CN1841196A - X-ray sensitive resin composition, protruded body and barrier body formed thereby, forming method thereof and liquid crystal display element - Google Patents

X-ray sensitive resin composition, protruded body and barrier body formed thereby, forming method thereof and liquid crystal display element Download PDF

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CN1841196A
CN1841196A CNA200610067016XA CN200610067016A CN1841196A CN 1841196 A CN1841196 A CN 1841196A CN A200610067016X A CNA200610067016X A CN A200610067016XA CN 200610067016 A CN200610067016 A CN 200610067016A CN 1841196 A CN1841196 A CN 1841196A
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methyl
separator
liquid crystal
ethyl
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一户大吾
浜口仁
梶田彻
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JSR Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators

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  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)
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Abstract

The object of this invention is to provide a radiation-sensitive resin composition which is suitably used for simultaneously forming protrusions and spacers of a vertical alignment liquid crystal display element. The radiation-sensitive resin composition for simultaneously forming the protrusions and the spacers for the vertical alignment liquid crystal display element is characterized to contain: a copolymer [A], obtained by copolymerizing an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride (a1), and an unsaturated compound (a2) other than the component (a1), a polymerizable unsaturated compound [B], and a radiation-sensitive polymerization initiator [C] having a specified structure, represented by ethanone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxy benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-acetyloxime).

Description

Radiation sensitive resin composition, the projection that forms by said composition and separator and forming method thereof, and liquid crystal display cells
Technical field
Projection and the separator that the present invention relates to the radiation sensitive resin composition of a kind of projection that is used for forming simultaneously the vertical-type liquid crystal display cells and separator (spacer), forms by said composition, the liquid crystal display cells that comprises this projection and separator.
Background technology
Display panels is widely used in flat-panel monitor at present.Particularly, along with for example popularization of OA such as personal computer and word processor equipment and LCD TV etc., the requirement of the display quality of the display panels (TFT-LCD) of TFT (thin film transistor (TFT)) mode is become more and more stricter.
Among TFT-LCD, TN (Twisted Nematic) type LCD is to use maximum now.This LCD makes by following method: differ 90 an inclined to one side film of spending in the outside of 2 transparency electrodes configuration direction of orientation, and in the inboard configuration of two transparency electrodes alignment films; Between two alignment films, dispose nematic crystal, the direction of orientation of liquid crystal is reversed to another electrode side from an electrode side with the angle of 90 degree.When nonpolarized light under this state during incident, the rectilinearly polarized light that has passed a polarizing plate passes liquid crystal, its change of polarized direction, so it can pass another polarizing plate, forms bright state.Then, when making liquid crystal molecule upright when applying voltage to two electrode persons, the rectilinearly polarized light that arrives liquid crystal passes like this, can not pass another polarizing plate, forms dark state.After this, when stopping to apply voltage once more, just revert to bright state.
Though, because in recent years technical progress, at aspects such as the contrast in front and color reprodubilities, this TN type LCD become with CRT quite or more superior.But TN type LCD still has a big problem to need to solve, and that is exactly that the visual angle is narrow.
As the method that addresses this is that, developed STN (Super TwistedNematic) type LCD and MVA (Multi-domain Vertically Aligned) type LCD (vertical alignment-type liquid crystal display panel).Wherein, STN type LCD is the chiral reagent of sneaking in the nematic crystal of TN type LCD as optical active substance, with the axis of orientation of liquid crystal molecule turn round between 2 cube electrodes turnback or more than.In addition, MVA type LCD will have the negative type liquid crystal of negative dielectric constant anisotropy and the alignment films combination of vertical direction, not use the optically-active pattern of TN type LCD, and be to use the LCD of birefringent mode; Even under the state that does not apply voltage, also can roughly keep vertical direction in locational liquid crystal aligning direction near alignment films, therefore, excellence such as contrast, visual angle, and can not make milled processed of liquid crystal aligning etc., also excellent (with reference to non-patent literature 1 and patent documentation 1) aspect manufacturing process.
In MVA type LCD, can get a plurality of directions of orientation in order to make liquid crystal at a pixel region, as the region limits method can be to make the electrode that shows side for have the electrode of slit in 1 pixel region, and in the same pixel region on the electrode of light incident side, staggered in the slit and the position of electrode, formation has the projection (for example, triangular pyramidal, semi-convex lens shaped etc.) on inclined-plane.
This projection can form by photoetching process usually, and photoetching process has can microfabrication, control the advantage of shape easily.
On the other hand, the separator of regulation must be set in liquid crystal panel, thereby 2 substrates are kept certain intervals.At present, use separator particles such as beaded glass with regulation particle diameter, plastic bead as this separator.But, these separator particles stochastic distribution on glass substrate, so when having above-mentioned separator in valid pixel portion, can be subjected to the reflection of separator, incident light is scattered, and has the problem that the contrast of liquid crystal panel reduces.In order to address these problems, the use radiation sensitive resin composition has been proposed, beyond valid pixel portion, form the method for separator by photoetching process.
When use utilizes the photoetching process of radiation-sensitive resin to form projection and forms separator, can make to use the same method, but the following performance that requires separately is different.
(1) projection is different with the desired thickness of separator.
(2) desired shape difference is respectively that projection is semi-convex lensing, and separator is a column or suitable coniform.
In addition, owing to must on projection, form alignment films, so when in subsequent handling, forming alignment films,, require aligning film material that enough coatings are arranged in order not produce repulsion.
On the other hand, can be in order to make liquid crystal panel owing to external pressure is not out of shape, separator also must have very high compression strenght.
In addition, projection, separator also must have enough holding capacity to the heat that applies in the panel assembling procedure afterwards.
When forming alignment films on projection, if the coning angle of the relative substrate of projection is excessive, for example be 30 degree or when above, then on the top of projection, the printing that can produce alignment films is bad, after panel formed, the possibility that poor display takes place uprised.Therefore, the coning angle of the relative substrate of projection be preferably 30 the degree or below.
As mentioned above,, must use different radiation-sensitive materials up to now, use different operations to form because projection requires different shapes, different chemical property with separator.In addition, the use negative photosensitive material is also disclosed in patent documentation 2, form the imagination of projection and separator simultaneously, but in this communique and the concrete scheme of the unexposed radiation-ray sensitive composition that can in this purposes, use, also do not know to be used for forming simultaneously the radiation-ray sensitive composition of projection and separator, so need provide this material strongly.
[non-patent literature 1] military Tian Youguang, liquid crystal, Japanese liquid crystal association, on April 25th, 1999, Vol.3, No.2,117
[patent documentation 1] spy opens flat 11-258605 communique
[patent documentation 2] spy opens the 2001-83517 communique
In addition, in recent years, from the large tracts of landization of liquid crystal display cells with improve viewpoint such as productivity, the maximization of glass mother board (for example, 1,500 * 1, about 800mm) fast development.Yet, (about 680 * 880mm) is littler than means of mask dimensions for the size of present substrate, thus can adapt with the overall exposing mode, but when being large substrate, almost can't make the mask with the measure-alike degree of this substrate, be difficult to adapt to the overall exposing mode.
Therefore, as the Exposure mode that adapts to large substrate, advocate the substep Exposure mode.But the substep Exposure mode is that a substrate is exposed several times, when each exposure, makes aligned in position and branch moved further need spended time, compares with the overall exposing mode, can think to reduce the problem of productive capacity.
In addition, in the overall exposing mode, can be 3,000J/m 2About exposure, but when exposing, must make the exposure of each time lower at substep, the existing radiation sensitive resin composition that uses in the formation of separator is difficult to 1 200J/m up to now 2Or enough separator shape and the thickness of formation under the following exposure.
Summary of the invention
The present invention proposes according to above problem, and its purpose is to provide a kind of radiation sensitive resin composition, by projection and the separator that said composition forms, has the liquid crystal display cells of this projection and separator; Wherein this radiation sensitive resin composition is a high sensitivity, even 1, and 200J/m 2Or also can obtain enough shapes under the following exposure, be suitable for forming simultaneously the projection and the separator of vertical alignment-type liquid crystal display device.
