercaptopropionic acid ester) etc.

The usage ratio of other Photoepolymerizationinitiater initiater, with respect to the full Photoepolymerizationinitiater initiater of 100 weight portions, preferred 100 weight portions or following, more preferably 80 weight portions or following, preferred especially 60 weight portions or following.At this moment, if the usage ratio of other Photoepolymerizationinitiater initiater surpasses 100 weight portions, probably can damage the desired effect of the present invention.

-adjuvant-

In the photosensitive polymer combination (1), in the scope of the harmless desired effect of the present invention, as required, can mix mentioned component adjuvant in addition.

For example, in order to improve coating, can mixed surfactant.This surfactant can suit to use fluorine surfactant and silicone surfactant.

As fluorine surfactant, can suiting, it is terminal to use, the compound that has fluoro-alkyl or fluoro alkylidene in main chain and the side chain at least one position is as its instantiation, can enumerate 1,1,2,2-tetrafluoro octyl group (1,1,2,2-tetrachloro propyl group) ether, 1,1,2,2-tetrachloro octyl group hexyl ether, the sweet glycol two (1 of eight methylene, 1,2,2-tetrachloro butyl) ether, the sweet glycol (1,1 of six ethylidene, 2,2,3,3-chlordene amyl group) ether, the sweet glycol two (1 of eight propylidene, 1,2,2-tetrachloro butyl) ether, the sweet glycol two (1,1 of six propylidene, 2,2,3,3-hexafluoro amyl group) ether, the perfluor sodium dodecylsulphonate, 1,1,2,2,8,8,9,9,10,10-ten fluorine dodecanes, 1,1,2,2,3,3-hexafluoro decane, the fluoro-alkyl benzene sulfonic acid sodium salt, the fluoro-alkyl sodium sulfonate, the fluoro-alkyl carboxylic acid sodium, the fluoro-alkyl polyoxyethylene ether, two glycerine four (fluoro-alkyl polyoxyethylene ether), iodate fluoro-alkyl ammonium, the fluoro-alkyl betaine, the fluoro-alkyl polyoxyethylene ether, the perfluoroalkyl poly oxyethanol, the perfluoroalkyl alkoxide, fluoroalkyl ester etc.

In addition, as these commercially available products, can enumerate for example BM-1000, BM-1100 (more than, BM CHEMIE society system), メ ガ Off ア Star Network F 142D, same F172, with 173, same F183, same F178, same F191, same F471, same F476 (above big Japanese ink chemical industry (strain) system), Off ロ ラ-De FC, 170C, FC-171, FC-430, FC-431 (above Sumitomo ス リ-エ system (strain) system), サ-Off ロ Application S-112, same S-113, same S-131, same S-141, same S-145, same S-382, same SC-101, same SC-102, same SC-103, same SC-104, same SC-105, same SC-106 (more than, Asahi Glass (strain) system), エ Off ト Star プ EF301, with 303, with 352 (more than, new autumn fields changes into (strain) system), Off -ジ エ Application ト FT-100, same FT-110, same FT-140A, same FT-150, same FT-250, same FT-251, same FTX-251, same FTX-218, same FT-300, same FT-310, same FT-400S (more than, (strain) ネ オ ス system) etc.

In addition, as the silicone surfactant, for example can enumerate with ト-レ シ リ コ-Application DC3PA, same DC7PA, same SH11PA, same SH21PA, same SH28PA, same SH29PA, same SH30PA, same SH-190, same SH-193, same SZ-6032, same SF-8428, same DC-57, same DC-190 (more than, east レ ダ ウ コ-ニ Application グ シ リ コ-Application (strain) system), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, trade name product solds such as TSF-4452 (more than, the シ リ of GE Toshiba コ-Application (strain) system).

In addition, as the surfactant beyond above-mentioned, can enumerate for example polyoxyethylene alkyl ether classes such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyl 10 oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-nonyl phenyl ether; Nonionic class surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate, polyoxyethylene distearate, or, can enumerate KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), Port リ Off ロ-No.57,95 (common prosperity society oil chemistry industry (strain) system) etc. as commercially available product.

These surfactants can separately or mix 2 kinds or above use.

The combined amount of surfactant with respect to 100 weight portion multipolymers [A], is preferably 5 weight portions or following, more preferably 2 weight portions or following.At this moment, if the combined amount of surfactant surpasses 5 weight portions, exist during coating the coarse tendency of film takes place easily.

In addition, for the cohesive of further raising with matrix, can the hybrid bonding auxiliary agent.

As above-mentioned bonding agent; be preferably the functional silanes coupling agent; as the example; can enumerate and have carboxyl; methacryl; isocyanate group; epoxy radicals isoreactivity functional group's silane coupling agent; more specifically; can enumerate the trimethoxysilyl benzoic acid; γ-methacryloxypropyl trimethoxy monosilane; vinyl triacetyl oxygen base monosilane; the vinyl trimethoxy monosilane; γ-isocyanate group propyl triethoxy monosilane; γ-glycidoxypropyl trimethoxy monosilane; 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy monosilane etc.

These bonding agents can separately or mix 2 kinds or above use.

The combined amount of bonding agent with respect to 100 weight portion multipolymers [A], is preferably 20 weight portions or following, more preferably 10 weight portions or following.At this moment, if the combined amount of bonding agent surpasses 20 weight portions, there is the tendency that the development image retention takes place easily.

Can add other adjuvant.As purposes such as the raisings of storage stability and add.Particularly, can enumerate sulphur, quinones, hydroquinones, polyoxy compounds, amine, nitroso compound.As the example, can enumerate 4-metoxyphenol, N-nitroso--N-phenyl hydramine aluminium etc.Preferably with 3.0 weight portions or following, more preferably 0.001～0.5 weight portion uses with respect to 100 weight portion multipolymers [A] for they.If surpass under the situation of 3.0 weight portions, can not obtain enough susceptibilitys, pattern form is variation also.

In addition,, can add N-(alkoxy methyl) ethylene glycol carbamide compound in order to improve thermotolerance, have in N-(alkoxy methyl) melamine compound and 1 molecule 2 officials can and the compound of above epoxy radicals.As the instantiation of above-mentioned N-(alkoxy methyl) ethylene glycol carbamide compound, can enumerate N, N, N, N-four (methoxy) ethylene glycol urea, N, N, N, N-four (ethoxyl methyl) ethylene glycol urea, N, N, N, N-four (just-propoxyl group methyl) ethylene glycol urea, N, N, N, N-four (different-the propoxyl group methyl) ethylene glycol urea, N, N, N, N-four (just-butoxymethyl) ethylene glycol urea, N, N, N, N-four (uncle-butoxymethyl) ethylene glycol urea etc.Wherein, especially, preferred N, N, N, N-four (methoxy) ethylene glycol urea.As the instantiation of above-mentioned N-(alkoxy methyl) melamine compound, can enumerate N, N, N, N, N, N-six (methoxy) melamine, N, N, N, N, N, N-six (ethoxyl methyl) melamine, N, N, N, N, N, N-six (n-propoxymethyl) melamine, N, N, N, N, N, N-six (isopropoxy methyl) melamine, N, N, N, N, N, N-six (n-butoxy methyl) melamine, N, N, N, N, N, N-six (tert-butoxy methyl) melamine etc.Wherein especially, preferred N, N, N, N, N, N-six (methoxy) melamine.As this class commercially available product, can enumerate ニ カ ラ Star Network N-2702, MW-30M (more than, be three and ケ ミ カ Le (strain) system) etc.