According to the present invention, above-mentioned problem first is to be used for forming simultaneously the projection of vertical alignment-type liquid crystal display device and the radiation sensitive resin composition of separator realizes that this radiation sensitive resin composition is characterised in that by a kind of: comprise,
The multipolymer that [A] obtains following (a1)～(a2) copolymerization, wherein (a1) is unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, (a2) is other unsaturated compound beyond (a1) composition;
[B] polymerizable unsaturated compound; With
The radiation-sensitive polymerization initiator that [C] formed by the compound shown in following formula (1) or (2),
Figure A20061006701600081
Here, R 1Be that to be selected from carbon number be that 1～20 alkyl, carbon number are 3～8 naphthenic base or phenyl groups, R 2, R 3Be respectively that to be selected from hydrogen atom, carbon number be that 1～20 alkyl, carbon number are that 3～8 naphthenic base, replacement or unsubstituted phenyl or carbon number are the group of 7～20 alicyclic group (except carbon number is 7～8 naphthenic base), the substituting group of above-mentioned substituted-phenyl is that carbon number is that 1～6 alkyl, carbon number are 1～6 alkoxy, phenyl and halogen atom, R 4Be that to be selected from carbon number be that 4～20 oxygen-containing heterocycle, carbon number are that 4～20 nitrogen heterocycle or carbon number are the group of 4～20 sulfur heterocyclic ring base, R 5Be that to be selected from hydrogen, carbon number be that 1～12 alkyl or carbon number are the group of 1～12 alkoxy, n is 1～5 integer, and m is 0～5 integer, n+m≤5,
Figure A20061006701600091
Here, R 1, R 2, R 3, R 4, R 5, m and n definition same as described above, 1 is the integer of 0-6, R 1, R 2, R 3, R 4, R 5, m, n and 1 be separate.
Above-mentioned problem of the present invention, second is to realize by a kind of formation method that forms projection and separator simultaneously, the method is characterized in that: the following operation that contains following order record at least:
(1) operation of the above-mentioned radiation sensitive resin composition film of formation on substrate,
(2) with the operation of at least one exposure of this film,
(3) operation of developing of this film after will exposing and
(4) operation of this film heating after will developing.
Above-mentioned problem of the present invention thirdly is to realize by projection and separator that the radiation sensitive resin composition by above-mentioned record forms.
Above-mentioned problem of the present invention, the 4th is that the projection by having above-mentioned record and the liquid crystal display cells of separator are realized.
Description of drawings
Fig. 1 is the synoptic diagram of the section shape of illustration separator.
Embodiment
Below, the present invention is described in detail.
Radiation sensitive resin composition
[A] multipolymer:
[A] multipolymer that uses in the radiation sensitive resin composition of the present invention is with (a1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, and (a2) other unsaturated compound copolymer beyond (a1) composition obtains.
In each composition that constitutes [A] multipolymer, as (a1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides (they being generically and collectively referred to as " (a1) unsaturated carboxylic acid compounds "), can list for example monocarboxylic acid classes such as acrylic acid, methacrylic acid, crotonic acid, 2-acryloxy ethyl succinic acid, 2-methacryloxyethyl succinic acid, 2-acryloxy ethyl hexahydrophthalic acid, 2-methacryloxyethyl hexahydrophthalic acid; Dicarboxylic acids classes such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid; The anhydrides of above-mentioned dicarboxylic acids etc.
In these (a1) unsaturated carboxylic acid compounds, from [A] multipolymer of copolyreaction, gained to the dissolubility of alkaline-based developer and acquisition aspect easily, preferred acrylic acid, methacrylic acid, 2-acryloxy ethyl succinic acid, 2-methacryloxyethyl succinic acid etc.
In [A] multipolymer, (a1) the unsaturated carboxylic acid compounds can use separately, also two or more can be mixed the back and use.
In [A] multipolymer, be 5～60 weight % from the containing ratio of the repetitive of (a1) unsaturated carboxylic acid compounds, be preferably 10～50 weight %, more preferably 15～40 weight % (wherein, (a1)+(a2)=100 weight %, down with).At this moment, during less than 5 weight %, the dissolubility of alkaline-based developer there is the trend of reduction from the containing ratio of the repetitive of (a1) unsaturated carboxylic acid compounds; On the other hand, if surpass 60 weight %, then this multipolymer has the danger that becomes excessive to the dissolubility of alkaline-based developer.
As (a2) other unsaturated compound, at first can list the unsaturated compound that contains epoxy radicals.
As the unsaturated compound that contains epoxy radicals, can list for example glycidyl acrylate, acrylic acid 2-methyl ethylene oxidic ester, acrylic acid 4-hydroxyl butyl ester glycidol ether, acrylic acid-3,4-epoxy butyl ester, acrylic acid-6,7-epoxy heptyl ester, acrylic acid 3, acrylic acid epoxy (ring) alkyl esters such as 4-epoxycyclohexyl ester;
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 (ring) alkyl esters such as 4-epoxycyclohexyl ester;
α-Yi Jibingxisuan ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, α-Yi Jibingxisuan 6,7-epoxy heptyl ester, α-Yi Jibingxisuan 3, other alpha-alkyl acrylic acid epoxy (ring) alkyl esters such as 4-epoxycyclohexyl ester;
Neighbour-vinyl benzyl glycidol ether ,-diglycidyl ethers such as vinyl benzyl glycidol ether, right-vinyl benzyl glycidol ether etc.
Contain in the unsaturated compound of epoxy radicals at these, intensity aspect from copolyreaction and separator and bump material, preferable methyl glycidyl acrylate, methacrylic acid-2-methyl ethylene oxidic ester, methacrylic acid 6,7-epoxy heptyl ester, acrylic acid 4-hydroxybutyl ester glycidol ether, neighbour-vinyl benzyl glycidol ether ,-vinyl benzyl glycidol ether, right-vinyl benzyl glycidol ether etc.
In [A] multipolymer, (a2) unsaturated compound that contains epoxy radicals can use separately, also can two or more mix the back and use.
In addition, as (a2) other unsaturated compound, except the above-mentioned unsaturated compound that contains epoxy radicals, can also list for example alkyl-acrylates such as methyl acrylate, acrylic acid n-propyl, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate;
Alkyl methacrylates such as methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-butyl propionate, the secondary butyl ester of methacrylic acid, metering system tert-butyl acrylate;
Acrylic acid cyclohexyl ester, acrylic acid 2-methylcyclohexyl ester, acrylic acid three ring [5.2.1.0 2.6] last of the ten Heavenly stems-8-base ester, acrylic acid 2-(three ring [5.2.1.0 2.6] decane-8-base oxygen base) acrylate cyclic ester classes such as ethyl ester, acrylic acid isophorone ester;
Methacrylic acid cyclohexyl ester, methacrylic acid 2-methylcyclohexyl ester, methacrylic acid three ring [5.2.1.0 2.6] last of the ten Heavenly stems-8-base ester, methacrylic acid 2-(three ring [5.2.1.0 2.6] decane-8-base oxygen base) methacrylic acid alicyclic esters classes such as ethyl ester, methacrylic acid isophorone ester;
Unsaturated dicarboxylic acid dialkyl esters such as diethyl maleate, DEF, diethyl itaconate;
Acrylic acid tetrahydrofuran-2-base ester, acrylic acid oxinane-2-base ester, acrylic acid 2-methyl oxinane-2-base ester etc. have the esters of acrylic acid that contains the oxygen five-ring heterocycles or contain the oxygen hexa-member heterocycle;
Methacrylic acid tetrahydrofuran-2-base ester, methacrylic acid oxinane-2-base ester, methacrylic acid 2-methyl oxinane-2-base ester etc. have the methyl acrylic ester that contains the oxygen five-ring heterocycles or contain the oxygen hexa-member heterocycle;
Styrene, α-Jia Jibenyixi ,-vinyl aromatic compounds such as methyl styrene, p-methylstyrene, p-methoxystyrene;
1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene equiconjugate dienes compound, and vinyl cyanide, methacrylonitrile, acrylamide, Methacrylamide, vinyl chloride, vinylidene chloride, vinyl acetate etc.
In (a2) other unsaturated compound beyond the above-mentioned unsaturated compound that contains epoxy radicals, from [A] multipolymer of copolyreaction and gained dissolubility aspect to aqueous alkali, preferred acrylic acid 2-methylcyclohexyl ester, metering system tert-butyl acrylate, methacrylic acid three ring [5.2.1.0 2.6] last of the ten Heavenly stems-8-base ester, styrene, p-methoxystyrene, methacrylic acid tetrahydrofuran-2-base ester, 1,3-butadiene etc.
In [A] multipolymer, unsaturated compound (a2) other unsaturated compound in addition that contains epoxy radicals can use separately, also can two or more mix the back use.
In [A] multipolymer, (a2) can use 2 kinds or more than, be 40～95 weight % from their total content of repetitive, be preferably 50～90 weight %, more preferably 60～85 weight %.At this moment, during less than 40 weight %, may producing when developing expands and solution viscosity occurs increases from the total content of the repetitive of (a2); If surpass 95 weight % on the other hand, then the dissolubility to developer solution may reduce.May produce and expand when developing and the solution viscosity increase.
[A] multipolymer for example can be in solvent suitably, in the presence of radical polymerization initiator, with (a1) unsaturated carboxylic acid compounds, (a2) (a1) in addition unsaturated polymerizable compound and make.
As the solvent that uses in the above-mentioned polymerization, can list for example alcohols such as methyl alcohol, ethanol, n-propanol, isopropyl alcohol; Ethers such as tetrahydrofuran, two  alkane; Ethylene glycol monoalkyl ether classes such as glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol monomethyl n-propyl ether, glycol monomethyl n-butyl ether; Ethylene glycol monoalkyl ether acetate classes such as ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, glycol monomethyl n-propyl ether acetic acid esters, glycol monomethyl n-butyl ether acetic acid esters;
Ethylene glycol monoalkyl ether propionic acid esters such as glycol monomethyl methyl ether propionic ester, ethylene glycol monomethyl ether propionic ester, glycol monomethyl n-propyl ether propionic ester, glycol monomethyl n-butyl ether propionic ester; Diglycol alkyl ethers such as diglycol monotertiary methyl ether, carbiphene, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diglycol 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; Dipropylene glycol monoalkyl ethers such as DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol Anaesthetie Ether, dipropylene glycol methyl ethyl 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;
Aromatic hydrocarbons such as toluene, dimethylbenzene; 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 classes such as 3-n-butoxy n-butyl propionate;
And methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, the hydroxacetic acid methyl esters, the hydroxacetic acid ethyl ester, the hydroxacetic acid n-propyl, the positive butyl ester of hydroxacetic 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 Methyl Acetate, the Methoxy acetic acid ethyl ester, the Methoxy acetic acid n-propyl, the positive butyl ester of Methoxy acetic acid, the ethoxy methyl acetate, the ethoxy ethyl acetate, the ethoxy n-propyl acetate, the ethoxy n-butyl acetate, the positive propoxy methyl acetate, the positive propoxy ethyl acetate, the positive propoxy n-propyl acetate, the positive propoxy n-butyl acetate, the n-butoxy methyl acetate, the n-butoxy ethyl acetate, the n-butoxy n-propyl acetate, other ester class such as n-butoxy n-butyl acetate etc.
In these solvents, optimize diglycol alkyl ether, propylene-glycol monoalky lether acetate esters, alkoxypropan acid alkyl ester class etc.
Above-mentioned solvent can use separately, also two or more can be mixed the back and use.
With respect to total amount 100 weight portions of (a1), (a2) composition, the consumption of above solvent is 150～450 weight portions, be preferably 200～400 weight portions.
In addition, there is no particular limitation as above-mentioned radical polymerization initiator, for example can list 2,2 '-azoisobutyronitrile, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (4-methoxyl-2,4-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, t-butylperoxy pivarate, 1, organic peroxides such as 1-two (tert-butyl hydroperoxide) cyclohexane; Hydrogen peroxide etc.
In addition, when using superoxide, it can be used as the oxidation-reduction type initiating agent with reductive agent as radical polymerization initiator.
These radical polymerization initiators can use separately, also two or more can be mixed the back and use.
With respect to total amount 100 weight portions of (a1), (a2) composition, the consumption of radical polymerization initiator is 1～20 weight portion, is preferably 3～15 weight portions.
Fashionable at radical polymerization, in addition, can also use together with surfactant, chain-transferring agent etc.
In addition, the free radical polymerization condition is that temperature is 50～110 ℃, is preferably 60～100 ℃, and polymerization time is 180～480 minutes, is preferably about 240～420 minutes.
The polystyrene conversion weight-average molecular weight (hereinafter, being called " Mw ") of the gel permeation chromatography (GPC) of [A] multipolymer is 2,000～100,000, is preferably 5,000～50,000.At this moment, at Mw less than 2,000 o'clock, reductions such as the alkali-developable of filming of gained, residual film ratio, perhaps impaired danger such as pattern form, thermotolerance; On the other hand, if surpass 100,000, then there is sharpness to reduce or the impaired danger of pattern form.
The molecular weight of [A] multipolymer can be regulated with respect to the chain-transferring agent of the amount of the amount of the total amount of multipolymer (a1), (a2) composition, radical polymerization initiator, polymerization time, polymerization temperature, use by solvent.
[B] polymerizable unsaturated compound:
[B] polymerizable unsaturated compound is by in the presence of the radiation-sensitive polymerization initiator, by the unsaturated compound formation of radioactive ray exposure polymerization.
Have no particular limits as this [B] polymerizable unsaturated compound, for example, preferred simple function, 2 officials can, 3 officials can or above (methyl) esters of acrylic acid, this is because its copolymerization is good, can improve the projection of gained and the intensity of separator.
As above-mentioned simple function (methyl) esters of acrylic acid, can list for example acrylic acid 2-hydroxyethyl ester, methacrylic acid 2-hydroxyethyl ester, carbiphene acrylate, carbiphene methacrylate, acrylic acid isophorone ester, methacrylic acid isophorone ester, acrylic acid 3-methoxyl butyl ester, methacrylic acid 3-methoxyl butyl ester, (2-acryloxy ethyl) (2-hydroxypropyl) phthalic ester, (2-methacryloxyethyl) (2-hydroxypropyl) phthalic ester etc.In addition, as commercially available product, for example can list ア ロ ニ Star Network ス M-101, ア ロ ニ Star Network ス M-111, ア ロ ニ Star Network ス M-114 (more than, East Asia synthetic (strain) system); KAYARAD TC-110S, KAYARAD TC-120S (more than, Japanese chemical drug (strain) system); Commodity such as PVC ス コ one ト 158, PVC ス コ one ト 2311 (more than, Osaka organic chemistry industry (strain) system).
In addition, (methyl) esters of acrylic acid as above-mentioned 2 officials energy, can list for example glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 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, the modification of polyester two ends (methyl) propenyl, the modification of polypropylene glycol two ends (methyl) propenyl, gather 1, the modification of 4-butylene glycol two ends (methyl) propenyl.In addition, as commercially available product, can list for example ア ロ ニ Star Network ス M-210, ア ロ ニ Star Network ス M-240, ア ロ ニ Star Network ス M-6200 (more than, East Asia synthetic (strain) system), KAYARAD HDDA, KAYARADHX-220, KAYARAD R-604 (more than, Japan's chemical drug (strain) system), PVC ス コ one ト 260, PVC ス コ one ト 312, PVC ス コ one ト 335HP (more than, Osaka organic chemistry industry (strain) system), U-108A, U-200AX, UA-4100, UA-4400, UA340P, UA-2235PE, UA-160TM, UA-6100, U-2PPA200A (more than, Xin Zhong village chemical industry (strain) system) etc., UN-9000PEP, UN-9200A, UN-7600, UN-5200, UN-1003, UN-1255, UN-6060PTM, UN-6060P, SH-500B (more than, on the root industry (strain) system) etc. commodity.
In addition, as above-mentioned 3 officials can or above (methyl) esters of acrylic acid, can list 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; And as 9 officials can or above (methyl) esters of acrylic acid, can list and have straight-chain alkyl-sub-and alicyclic structure and have the compound of 2 or more a plurality of isocyanates and in molecule, have 1 or more a plurality of hydroxyl and have multifunctional polyurethane acrylic ester compound that the compound reaction of 3,4 or 5 acryloxies and/or methacryloxy obtains etc.
As 3 officials can or the commercially available product of above (methyl) esters of acrylic acid, can list for example ア ロ ニ Star Network ス M-309, ア ロ ニ Star Network ス M-400, ア ロ ニ Star Network ス M-405, ア ロ ニ Star Network ス M-450, ア ロ ニ Star Network ス M-7100, ア ロ ニ Star Network ス M-8030, ア ロ ニ Star Network ス M-8060, ア ロ ニ Star Network ス TO-1450 (more than, East Asia synthetic (strain) system), KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 (more than, Japan's chemical drug (strain) system), PVC ス コ one ト 295, PVC ス コ one ト 300, PVC ス コ one ト 360, PVC ス コ one ト GPT, PVC ス コ one ト 3PA, PVC ス コ one ト 400 (more than, Osaka organic chemistry industry (strain) system) etc.As the commercially available product that contains multifunctional polyurethane esters of acrylic acid, can list ニ ユ one Off ロ Application テ イ ア R-1150 (more than, the first industrial pharmacy (strain) system), KAYARADDPHA-40H (more than, Japan's chemical drug (strain) system), U-4HA, U-6HA, U-6LPA, U-15HA, UA-32P, U-324A, U-4H, U-6H (more than, Xin Zhong village chemical industry (strain) system), UN9000H, UN-3320HA, UN-3320HB, UN-3320HC, UN-901T, UN-1200TPK (more than, industry (strain) system on the root) etc.
These simple functions, 2 officials can, 3 officials can or above (methyl) esters of acrylic acid in, more preferably 2 officials can or above (methyl) esters of acrylic acid, be preferably polyester two terminal propenyl modifications, trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol five acrylate, dipentaerythritol acrylate especially and contain commercial goods of multifunctional polyurethane acrylic ester compound etc.
Above-mentioned simple function, 2 officials can, 3 officials can or above (methyl) esters of acrylic acid can use separately, also can two or more mix the back and use.
In radiation sensitive resin composition of the present invention, with respect to 100 weight portions [A] multipolymer, the consumption of [B] polymerizable unsaturated compound is preferably 1～120 weight portion, more preferably 3～100 weight portions.At this moment, at the consumption of [B] multipolymer unsaturated compound during less than 1 weight portion, when developing, may produce develop incomplete; On the other hand, if surpass 120 weight portions, then the adaptation of the projection of gained and separator has the trend of reduction.