As have in 1 molecule 2 officials can or the compound of above epoxy radicals, can enumerate ethylene glycol diglycidylether, diethylene glycol diglycidyl ether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol glycidol ether, polypropylene glycol glycidol ether, neopentyl glycol glycidol ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, hydrogenation bisphenol A diglycidyl ether, bisphenol A diglycidyl ether etc.Instantiation as these commercially available products, can enumerate エ Port ラ イ ト 40E, エ Port ラ イ ト 100E, エ Port ラ イ ト 200E, エ Port ラ イ ト 70P, エ Port ラ イ ト 200P, エ Port ラ イ ト 400P, エ Port ラ イ ト 40E, エ Port ラ イ ト 1500NP, エ Port ラ イ ト 1600, エ Port ラ イ ト 80MF, エ Port ラ イ ト 100MF, エ Port ラ イ ト 4000, エ Port ラ イ ト 3,002 (more than, common prosperity society chemistry (strain) system) etc.They can be separately or 2 kinds or above being used in combination.

Composition solution

Photosensitive polymer combination (1), in use, usually can be with multipolymer [A], polymerizable compound [B], Photoepolymerizationinitiater initiater constituents such as [C] are dissolved in the appropriate solvent, are mixed with composition solution.

As the solvent that uses in the preparation of above-mentioned composition solution, can use and to dissolve each composition that constitutes photosensitive polymer combination (1) equably, and not with the solvent of each composition reaction, as its instantiation, can enumerate with for the identical solvent of the illustrated solvent of polymerization of making multipolymer [A].

In these solvents, dissolving energy from each composition, set out with the viewpoint of the easiness of the formation of filming with the reactivity of each composition, preferably make spent glycol azanyl ethers, ethylene glycol azanyl ether acetic acid ester class, diethylene glycol alkyl ether and propylene-glycol monoalky lether acetate esters, alkoxypropan acid alkyl ester class etc.

Above-mentioned solvent can separately or mix 2 kinds or above use.

In addition, when compositions formulated solution, can unite the use high boiling solvent with above-mentioned solvent.

As above-mentioned high boiling solvent, can enumerate for example N-NMF, N, dinethylformamide, N-methyl formyl aniline, N-methylacetamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide, benzylisoeugenol, hexyl ether, ethinyl acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, carbonic allyl ester, glycol monomethyl phenyl ether acetic acid esters etc.

These high boiling solvents can separately or mix 2 kinds or above use.

Composition prepared solution so as required, can filter the back for use with the millipore filter about 0.2～0.5 μ m etc.

Photosensitive polymer combination (1), especially, suitable conduct will form the material that liquid crystal board or touch pad etc. similarly are the spacer of plate use.

Display panel used spacer

When usability photosensitive resin composition (1) forms display panel used spacer, after composition solution is applied to substrate surface, removes by prebake conditions and to desolvate, formation is filmed.

As the coating process of composition solution, can adopt for example suitable method such as spray-on process, cylinder rubbing method, method of spin coating.

In addition, the condition of prebake conditions, according to the kind of each composition, blending ratio etc. and different, usually, about 70～90 ℃, 1～15 minute.

Then, on the filming of prebake conditions, insert the mask and the polymerization that exposes of predetermined pattern after, by developing liquid developing, remove part not and form pattern.

As the radioactive ray that exposure is used, suitable visible light, ultraviolet ray, far ultraviolet, electron beam, X ray etc., the radioactive ray of optimal wavelength in 190～450nm scope selected.

As developing method, for example can enumerating liquid, to contain method, infusion process, middle pouring method etc. any, and development time is generally 30～180 seconds.

As above-mentioned developer solution, can use for example inorganic bases such as NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium methyl silicate, ammonium; Armeen such as ethamine, n-propylamine class; Secondary aliphatic amine such as diethylamine, di-n-propylamine; Tertiary amines such as trimethylamine, methyl diethylamide, ethyl dimethyl amine, triethylamine; Tertiary alkanol amines such as dimethylethanolamine, methyldiethanolamine, triethanolamine; Pyrroles, piperidines, N-methyl piperidine, N-crassitude, 1,8-diazabicyclo [5.4.0]-7-undecylene, 1,5-diazabicyclo [4.3.0]-alicyclic tertiary amines such as 5-nonene; Aromatic tertiary amines such as pyridine, trimethylpyridine, lutidines, quinoline; The aqueous solution of alkali compounds such as quaternary ammonium salt such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide.