[C] radiation-sensitive polymerization initiator:
[C] radiation-sensitive polymerization initiator is preferably formed by O-acetyl group oxime type light trigger, the compound of particularly above-mentioned formula (1) or (2) expression (below, be called " Photoepolymerizationinitiater initiater [C] ").
Photoepolymerizationinitiater initiater of the present invention refers to: by visible rays, ultraviolet ray, far ultraviolet, charged particle beam, the exposure of X ray isoradial, the polymerization of initiated polymerization compound [B] produces the composition of active seed.
In the Photoepolymerizationinitiater initiater [C] shown in aforementioned formula (1) or (2), R 1Be that to be selected from carbon number be that 1～20 alkyl, carbon number are 3～8 naphthenic base or phenyl groups.R 2And R 3Be respectively that to be selected from hydrogen atom, carbon number be that 1～20 alkyl, carbon number are that 3～8 naphthenic base, replacement or unsubstituted phenyl or carbon number are the group of 7～20 alicyclic group (remove carbon number and be 7～8 naphthenic base beyond).The substituting group of above-mentioned substituted-phenyl is that carbon number is that 1～6 alkyl, carbon number are 1～6 alkoxy, phenyl and halogen atom.These substituting groups can be 1-5.R 4Be that to be selected from carbon number be that 4～20 oxygen-containing heterocycle, carbon number are that 4～20 nitrogen heterocycle or carbon number are 4～20 sulfur heterocyclic ring base.R 5Be that to be selected from hydrogen, carbon number be that 1～12 alkyl or carbon number are the group of 1～12 alkoxy.N is 1～5 integer, and m is 0～5 integer, and n+m≤5,1 are 0～6 integers.
As the R in formula (1) or (2) 1Carbon number be that 1～20 alkyl can be the straight or branched alkyl, specifically can list 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.As carbon number is 3～8 naphthenic base, can exemplify out for example cyclopentyl, cyclohexyl etc.
In addition, R 2, R 3Carbon number be that 1～20 alkyl can be straight or branched, specifically can list 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.As carbon number is 3～8 naphthenic base, can exemplify out for example cyclopentyl, cyclohexyl etc.
As R 2, R 3The substituent carbon number of substituted-phenyl be that 1～6 alkyl can be straight chain, side chain, ring-type, specifically can list methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl etc.
In addition, be that 1～6 alkoxy can be straight chain, side chain, ring-type as carbon number, specifically can list methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, tert-butoxy etc.As halogen atom, can list for example fluorine atom, chlorine atom etc.
As carbon number is 7～20 alicyclic group (except carbon number is 7～8 naphthenic base), can list for example bicyclic alkyl, tricyclic alkyl, spiro cycloalkyl group, tricyclic alkyl, contain the terpene skeleton group, contain the group of diamantane skeleton etc.
R 4Carbon number be 4～20 nitrogen heterocycle, carbon number is 4～20 oxygen-containing heterocycle, carbon number is 4～20 sulfur heterocyclic ring base, can list for example thiophane (チ オ ラ ニ Le) base, azepines (ア ゼ ピ ニ Le) base, dihydro azepines base, two  alkyl, triazinyl, (オ キ サ チ ア ニ Le) base, thiazole (チ ア ゾ one リ Le) base, the  diazine, two  indanyls, ジ ヒ ア Na Off レ ニ Le, furyl, thiophenyl, pyrrole radicals, the  oxazolidinyl, different  oxazolidinyl, thiazole (チ ア ゾ リ Le) base, isothiazolyl, pyrazolyl, the furazan base, pyranose, pyridine radicals, pyridazinyl, pyrimidine radicals, pyrazinyl, pyrrolidinyl, morpholinyl, piperazinyl, the quinine base, indyl, isoindolyl, benzofuranyl, the benzo thiophenyl, indolinyl, the chromene base, quinolyl, isoquinolyl, purine radicals (プ リ ニ Le base), quinazolyl, the cinnolines base, phthalazinyl, pteridyl, carbazyl, acridinyl, phenanthridinyl, the thioxanthene base, phenazinyl, the phenothiazine base, phenol thiophene  base, phenol  piperazine base, thienyl, tetrahydrofuran, THP trtrahydropyranyl etc.Wherein, preferred especially tetrahydrofuran base, THP trtrahydropyranyl etc.
As R 5Carbon number be that 1～12 alkyl can be straight chain, side chain or ring-type, specifically can list 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, be that 1～12 alkoxy can be straight chain, side chain or ring-type as carbon number, specifically can list methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentyloxy etc.
As R 5, wherein be preferably methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, methoxyl, ethoxy especially.
N is preferably 1.M is preferably any of 0,1 or 2, is preferably 1 especially.In addition, 1 is preferably any of 0,1 or 2, is preferably 1 especially.
As the object lesson of this compound [C], can list:
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-2-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-2-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-2-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-2-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-3-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-3-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-3-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-3-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-2-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-2-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-2-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-2-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-3-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-3-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-3-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-3-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl acetyl group oxime)
Ethyl ketone, 1-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-two  alkyl) methoxybenzoyl base]-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime) etc.
Wherein, be preferably ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime); Ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime); Ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime); Ethyl ketone; 1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-; 1-(O-acetyl group oxime) and ethyl ketone; 1-[9-ethyl-6-[2-methyl-4-(2; 2-dimethyl-1; 3-two  alkyl) methoxybenzoyl base]-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime).
These Photoepolymerizationinitiater initiaters [C] can be separately or two or more together use.
As Photoepolymerizationinitiater initiater [C], also can use in addition O-acyl group oxime type Photoepolymerizationinitiater initiater of above-mentioned formula (1) (below, be called " Photoepolymerizationinitiater initiater [C-2] ") simultaneously.
Instantiation as these Photoepolymerizationinitiater initiaters [C-2] can exemplify out, and 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.Among them, preferred especially 1,2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oximes).Photoepolymerizationinitiater initiater [C-2] preferably uses 30 weight % or following of Photoepolymerizationinitiater initiater [C].
In the present invention, by using [C] radiation-sensitive polymerization initiator, even 1,200J/m 2Or under the following exposure, also can reach enough sensitivity, and can obtain having good fusible projection and separator.
In radiation sensitive resin composition of the present invention, with respect to 100 weight portions [B] polymerizable unsaturated compound, the consumption of [C] radiation-sensitive polymerization initiator is preferably 5～30 weight portions, more preferably 5～20 weight portions.At this moment, the consumption of [C] radiation-sensitive polymerization initiator is during less than 5 weight portions, and the residual film ratio during development has the tendency of reduction; On the other hand, if surpass 30 weight portions, unexposed dissolubility to alkaline-based developer has the tendency of reduction when then developing.
In addition, in radiation sensitive resin composition of the present invention, one or more other radiation sensitive resin composition and [C] radiation-sensitive polymerization initiator can also be used together.
As above-mentioned other Photoepolymerizationinitiater initiater, can exemplify out such as, diimidazole compounds, styrax compounds, acetophenone compounds, Benzophenones compound, α-cyclohexadione compounds, multinuclear quinones, xanthone compounds, phosphine compound, compound in triazine class etc.Among them, preferred acetophenone compounds (below, be sometimes referred to as " (D) composition "), diimidazole compounds (below, be sometimes referred to as " (E) composition ").As above-mentioned other radiation-sensitive polymerization initiator, can list for example acetophenone compounds, diimidazole compounds, styrax compounds, Benzophenones compound, α-cyclohexadione compounds, multinuclear quinones, thioxanthones compounds, phosphine compound, compound in triazine class etc., wherein, preferred acetophenone compounds, diimidazole compounds etc.
(D) composition: acetophenone compounds
In addition,, can list for example alpha-hydroxy ketones, alpha-amido ketone compounds, the compound beyond these etc. as above-mentioned acetophenone compounds.
As the instantiation of alpha-hydroxy ketones, can list for example 1-phenyl-2-hydroxy-2-methyl-third-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl-third-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 1-hydroxycyclohexylphenylketone etc.As the instantiation of above-mentioned alpha-amido ketone compounds, can list for example 2-methyl isophthalic acid-[4-(methyl sulfenyl) phenyl]-2-morpholinyl-third-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-Ding-1-ketone, 2-(4-methyl benzoyl)-2-dimethylamino-1-(4-morpholinyl phenyl)-Ding-1-ketone etc.Instantiation as the compound beyond these for example can list 2,2-dimethoxy-acetophenone, 2,2-diethoxy acetophenone, 2,2-dimethoxy-2-phenyl acetophenone etc.
These acetophenone compounds can use separately, also two or more can be mixed the back and use.
By using these acetophenone compounds, can further improve the shape and the compression strenght of sensitivity, separator and projection.
(E) composition: diimidazole compounds
Instantiation as the diimidazole compounds can list for example 2,2 '-two (2-chlorophenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2-bromo phenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2-chlorophenyls)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4-dichloro-phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4,6-trichlorobenzene base)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2-bromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4-dibromo-benzene base)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4,6-tribromo-benzene base)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole etc.
In these diimidazole compounds, preferred 2,2 '-two (2-chlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4-dichloro-phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4,6-trichlorobenzene base)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole etc., preferred especially 2,2 '-two (2,4-dichloro-phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole.
Above-mentioned diimidazole compounds can use separately, also two or more can be mixed the back and use.
By using these diimidazole compounds, can further improve sensitivity, resolution and adaptation.
In addition, in order to increase the sensitivity of diimidazole compounds, can add aliphatic category with dialkyl amido or aromatic series compounds (below, be called " sensitizer [E-2] ").
Instantiation as above-mentioned sensitizer [E-2], can list 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, be preferably 4,4 '-two (diethylamino) benzophenone.
Above-mentioned sensitizer [E-2] can use separately, also multiple mixing back can be used.
Relative 100 weight portions [A], the use amount of sensitizer [E-2] preferably contains the 0.1-50 weight portion, more preferably contains the 1-20 weight portion.
The consumption of sensitizer [E-2] is during less than 0.1 weight portion, has the separator that gained takes place and the film of projection and reduces or the bad tendency of pattern form, in addition, if surpass 50 weight portions, has the bad tendency of the pattern form of generation equally.
When using the diimidazole compounds, can add sulfur alcohol compound (below, be sometimes referred to as " sulfur alcohol compound [E-3] ") as the hydrogen supply compound.The diimidazole compounds breaks by the Benzophenones compound sensitizing with dialkyl amido, produces imidazole radical.Can't show high polymerization energy of initiation in this occasion, the separator of gained mostly is the undesirable like this shape of turbination shape greatly.This problem can be by at the diimidazole compounds with have in the system of Benzophenones compound coexistence of dialkyl amido, adds sulfur alcohol compound [E-3] and alleviates.By imidazole radical being provided hydroperoxyl radical, and produce neutral imidazoles and have the compound of the sulphur free radical of high polymerization energy of initiation from sulfur alcohol compound.Thus, separator be shaped as preferred along coniform.
Relative 100 weight portion compounds [C], the usage ratio of above-mentioned sulfur alcohol compound [E-3] preferably contains the 0.1-50 weight portion, more preferably contains the 1-20 weight portion.The consumption of sulfur alcohol compound [E-3] is during less than 0.1 weight portion, has the separator that gained takes place and the film of projection and reduces or the bad tendency of pattern form, in addition, if surpass 50 weight portions, has the bad tendency of the pattern form of generation equally.
As its instantiation, can list for example 2-mercaptobenzothiazole, 2-sulfydryl benzoxazol, 2-mercaptobenzimidazole, 2-sulfydryl-5-methoxyl benzo thiazole, 2-sulfydryl-aromatic mercaptans such as 5-methoxyl benzo imidazoles; The single mercaptan of aliphatics such as 3-mercaptopropionic acid, 3-mercapto-propionate, 3-mercaptopropionic acid ethyl ester, 3-mercaptopropionic acid monooctyl ester; As 2 officials can or more polyfunctional aliphatics mercaptan can exemplify out 3,6-two oxa-s-1,8-suffering-two mercaptan, pentaerythrite four (mercaptoacetate), pentaerythrite four (3-mercaptopropionic acid ester) etc.
As above-mentioned thioxanthones compounds, can list 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2,4-dichloro-thioxanthones etc.
As above-mentioned phosphine compound, can list oxidation 2,4,6-trimethylbenzoyl diphenylphosphine, oxidation 2,4,6-trimethylbenzoyl phenylethyl phosphine, oxidation two (2,4, the 6-trimethylbenzoyl) Phenylphosphine etc.
The usage ratio of other Photoepolymerizationinitiater initiater is preferably 100 weight portions or following with respect to whole Photoepolymerizationinitiater initiaters 100 weight portions, and more preferably 80 weight portions or following are preferably 60 weight portions or following especially.At this moment, if the usage ratio of other Photoepolymerizationinitiater initiater surpasses 100 weight portions, then may damage the desired effect of the present invention.
Adjuvant:
In the scope of not damaging the desired effect of the present invention, in radiation sensitive resin composition of the present invention, as required, except adding mentioned component, can also add adjuvants such as surfactant, adhesive aid, preserving stabilizer, thermotolerance improving agent.
Above-mentioned surfactant is the composition with the effect that improves coating, preferred fluorine class surfactant and silicone based surfactant.
Be preferably endways as above-mentioned fluorine class surfactant, the compound that has fluoro-alkyl or fluoro alkylidene at least one position of main chain and side chain as its concrete example, can list 1,1,2,2-tetrafluoro octyl group (1,1,2, the 2-tetrafluoro is for n-pro-pyl) ether, 1,1,2, the 2-tetrafluoro is for n-octyl (n-hexyl) ether, eight ethylene glycol bisthioglycolates (1,1,2,2-tetrafluoro normal-butyl) ether, six ethylene glycol (1,1,2,2,3,3-hexafluoro n-pentyl) ether, eight propylene glycol two (1,1,2,2-tetrafluoro normal-butyl) ether, six propylene glycol two (1,1,2,2,3,3-hexafluoro n-pentyl) ether, 1,1,2,2,3,3-hexafluoro n-decane, 1,1,2,2,8,8,9,9,10,10-ten fluorine n-dodecanes, perfluor n-dodecane sodium sulfonate and, fluoro-alkyl benzene sulfonic acid sodium salt class, fluoro-alkyl sodium phosphite class, fluoro-alkyl carboxylic acid sodium class, the fluoro-alkyl polyethenoxy ether class, two glycerine four (fluoro-alkyl polyoxyethylene groups ether) class, fluoro-alkyl ammonium iodine compound class, the sweet Lay bases of fluoro-alkyl, the fluoro-alkyl polyethenoxy ether class, perfluoroalkyl poly oxyethanol class, perfluoroalkyl alkoxide class, fluorine class alkyl esters etc.
Commercial goods as fluorine class surfactant, can list for example commodity BM-1000 by name, BM-1100 (more than, BMCHEMIE (strain) system), メ ガ Off ア Star Network F142D, メ ガ Off ア Star Network F172, メ ガ Off ア Star Network F173, メ ガ Off ア Star Network F183, メ ガ Off ア Star Network F178, メ ガ Off ア Star Network F191, メ ガ Off ア Star Network F471, メ ガ Off ア Star Network F476 (more than, big Japanese ink chemical industry (strain) system), Off ロ ラ one De FC-170C, Off ロ ラ one De FC-171, Off ロ ラ one De FC-430, Off ロ ラ one De FC-431 (more than, Sumitomo ス リ one エ system (strain) system), サ one Off ロ Application S-112, サ one Off ロ Application S-113, サ one Off ロ Application S-131, サ one Off ロ Application S-141, サ one Off ロ Application S-145, サ one Off ロ Application S-382, サ one Off ロ Application SC-101, サ one Off ロ Application SC-102, サ one Off ロ Application SC-103, サ one Off ロ Application SC-104, サ one Off ロ Application SC-105, サ one Off ロ Application SC-106 (more than, Asahi Glass (strain) system), エ Off ト Star Block EF301, Off ト Star Block EF303, Off ト Star Block EF352 (more than, new autumn fields changes into (strain) system), Off one ジ エ Application ト FT-100, Off one ジ エ Application ト FT-110, Off one ジ エ Application ト FT-140A, Off one ジ エ Application ト FT-150, Off one ジ エ Application ト ト FT-250, Off one ジ エ Application ト FT-251, Off one ジ エ Application ト FTX-251, Off one ジ エ Application ト FTX-218, Off one ジ エ Application ト FT-300, Off one ジ エ Application ト FT-310, Off one ジ エ Application ト FT-400S (more than, ネ オ ス (strain) system) etc.
As above-mentioned silicon-type surfactant, can list for example commodity ト one レ シ リ コ one Application DC3PA by name as the commercial goods, ト one レ シ リ コ one Application DC7PA, ト one レ シ リ コ one Application SH11PA, ト one レ シ リ コ one Application SH21PA, ト one レ シ リ コ one Application SH28PA, ト one レ シ リ コ one Application SH29PA, ト one レ シ リ コ one Application SH30PA, ト one レ シ リ コ one Application SH-190, ト one レ シ リ コ one Application SH-193, ト one レ シ リ コ one Application SZ-6032, ト one レ シ リ コ one Application SF-8428, ト one レ シ リ コ one Application DC-57, ト one レ シ リ コ one Application DC-190 (more than, east レ ダ ウ コ one ニ Application グ シ リ コ one Application (strain) system), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, the commodity of TSF-4452 (more than, GE Toshiba シ リ コ one Application (strain) system) etc.