In addition, in the aqueous solution of above-mentioned alkali compounds, can add water-miscible organic solvent and/or surfactants such as methyl alcohol, ethanol in right amount.

After the development,, for example washed 30～90 seconds by for example washing etc., remove part not after, form the pattern of regulation by blowing compressed air or compressed nitrogen.

Then, this pattern by heating arrangements such as electric hot plates, electric furnace, in set point of temperature, 150～250 ℃ of heating stipulated times for example, for example on electric hot plate 5～30 minutes, in electric furnace for example 30～90 minutes, by heat treated, is obtained the purpose spacer.

Here, if the composition of the preferred photosensitive polymer combination of particular instantiation (1) then is following (i)～(vii) described.

(i) composition of formation multipolymer [A] is: unsaturated carboxylic acid class monomer (a1) is by being selected from acrylic acid, methacrylic acid and maleic anhydride independent or 2 kinds or above potpourri formation, the monomer (a2) that contains epoxy radicals is by being selected from glycidyl methacrylate, methacrylic acid 6,7-epoxy heptyl ester, neighbour-vinyl benzyl glycidol ether, between-vinyl benzyl glycidol ether and right-vinyl benzyl glycidol ether separately or 2 kinds or above potpourri constitute, other monomer (a3) is by acrylic acid 2-methyl cyclohexane ester, the metering system tert-butyl acrylate, methacrylic acid three ring [5.2.1.0 ^2,6] decane-8-base, styrene, p-methoxystyrene, tetrahydrofurfuryl methacrylate and 1,3-butadiene separately or the composition that constitutes of 2 kinds or above potpourri.

(ii) in multipolymer [A], the containing ratio of unsaturated carboxylic acid class monomer (a1) repeat units derived is 5～40 weight %, 10～30 weight % more preferably, containing ratio by the monomer that contains epoxy radicals (a2) repeat units derived is 10～70 weight %, 20～60 weight % more preferably, the containing ratio of other monomer (a3) repeat units derived is 10～70 weight %, more preferably the composition of 20～50 weight % above-mentioned (i).

(iii) polymerizable compound [B] be simple function, 2 officials can or 3 officials can or above (methyl) esters of acrylic acid, preferred especially 3 officials can or above-mentioned (i) or the composition (ii) of above (methyl) esters of acrylic acid.

(iv) Photoepolymerizationinitiater initiater [C] is any one composition among above-mentioned (i)～(iii) of O-acyl group oxime type Photoepolymerizationinitiater initiater.

(the vii) use amount of polymerizable compound [B], with respect to 100 weight portion multipolymers [A], be 50～140 weight portions, 60～120 weight portions more preferably, the use amount of Photoepolymerizationinitiater initiater [C], with respect to 100 weight portion polymerizable compounds [B], be 5～30 weight portions, above-mentioned (i) of 5～20 weight portions～(any composition vi) more preferably.

With photosensitive polymer combination of the present invention (1) is that the design size that can be formed in faithful reappearance mask pattern under the ISO can be provided, and with the cohesive excellence of substrate, at 150mJ/cm ²Or also can obtain sufficient spacer shape and thickness under the following exposure, the also photosensitive polymer combination of excellent display panel used spacer such as intensity, thermotolerance in addition.

Below, show embodiment and comparative example, be described more specifically the present invention, but the present invention is not limited to these embodiment.

Synthesis example 1

In the flask that possesses cooling tube, stirrer, add 5 weight portions 2,2 '-azo two (2, the 4-methyl pentane nitrile), 200 weight portion diethylene glycol methyl ethyl ethers, the 18 weight portion methacrylic acids of packing into continuously again, 40 weight portion glycidyl methacrylate, 5 parts by weight of styrene, 32 weight portion methacrylic acids, three ring [5.2.1.0 ^2,6] after the displacement of decane-8-base, nitrogen, the limit is slowly stirred the limit and added 5 weight portion 1,3-butadienes, makes solution temperature rise to 70 ℃, remains on this temperature and makes its polymerization in 5 hours, obtains the solution of multipolymer [A-1].