In addition, as the surfactant beyond above-mentioned, can enumerate the polyoxyethylene alkyl ether class of polyoxyethylene lauryl ether, polyoxyethylene stearyl acyl group ether, polyoxyethylene oleyl ether etc.; The polyoxyethylene aryl ethers of polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-nonyl phenyl ether etc.; The nonionic surfactant of the polyoxyethylene dialkyl of polyoxyethylene dilaurate, polyoxyethylene distearate etc. etc.; And, for example can list commodity such as KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), Port リ Off ロ one No.57, Port リ Off ロ one No.95 (more than, common prosperity society chemistry (strain) system) as the commercial goods.
Above-mentioned surfactant can use separately, two or more can be mixed and use.
With respect to 100 weight portions [A] multipolymer, the use level of surfactant is 5 weight portions or following and then 2 weight portions or following preferably preferably.At this moment, when the surfactant use level surpasses 5 weight portions, the coarse tendency of produced film when coating is easily arranged.
Above-mentioned adhesive aid is the composition with effect of the adaptation of improving projection and separator and matrix, is preferably the functional silanes coupling agent.
As above-mentioned functional silanes coupling agent, can list the reactive functional based compound that for example has carboxyl, methacryl, vinyl, isocyanate group, epoxy radicals etc.More specifically, can list trimethoxysilyl benzoic acid, gamma-methyl allyl acyloxypropyl trimethoxysilane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-isocyanate group propyl-triethoxysilicane, γ-glycidoxypropyltrime,hoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane etc.
These adhesive aids can use separately, also two or more can be mixed and use.
With respect to [A] copolymer 1 00 weight portion, the combined amount of adhesive aid preferably 20 weight portions or following, more preferably below 10 weight portions.At this moment, if the combined amount of adhesive aid surpasses 20 weight portions, then have to be easy to generate the incomplete tendency of developing.
As above-mentioned preserving stabilizer, can list for example sulphur, quinones, hydroquinones, polyoxy compounds, amine, nitro nitroso compound etc., more specifically can enumerate 4-metoxyphenol, N-nitroso--N-phenyl hydramine aluminium etc.
These preserving stabilizers can use separately, or mix two or more uses.
With respect to 100 weight portions [A] multipolymer, the use level of preserving stabilizer is 3 weight portions or following, 0.001～0.5 weight portion more preferably preferably.At this moment, when the combined amount of preserving stabilizer surpasses 3 weight portions, possible desensitization infringement graphics shape.
As above-mentioned thermotolerance improving agent, can list for example N-(alkoxy methyl) glycoluril compounds, N-(alkoxy methyl) melamine compound, have compound of 2 or more a plurality of epoxy radicals etc.
As above-mentioned N-(alkoxy methyl) glycoluril compounds, can list for example N, N, N, N-four (methoxy) glycoluril, N, N, N, N-four (ethoxyl methyl) glycoluril, N, N, N, N-four (n-propoxymethyl) glycoluril, N, N, N, N-four (isopropoxy methyl) glycoluril, N, N, N, N-four (n-butoxy methyl) glycoluril, N, N, N, N-four (tert-butoxy methyl) glycoluril etc.
In these N-(alkoxy methyl) glycoluril compounds, particularly preferably be N, N, N, N-four (methoxy) glycoluril.
As above-mentioned N-(alkoxy methyl) melamine compound, can list for example 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.
In these N-(alkoxy methyl) melamine compound, particularly preferably be N, N, N, N, N, N-six (methoxy) melamine, as its commercially available product, for example can enumerate the commodity of ニ ガ ラ Star Network N-2702, ニ カ ラ Star Network MW-30M (more than, three and chemistry (strain) system) etc.
In addition, as compound with above-mentioned 2 or more a plurality of epoxy radicals, can enumerate for example ethylene glycol diglycidylether, the diglycol diglycidyl ether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, the hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, orthoresol phenolic aldehyde type epoxy resin.In addition, as commercially available product, can enumerate for example 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 1500NP, エ Port ラ イ ト 1600, エ Port ラ イ ト 80MF, エ Port ラ イ ト 100MF, エ Port ラ イ ト 3002, エ Port ラ イ ト 4000 (more than, common prosperity society chemistry (strain) system), EOCN102, EOCN103S, EOCN104S, EOCN1020, EOCN1025, EOCN1027 (Japanese chemical drug (strain) system), エ ピ コ one ト 180S commodity such as (ジ ヤ パ Application エ Port キ シ レ ジ Application corporate systems).
These thermotolerance improving agents can use separately, also two or more can be mixed and use.
With respect to 100 weight portions [A] multipolymer, the combined amount of thermotolerance improving agent is 30 weight portions or following preferably, more preferably 20 weight portions or following.At this moment, if the combined amount of thermotolerance improving agent surpasses 30 weight portions, then the storage stability of radiation sensitive resin composition has the trend of reduction.
Radiation sensitive resin composition of the present invention preferably uses the composition solution that is dissolved in the appropriate solvent.
Can use each composition that can dissolve the formation radiation sensitive resin composition equably as above-mentioned solvent, and do not react with each composition, has suitable volatile solvent, dissolving energy from each composition, set out with the reactivity and the easy viewpoint of filming that forms of each composition, be preferably alcohols, the ethylene glycol monoalkyl ether acetate class, diglycol monotertiary alkyl ether acetic acid esters, the diglycol alkyl ether, the propylene-glycol monoalky lether acetate esters, alkoxypropan acid alkyl ester classes etc. particularly preferably are phenmethylol, the 2-phenylethanol, 3-phenyl-1-propyl alcohol, glycol monomethyl n-butyl ether acetic acid esters, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diglycol ethyl-methyl ether, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters etc.
Above-mentioned solvent can use separately, also two or more can be mixed the back and use.
In the present invention, further, also high boiling solvent and above-mentioned solvent are used together.
As above-mentioned high boiling solvent, can list for example N-NMF, N, dinethylformamide, N-methyl formyl aniline, N-methylacetamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), benzylisoeugenol, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, phenmethylol, 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 use separately, also two or more can be mixed and use.
In all solvents, the consumption of high boiling solvent is preferably 50 weight % or following, more preferably 30 weight % or following.
In addition, normally to make the concentration of the solid state component of radiation sensitive resin composition of the present invention be 15～45 weight % to the consumption of above solvent, be preferably the amount about 20～40 weight %.
In addition, the composition solution of above-mentioned modulation also the millipore filter about usage aperture 0.5 μ m etc. filter the back and use.
Radiation sensitive resin composition of the present invention is suitable for forming the projection and the separator of vertical alignment-type liquid crystal display device very much.
The formation method of projection and separator
Below, describe for the method for using radiation sensitive resin composition of the present invention to form projection of the present invention and separator.
The formation method of projection of the present invention and separator comprises the following operation of following order record at least.
(i) operation of formation radiation sensitive resin composition film of the present invention on substrate,
(ii) with the operation of at least a portion of this film exposure,
The operation of this film after (iii) development exposes, and
The operation that (iv) adds this film after the thermal development.
Below, describe successively for these operations.
(i) operation
Form nesa coating on the one side of transparency carrier, after applying radiation sensitive resin composition on this nesa coating, being preferably composition solution, heating coated side (prebake conditions) forms film.
As the transparency carrier that is used to form separator, can list for example glass substrate, resin substrate etc.More specifically, can enumerate the glass substrate of soda-lime glass, alkali-free glass etc.; The resin substrate that the plastics of polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide etc. form.
As the nesa coating that on the one side of transparency carrier, is provided with, can enumerate by tin oxide (SnO 2) the NESA film (registered trademark of U.S. PPG society), the indium oxide-tin oxide (In that form 2O 3-SnO 2) the ITO film that forms etc.
As forming the method that photosensitive polymer combination of the present invention is filmed, for example can be undertaken by (1) rubbing method, (2) dry film method.
As the painting method of composition solution, for example can adopt suitable method such as gunite, rolling method, spin coating method (spin-coating method), slot coated method, scraping article cladding process, ink jet cladding process, preferred especially spin-coating method, slot coated method.
In addition, when (2) the dry film method of employing forms filming of photosensitive polymer combination of the present invention, this dry film is at substrate film, is preferably on the flexible substrate film, (below, be called " photonasty dry film ") that the photosensitive layer that lamination is formed by photosensitive polymer combination of the present invention forms.
The dry film of above-mentioned photonasty is after being coated with photosensitive polymer combination of the present invention on the substrate film, being preferably liquid composition, drying, and the laminated photosensitive layer forms.Substrate film as the dry film of photonasty for example can use film of synthetic resin such as polyethylene terephthalate (PET), tygon, polypropylene, polycarbonate, Polyvinylchloride.That the thickness of substrate film is suitable is 15～125 μ m.The thickness of the photosensitive layer of gained is preferably about 1～30 μ m.
In addition, the dry film of photonasty can be preserved by further lamination diaphragm on this photosensitive layer when not using.This diaphragm is not peeled off when not using, and can easily peel off in use, so suitable release property must be arranged.As the diaphragm that satisfies this condition, for example can list on the surface of synthetic resin such as PET film, polypropylene film, polyethylene film, polyvinyl chloride film, apply or film that the silicone based release agent of sintering forms.The thickness of diaphragm is generally about 25 μ m.
In addition, the condition of prebake conditions is according to the kind of each composition, blending ratio etc. and different, usually under 70～120 ℃, for about 1-15 minute.
(ii) operation
Then, with at least a portion exposure of the film that forms.At this moment, when on the part of film, exposing, by having the photomask exposure of compulsory figure.At this moment, if consider productivity, preferably to the zone that forms projection with as the zone of separator, with identical in fact exposure exposure.At this moment, at exposing clearance one regularly, the A/F of mask is more little, and the illumination for exposure degree is low more, so degree of crosslinking is low more, the result is to flow the generation difference in height during baking of back easily.
In addition, can also expose by pattern mask with the little part of big part of radioactive ray transmitance and radioactive ray transmitance.
The radioactive ray that use during as exposure can use for example visible rays, ultraviolet ray, far ultraviolet, electron beam, X ray etc., and preferred wavelength range is the radioactive ray of 190～450nm, especially preferably contains the ultraviolet radioactive ray of 365nm.
Exposure is that the radioactive ray wavelength of measuring exposure by photometer (OAI model 356, OAI Optical AssociatesInc. make) is the value of the intensity of 365nm, normally 100～3, and 000J/m 2, be preferably 200～1,200J/m 2
(iii) operation
Then, develop, remove the figure that part not forms regulation by the film after will exposing.
As the developer solution that is used to develop, preferred alkaline-based developer can list inorganic bases such as NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium methyl silicate, ammonia as its example; Armeen such as ethamine, n-propylamine class; Aliphatic secondary such as diethylamine, di-n-propylamine amine; The aliphatic tertiary amine class of trimethylamine, methyl-diethyl-amine, dimethyl amine, triethylamine etc.; Pyrroles, piperidines, N-methyl piperidine, N-crassitude, 1,8-diazabicylo [5.4.0]-7-undecylene, 1, the alicyclic tertiary amines of 5-diazabicylo [4.3.0]-5-nonene etc.; The aromatic tertiary amine of pyridine, trimethylpyridine, lutidines, quinoline etc.; Dimethylethanolamine, alkanolamine such as methyldiethanolamine, triethanolamine; The aqueous solution of alkali compounds such as quaternary ammonium salt such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide.
In addition, use after in the aqueous solution of above-mentioned alkali compounds, also can adding the water-miscible organic solvent such as methyl alcohol, ethanol of appropriate amount and surfactant.
As developing method, also can contain any one method of liquid method, infusion process, spray process etc., development time is normally about 10～180 seconds.
After the development, for example the flowing water washing is after 30～90 seconds, for example by pressurized air or the desirable figure of the air-dry formation of compressed nitrogen.
(iv) operation
Then, the figure that obtains is arrived set point of temperature, for example 150～250 ℃, stipulated time by for example heating arrangement such as hot plate, baking oven heating (back baking), for example for be 5～30 minutes on the hot plate, for being 30～180 minutes in the baking oven, projection that can obtain stipulating and separator.
Radiation sensitive resin composition of the present invention is highly sensitive, can form the projection and the separator of vertical alignment-type liquid crystal display device simultaneously, enough graphics shapes can be obtained, projection and separator that all excellent vertical alignment-type liquid crystal display device such as adaptation, thermotolerance of separator intensity, anti-abrasive property and transparency carrier uses can be formed.
In addition, vertical alignment-type liquid crystal display device of the present invention have graphics shape, separator intensity, anti-abrasive property, with all excellent projection and the separators of various performances such as the adaptation of transparency carrier, thermotolerance, through also demonstrating high reliability for a long time.
Embodiment
Below, with embodiment embodiments of the present invention are carried out more specific description.Here, part and % are weight basis.
Synthesis example 1
In the flask that possesses cooling tube, stirring machine, add 5 part 2,2 '-azoisobutyronitrile and 250 parts of diglycol methyl ethyl ethers then, add 35 parts of 2-methacryloxyethyl succinic acids, 25 parts of n-BMAs, 35 parts of benzyl methacrylates, behind the nitrogen replacement, add 5 weight portion 1,3-butadienes again, slowly stir and the temperature of solution is risen to 90 ℃, under this temperature, keep carrying out polymerization in 5 hours, obtain solid component concentration and be [A] copolymer solution of 28.0%.With it as [A-1] polymkeric substance.
[A-1] polymkeric substance of gained uses GPC (gel permeation chromatography) HLC-8020 (trade name, eastern ソ one (strain) system) to measure Mw, is 12,000.
Synthesis example 2
In the flask that possesses cooling tube, stirring machine, add 5 weight portions 2,2 '-azo two (2, the 4-methyl pentane nitrile) and 200 parts of diglycol methyl ethyl ethers, then, 18 parts of methacrylic acids of adding, 40 parts of glycidyl methacrylate, 5 parts by weight of styrene, 32 parts of methacrylic acids three encircle [5.2.1.0 2.6] last of the ten Heavenly stems-8-base ester, nitrogen replacement after, add 5 parts of 1,3-butadienes again, slowly stir and the temperature of solution risen to 70 ℃, keep this temperature to carry out polymerization in 5 hours, obtain the solution of multipolymer [A-2].
The solid component concentration of this solution is 33.0 weight %, and the Mw of multipolymer [A-2] is 11,000.
Embodiment 1
The preparation of composition solution
With 100 parts of [A] copolymer solution multipolymers [A-1] that obtain by synthesis example 1 as [A] composition; the ethyl ketone of the dipentaerythritol acrylate of 60 parts of conducts [B] composition (trade name KAYARAD DPHA, Japanese chemical drug (strain) system), 5 parts of conducts [C] composition; 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran methoxybenzoyl base)-9.H.-carbazole-3-yl]-; 1-(O-acetyl group oxime) mixes; be dissolved in the propylene glycol monomethyl ether; make solid component concentration become 30%; millipore filter with aperture 0.5 μ m filters compositions formulated solution then.
The formation of projection and separator
After using rotary jet to apply above-mentioned composition solution on the alkali-free glass substrate, prebake conditions formed the film of thickness 4.0 μ m in 3 minutes on 80 ℃ hot plate.
Then, pass through the photomask of the figure of residual 5 μ m and 15 μ m circle on the film that obtains, with exposure slit 200 μ m, the intensity of 365nm is 250W/m 24 seconds of ultraviolet exposure.The actual exposure amount of this moment is equivalent to 1000J/m 2Then, with the potassium hydroxide aqueous solution of 0.05 weight % 25 ℃ develop the stipulated time down after, with pure water washing 1 minute, heating 60 minutes in 220 ℃ baking oven again, single exposure forms projection and separator simultaneously.The photomask of the figure by residual 5 μ m forms projection, and the photomask of the figure of the circle by residual 15 μ m forms separator.
Then, according to following main points, carry out various evaluations.Evaluation result is as shown in table 2.
(1) sensitivity evaluation
In the figure of gained, the residual film ratio after the development be 90% or above sensitivity be 1200J/m 2Or when following, can think that sensitivity is good.
(2) evaluation of section shape
The projection that gets with scanning electron microscope observation post and the section shape of separator are estimated according to whether according with any of A～E shown in Figure 1.For the situation of projection, when section shape is the such semi-convex lensing of Fig. 1 (D), be good; When being the such equilateral triangle of Fig. 1 (E), be bad from the coating of alignment films.
On the other hand, for the situation of separator, when forming such suitable coniform of the such column of Fig. 1 (A) or Fig. 1 (B), section shape is good.With respect to this, for the inverted cone-shaped (section shape is the edge of the film surface del longer than the edge of substrate-side) shown in Fig. 1 (C) time, the later stage during milled processed since figure very likely peel off, so section shape is bad.
(3) evaluation of separator intensity
To the separator of gained, with slight compression testing machine (trade name MCTM-200, (strain) Shimadzu Seisakusho Ltd. make), press son with the plane of diameter 50 μ m, with the load speed of 2.6mN/s, the deflection when measuring the load that adds 10mN (measuring temperature is 23 ℃).This value can think that at 0.5 μ m or when following the intensity of separator is good.
(4) evaluation of anti-abrasive property
After will being coated on the substrate that is formed with separator with the liquid crystal orientation film coating as the AL3046 (trade name, JSR (strain) system) of aligning agent for liquid crystal with printing machine, drying be 1 hour under 180 ℃, forms filming of thickness 0.05 μ m aligning agent for liquid crystal.
Then, on this is filmed, use the muller of the roller with coiling polyamide system cloth to carry out milled processed, the rotating speed of roller is that the translational speed of 500rpm, objective table is 1cm/s.Estimating figure this moment has or not and is cut or peels off.
(5) evaluation of adaptation
Except not using the photomask, implement in the same manner with the formation of above-mentioned separator, form cured film.Then, estimate according to the gridiron pattern adhesive tape method of 8.52 in the viscosity test of JIS K-5400 (1900) 8.5.Tessellated quantity residual in this moment 100 the gridiron pattern is as shown in table 2.