The solid component concentration of this solution is 33.0 weight %, and the Mw of multipolymer [A-1] is 11,000.

Synthesis example 2

In the flask that possesses cooling tube, stirrer, add 7 weight portions 2,2 '-azo two (2, the 4-methyl pentane nitrile), 200 weight portion diethylene glycol methyl ethyl ethers, the 18 weight portion methacrylic acids of packing into continuously again, 20 weight portion glycidyl methacrylate, 5 parts by weight of styrene, 32 weight portion methacrylic acids, three ring [5.2.1.0 ^2,6] decane-8-base, 25 weight portion tetrahydrofurfuryl methacrylates, after the nitrogen displacement, slowly stir on the limit, and the limit makes solution temperature rise to 70 ℃, remains on this temperature 5 hours and makes its polymerization, obtains the solution of multipolymer [A-2].

The solid component concentration of this solution is 33.4 weight %, and the Mw of multipolymer [A-2] is 9,000.

Embodiment 1

The preparation of composition solution

With 100 weight portions (solid constituent) as synthesis example 1 gained multipolymer [A-1] solution of multipolymer [A], 80 weight portions as the KAYARADDPHA (Japanese chemical drug (strain) system) of polymerizable compound [B], 8 weight portions 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl as Photoepolymerizationinitiater initiater [C]]-after two suberyl-1-ketoxime-O-acetic acid esters is dissolved in and makes solid component concentration be 35 weight % in the propylene glycol monomethyl ether; millipore filter with aperture 0.2 μ m filters compositions formulated solution (S-1).

(I) formation of spacer

After being coated on above-mentioned composition on the alkali-free glass substrate with spinner, baking formed filming of thickness 6.0 μ m in 3 minutes on 90 ℃ of electric hot plates.

Insert the mask of the remaining pattern in 10 μ m angles on as above gained is filmed, exposure slit is 150 μ m, passes through exposure intensity 300W/m at wavelength 365nm ²Ultraviolet ray expose.Then, at 25 ℃, develop after 60 seconds, with purified rinse water 1 minute with the sodium hydrate aqueous solution of 0.05 weight %.And, in electric furnace, formed spacer in 120 minutes 150 ℃ of heating.

(II) evaluation of sharpness

In above-mentioned (I) gained pattern, the residual film ratio after the development (thickness after the development/initial stage thickness * 100) be used in 90% or above light sensitivity under the minimum pattern size estimate.Pattern dimension is little promptly to be that sharpness is good.

(III) light sensitivity evaluation

In above-mentioned (I) gained pattern, if develop the back residual film ratio 90% or above light sensitivity be 150mJ/cm ²Or below, illustrate that light sensitivity is good.

(IV) evaluation of pattern cross sectional shape

With the result that the cross sectional shape of above-mentioned (I) gained pattern is observed with scanning electron microscope, its shape is equivalent to a kind of shape among as shown in Figure 1 A～C.Resemble that pattern edge illustrates that for the situation along taper pattern form is good the A.Resemble that pattern edge is vertical situation about forming the B, illustrate the pattern shape bases this well.

In addition, shown in C among Fig. 1, be near the shape of back taper (in the cross sectional shape film near surface than long substrate one side, upside-down triangle shape), because the possibility that pattern is peeled off when the friction process of back is very high, therefore such shape is bad.

(V) evaluation of compression strenght

The spacer compression strenght of above-mentioned (I) gained is estimated with miniature compression test (MCTM-200, (strain) Shimadzu Seisakusho Ltd. system).By the plane hammer of diameter 50 μ m, the deflection when measuring the loading that applies 10mN (mensuration temperature: 23 ℃).This value is 0.5 or when following, and compression strenght is good.The results are shown in table 2.

(VI) wearing quality evaluation

To be coated on above-mentioned (I) gained substrate as the AL3046 (ジ エ イ エ ス ア-Le (strain) system) of aligning agent for liquid crystal with printing machine with liquid crystal orientation film coating, 180 ℃ of dryings 1 hour, the formation dry film thickness was that the alignment agent of 0.05 μ m is filmed.

On this is filmed, by having volume the rubbing machine of cylinder of nylon cloth is arranged, carry out friction treatment second with number of revolutions of drum 500rpm, ladder translational speed 1cm/.This moment cutting or having or not of peeling off of spacer pattern are shown in table 2.

(VII) fusible evaluation

Except that not using the patterned mask, similarly implement with above-mentioned (I), form cohesive evaluation cured film, carry out adhesion test.In the adhesion test of test method(s) according to JIS K-5400 (1900) 8.5,8.52 reticulate pattern strips method.At this moment, Can Yu reticulate pattern number is shown in table 2.

(VIII) evaluation of storage stability

After the compositions formulated-15 ℃ of preservations, with the evaluation of above-mentioned (III) light sensitivity follow the trail of in the same manner after the development residual film ratio 90% or above necessary exposure through the time change, measure and preserve the relative value that the light sensitivity after back 3 months is compared with the light sensitivity after the firm preparation.

Embodiment 2～18, comparative example 1～10

In embodiment 1, to remove as [A] composition～[E] composition, outside kind, the amount of being put down in writing with table 1 used, similarly to Example 1, compositions formulated solution formed spacer, estimates.The addition of [B]～[E] is the weight ratio with respect to 100 weight portion polymerizable compounds [A].

In the table 1, following compounds represented in the abbreviation of composition.

(B-1): KAYARAD DPHA (Japanese chemical drug (strain) system)

(B-2): KAYARAD DPHA-40H (Japanese chemical drug (strain) system)

(C-1): 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-two suberyl-1-ketoxime-O-acetic acid esters

(C-2): 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-tetrahydrofuran methylmethane-1-ketoxime-O-acetic acid esters

(C-3): 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-bicycloheptane carboxylate

(C-4): 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-tristane carboxylate

(C-5): 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-adamantyl carboxylate

(C-6): 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-tetrahydrofuran methylmethane-1-ketoxime-O-bicycloheptane carboxylate

(C-R): 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-acetic acid esters (the チ バ ス ペ シ ヤ Le テ イ-system CGI-242 of ケ ミ カ Le ズ society)

(D-1): 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone (the チ バ ス ペ シ ヤ Le テ イ-system イ of ケ ミ カ Le ズ society Le ガ キ ユ ア 907)

(D-2): 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butanone-1 (the チ バ ス ペ シ ヤ Le テ イ-system イ of ケ ミ カ Le ズ society Le ガ キ ユ ア 369)

(E-1): 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline

(E-2): 4,4 '-two (diethylamino) benzophenone

(E-3): 2-mercaptobenzothiazole

In the table 1, this composition of mark "-" the expression interpolation.

Evaluation result is as shown in table 2.