(6) stable on heating evaluation
Except not using the photomask, implement in the same manner with the formation of above-mentioned separator, form cured film, afterwards, heating is 60 minutes in 240 ℃ baking oven, measures the thickness of heating front and back, estimates by residual film ratio (thickness after the heating * 100/ initial stage thickness).
Embodiment 2～8, comparative example 1～4
In embodiment 1, each composition of table 1 and 5 parts of γ-glycidoxypropyltrime,hoxysilane as bonding auxiliary agent, 0.5 part of FTX-218 as surfactant, 0.5 part of 4-metoxyphenol as preserving stabilizer are mixed, be dissolved in the propylene glycol monomethyl ether, so that after solid component concentration is 30%, millipore filter with aperture 0.5 μ m filters, the preparation composition solution.Afterwards, similarly to Example 1, form projection and separator, estimate similarly to Example 1.The result is as shown in table 2.
In table 1, each composition beyond the polymkeric substance, as described below.
B-1: dipentaerythritol acrylate (trade name KAYARAD DPHA)
B-2: contain multifunctional polyurethane acrylic ester compound commercially available product (trade name KAYARAD DPHA-40H)
[C] composition
C-1: ethanol, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran methoxybenzoyl base)-9.H.-carbazole-3-yl)-, 1-(O-acetyl group oxime)
C-2: ethyl ketone, 1-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-two  alkyl) methoxybenzoyl base]-9.H.-carbazole-3-yl]-, 1-(O-acetyl group oxime)
D-1:2-methyl isophthalic acid-(4-methyl thio-phenyl)-2-morpholinyl-third-1-ketone (trade name イ Le ガ キ ユ ア 907, チ バ ス ペ シ ヤ Le テ イ one ケ ミ カ Le ズ society system)
D-2:2-(4-methyl benzoyl)-2-(dimethylamino)-1-(4-morpholinyl phenyl)-Ding-1-ketone (trade name イ Le ガ キ ユ ア 379, チ バ ス ペ シ ヤ Le テ イ one ケ ミ カ Le ズ society system)
E-1:2,2 '-two (2,4-dichloro-phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole
E-2:2,2 '-two (2-chlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole
E-3:4,4 '-two (diethylamino) benzophenone
The E-4:2-mercaptobenzothiazoler
F-1:2, the 4-diethyl thioxanthone
F-2: oxidation 2,4,6-trimethylbenzoyl diphenylphosphine
Table 1
The composition kind The A composition The B composition The C composition
Kind Weight portion Kind Weight portion Kind Weight portion Kind Weight portion Kind Weight portion
Embodiment 1 (S-1) Polymer A-1 100 B-1 60 C-1 5 - - - -
Embodiment 2 (S-2) Polymer A-1 100 B-1 60 C-1 1 D-1 10 F-1 2.5
Embodiment 3 (S-3) Polymer A-1 100 B-1 60 C-1 1 D-2 10 - -
Embodiment 4 (S-4) Polymer A-1 100 B-1+B-2 40+20 C-1 5 - - E-2+E-3+E-4 10+10+5
Embodiment 5 (S-5) Polymer A-2 100 B-1 60 C-1 5 - - - -
Embodiment 6 (S-6) Polymer A-2 100 B-1 60 C-1 1 D-1 10 F-1 2.5
Embodiment 7 (S-7) Polymer A-2 100 B-1+B-2 40+20 C-1 1 - - E-2+E-3+E-4 10+10+5
Embodiment 8 (S-8) Polymer A-2 100 B-1+B-2 40+20 C-1 2 F-2 5 - -
Comparative example 1 (s-1) Polymer A-1 100 B-1 110 - - D-1 20 - -
Comparative example 2 (s-2) Polymer A-1 100 B-1 60 - - D-2 10 - -
Comparative example 3 (s-3) Polymer A-2 100 B-1 110 - - D-1 20 - -
Comparative example 4 (s-4) Polymer A-2 100 B-1 60 - - D-2 10 - -
Table 2
The composition kind Sensitivity (J/m 2) Section shape projection separator Separator intensity (μ m) Anti-abrasive property experiment has or not peels off Adaptation (/ 100) Thermotolerance (%)
Embodiment 1 (S-1) 700 D B 0.6 Do not have 100 80
Embodiment 2 (S-2) 800 D B 0.7 Do not have 100 81
Embodiment 3 (S-3) 1000 D A 0.6 Do not have 100 83
Embodiment 4 (S-4) 1000 D B 0.8 Do not have 100 82
Embodiment 5 (S-5) 600 D B 0.7 Do not have 1O0 93
Embodiment 6 (S-6) 700 D B 0.7 Do not have 100 93
Embodiment 7 (S-7) 800 D A 0.9 Do not have 100 92
Embodiment 8 (S-8) 800 D B 0.8 Do not have 100 90
Comparative example 1 (s-1) 2000 E C 0.5 Have 90 75
Comparative example 2 (s-2) 2500 D A 0.7 Do not have 100 78
Comparative example 3 (s-3) 1800 D B 0.6 Do not have 100 89
Comparative example 4 (s-4) 2200 D A 0.7 Do not have 100 90

Claims (4)

1. one kind is used for forming simultaneously the projection of vertical alignment-type liquid crystal display device and the radiation sensitive resin composition of separator, it is characterized in that: comprise,
The multipolymer that [A] obtains following (a1)～(a2) copolymerization, wherein (a1) is unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, (a2) is other unsaturated compound beyond (a1) composition;
[B] polymerizable unsaturated compound; With
The radiation-sensitive polymerization initiator that [C] formed by the compound shown in following formula (1) or (2),
Here, R 1Be that to be selected from carbon number be that 1～20 alkyl, carbon number are 3～8 naphthenic base or phenyl groups, R 2, R 3Be respectively that to be selected from hydrogen atom, carbon number be that 1～20 alkyl, carbon number are that 3～8 naphthenic base, replacement or unsubstituted phenyl or carbon number are the group of 7～20 alicyclic group (except carbon number is 7～8 naphthenic base), the substituting group of above-mentioned substituted-phenyl is that carbon number is that 1～6 alkyl, carbon number are 1～6 alkoxy, phenyl and halogen atom, R 4Be that to be selected from carbon number be that 4～20 oxygen-containing heterocycle, carbon number are that 4～20 nitrogen heterocycle or carbon number are the group of 4～20 sulfur heterocyclic ring base, R 5Be that to be selected from hydrogen, carbon number be that 1～12 alkyl or carbon number are the group of 1～12 alkoxy, n is 1～5 integer, and m is 0～5 integer, n+m≤5,
Here, R 1, R 2, R 3, R 4, R 5, m and n definition same as described above, 1 is the integer of 0-6, R 1, R 2, R 3, R 4, R 5, m, n and 1 be separate.
2. one kind forms the projection of vertical alignment-type liquid crystal display device and the formation method of separator simultaneously, it is characterized in that: contain the following operation of following order record,
(1) operation of filming of the radiation-ray sensitive composition that formation claim 1 is put down in writing on substrate,
(2) to the operation of this at least a portion of filming irradiation radioactive ray,
(3) developing procedure and
(4) heating process.
3. the projection and the separator of the vertical alignment-type liquid crystal display device that forms by the method for claim 2.
4. have the projection that is used to form vertical alignment-type liquid crystal display device that claim 3 puts down in writing and the liquid crystal display cells of separator.
CNA200610067016XA 2005-04-01 2006-03-31 X-ray sensitive resin composition, protruded body and barrier body formed thereby, forming method thereof and liquid crystal display element Pending CN1841196A (en)

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CN105068379A (en) * 2015-08-21 2015-11-18 田菱新材料（厦门）有限公司 Photosensitive resin component for silk-screen printing

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TW200846823A (en) * 2006-11-15 2008-12-01 Taiyo Ink Mfg Co Ltd Photosensitive composition
KR100895352B1 (en) * 2006-11-15 2009-04-29 다이요 잉키 세이조 가부시키가이샤 Black paste composition, method for black matrix pattern formation using the same, and its black matrix pattern
TWI477904B (en) * 2010-03-26 2015-03-21 Sumitomo Chemical Co Photosensitive resin composition
JP5631280B2 (en) * 2011-08-17 2014-11-26 富士フイルム株式会社 Photosensitive resin composition for photospacer and photospacer using the same
US10996518B1 (en) 2019-12-26 2021-05-04 Industrial Technology Research Institute Light switchable device

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CN103293854A (en) * 2012-02-23 2013-09-11 住友化学株式会社 Photosensitive resin composition
CN103293854B (en) * 2012-02-23 2019-05-17 住友化学株式会社 Photosensitive polymer combination
CN105068379A (en) * 2015-08-21 2015-11-18 田菱新材料（厦门）有限公司 Photosensitive resin component for silk-screen printing

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