Table 1

	The composition kind	Copolymer A		The B composition		The C composition		The D composition		The E composition
												Kind	Weight portion	Kind	Weight portion	Kind	Weight portion	Kind	Weight portion	Kind	Weight portion
		Embodiment 1	(S-1)	A-1	100	B-1	100	C-1	8	-	-											-	-
Embodiment 2	(S-2)											A-1	100	B-1	100	C-2	5	D-1	20	-	-
		Embodiment 3	(S-3)	A-1	100	B-1	100	C-3	10	D-2	15											-	-
Embodiment 4	(S-4)											A-1	100	B-1	100	C-4	5	D-1+D-2	10+10	-	-
		Embodiment 5	(S-5)	A-1	100	B-1	80	C-5	5	-	-											E-1+E-2+E-3	5+5+2.5
Embodiment 6	(S-6)											A-1	100	B-1	80	C-6	3	D-1	25	E-1+E-2+E-3	5+5+2.5
		Embodiment 7	(S-7)	A-1	100	B-1	80	C-1	5	D-2	20											E-1+E-2+E-3	5+5+2.5
Embodiment 8	(S-8)											A-1	100	B-1	100	C-1	5	D-1+D-2	10+10	E-1+E-2+E-3	5+5+2.5
		Embodiment 9	(S-9)	A-1	100	B-1	100	C-1+C-2	4+1	D-2	20											E-1+E-2+E-3	6+6+3
Embodiment 10	(S-10)											A-1	100	B-1+B-2	90+10	C-1	7	-	-	E-1+E-2+E-3	6+6+3
		Embodiment 11	(S-11)	A-1	100	B-1+B-2	90+10	C-2	5	D-1	10											E-1+E-2+E-3	5+5+2.5
Embodiment 12	(S-12)											A-1	100	B-1+B-2	90+10	C-1	5	D-2	15	E-1+E-2+E-3	5+5+2.5
		Embodiment 13	(S-13)	A-1	100	B-1+B-2	80+20	C-3	8	D-1+D-2	10+15											E-1+E-2+E-3	5+5+2.5
Embodiment 14	(S-14)											A-2	100	B-1+B-2	80+20	C-4	5	-	-	E-1+E-2+E-3	5+5+2.5
		Embodiment 15	(S-15)	A-2	100	B-1+B-2	60+40	C-5	5	D-1	25											E-1+E-2+E-3	6+6+3
Embodiment 16	(S-16)											A-2	100	B-1+B-2	80+20	C-6	5	D-2	30	E-1+E-2+E-3	6+6+3
		Embodiment 17	(S-17)	A-2	100	B-1+B-2	90+10	C-1	3	D-1+D-2	10+10											E-1+E-2+E-3	6+6+3
Embodiment 18	(S-18)											A-2	100	B-1+B-2	90+10	C-1+C-2	3+2	D-1+D-2	10+5	E-1+E-2+E-3	6+6+3
		Comparative example 1	(s-1)	A-1	100	B-1	100	-	-	D-1	20											-	-
Comparative example 2	(s-2)											A-1	100	B-1	100	-	-	D-2	20	-	-
		Comparative example 3	(s-3)	A-1	100	B-1	100	-	-	D-1+D-2	10+10											-	-
Comparative example 4	(s-4)											A-1	100	B-1	100	-	-	-	-	E-1+E-2+E-3	6+6+3
		Comparative example 5	(s-5)	A-1	100	B-1	80	-	-	D-1	15											E-1+E-2+E-3	6+6+3
Comparative example 6	(s-6)											A-1	100	B-1	80	-	-	D-2	15	E-1+E-2+E-3	6+6+3
		Comparative example 7	(s-7)	A-1	100	B-1	80	-	-	D-1+D-2	15+15											E-1+E-2+E-3	5+5+2.5
Comparative example 8	(s-8)											A-1	100	B-1	80	C-R	5	D-1+D-2	10+10	E-1+E-2+E-3	5+5+2.5
		Comparative example 9	(s-10)	A-2	100	B-1+B-2	90+10	C-R	5	D-1+D-2	10+10											E-1+E-2+E-3	5+5+2.5

Table 2

	The composition kind	Light sensitivity (mJ/cm 2)	Sharpness (μ m)	Section shape	Compression test (μ m)	Abrasion test has or not peels off	Cohesive (/ 100)	Storage stability
									Embodiment 1	(S-1)	150	10	B	0.51	Do not have	100	1.01
Embodiment 2	(S-2)	130	8	B	0.52	Do not have	100	1.02
									Embodiment 3	(S-3)	130	10	A	0.32	Do not have	100	1.02
Embodiment 4	(S-4)	120	8	A	0.32	Do not have	100	1.02
									Embodiment 5	(S-5)	100	10	B	0.48	Do not have	100	1.02
Embodiment 6	(S-6)	80	8	B	0.52	Do not have	100	1.02
									Embodiment 7	(S-7)	80	10	A	0.25	Do not have	100	1.02
Embodiment 8	(S-8)	80	8	A	0.27	Do not have	100	1.02
									Embodiment 9	(S-9)	70	8	A	0.28	Do not have	100	1.02
Embodiment 10	(S-10)	80	12	A	0.28	Do not have	100	1.02
									Embodiment 11	(S-11)	70	10	A	0.27	Do not have	100	1.03
Embodiment 12	(S-12)	70	12	A	0.25	Do not have	100	1.02
									Embodiment 13	(S-13)	60	10	A	0.26	Do not have	100	1.01
Embodiment 14	(S-14)	90	8	A	0.28	Do not have	100	1.02
									Embodiment 15	(S-15)	80	8	A	0.27	Do not have	100	1.02
Embodiment 16	(S-16)	80	8	A	0.25	Do not have	100	1.01
									Embodiment 17	(S-17)	70	8	A	0.26	Do not have	100	1.02
Embodiment 18	(S-18)	60	8	A	0.26	Do not have	100	1.02
									Comparative example 1	(s-1)	300	8	C	0.57	Have	80	1.1
Comparative example 2	(s-2)	270	10	A	0.36	Do not have	100	1.1
									Comparative example 3	(s-3)	250	8	A	0.32	Do not have	100	1.1
Comparative example 4	(s-4)	220	10	B	0.48	Do not have	100	1.1
									Comparative example 5	(s-5)	200	8	B	0.56	Do not have	100	1.1
Comparative example 6	(s-6)	180	10	A	0.27	Do not have	100	1.1
									Comparative example 7	(s-7)	160	8	A	0.29	Do not have	100	1.1
Comparative example 8	(s-8)	170	8	A	0.29	Do not have	100	1.2
									Comparative example 9	(s-10)	170	8	A	0.27	Do not have	100	1.2

Claims (3)

1. photosensitive polymer combination, it is characterized in that said composition contains [A] (a1) ethene unsaturated carboxylic acid and/or ethene unsaturated carboxylic acid anhydrides and (a2) contain the ethene unsaturated compound of epoxy radicals and (a3) multipolymer of other ethene unsaturated compound

[B] has the polymerizable compound of ethene unsaturated link, and

The Photoepolymerizationinitiater initiater that [C] is made of the represented compound of following formula (1)

In the formula (1), R ₁, R ₂Be respectively and be selected from hydrogen atom, the alkyl of carbon atom 1 several 1～20, the naphthenic base of carbon number 3～8, phenyl (but can be by the alkyl of carbon number 1～6, the alkoxy of carbon number 1～6, at least one of phenyl and halogen atom or above replacement), the alicyclic group of carbon number 7～20 (ア リ サ イ Network リ Star Network) (except the above-mentioned naphthenic base), the oxygen-containing heterocycle of carbon number 4～20, the nitrogen heterocycle of carbon number 4～20, the oxygen-containing heterocycle of carbon number 4～20, the functional group of the sulfur heterocyclic ring base of carbon number 4～20; But R ₁, R ₂In any one be the oxygen-containing heterocycle of the alkyl of carbon number 13～20, the alicyclic group of carbon number 7～20 (except the above-mentioned naphthenic base), carbon number 4～20, the nitrogen heterocycle of carbon number 4～20, the oxygen-containing heterocycle of carbon number 4～20, the sulfur heterocyclic ring base of carbon number 4～20; R ₃The alkyl of the straight chain shape of expression hydrogen atom or carbon number 1～12, a chain or ring-type, R ₄, R ₅And R ₆The alkyl of the straight chain shape of expression hydrogen atom or carbon number 1～6, a chain or ring-type.

2. the display panel used spacer that photosensitive polymer combination as claimed in claim 1 forms.

3. the display board that possesses display panel used spacer as claimed in claim 2.