CN101872123B - Radioactive rays sensitive resin compound, distance piece or protection film for liquid crystal display and forming method thereof - Google Patents

Radioactive rays sensitive resin compound, distance piece or protection film for liquid crystal display and forming method thereof Download PDF

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Publication number
CN101872123B
CN101872123B CN2010101677548A CN201010167754A CN101872123B CN 101872123 B CN101872123 B CN 101872123B CN 2010101677548 A CN2010101677548 A CN 2010101677548A CN 201010167754 A CN201010167754 A CN 201010167754A CN 101872123 B CN101872123 B CN 101872123B
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methyl
ether
acid
sensitive resin
resin composition
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CN101872123A (en
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中川刚志
佐野有香
坂井孝广
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JSR Corp
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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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing

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

Abstract

The invention relates to a radioactive rays sensitive resin compound, a distance piece or a protection film for a liquid crystal display and a forming method thereof. Micro concave-convex spots will not form on a coating film even if using a slit coating method. Through the method, coating can be speeded up, the compound solution can be saved and the radioactive rays sensitive resin compound for forming the radioactive rays sensitive resin compound for the liquid crystal display can be formed. The radioactive rays sensitive resin compound contains (A) alkali soluble resin, (B) polymerized unsaturated compound, (C) radioactive rays sensitive polymerization initiator and (D) a solvent with a formula (1), wherein R1 and R2 are straight or branch linked alkyl with a carbon number of 4 or 5. R1-O-R2 (1)

Description

Radiation sensitive resin composition, liquid crystal display are with partition or diaphragm and forming method thereof
Technical field
The present invention relates to the partition of radiation sensitive resin composition, liquid crystal display cells or diaphragm and forming method thereof.
Background technology
In liquid crystal display cells, keep certain in order to make two substrate distance (box gap), use partition particles such as beaded glass with regulation particle diameter, plastic bead at present.These partition particles are randomly dispersed on the transparency carrier such as glass substrate, thus if having the partition particle forming pixel region, then have and produce the phenomenon that mirrors the partition particle, the incident light scattering, the contrast of liquid crystal panel reduces such problem.Therefore, in order to address these problems, employing be by using the photoetching process of radiation sensitive resin composition, the zone beyond pixel region forms the method (patent documentation 1) of partition.
Liquid crystal display cells has on the color filter that forms on the substrate and disposes partition, and configuration thereon has the subtend substrate of counter electrode then, in the structure of box gap configuration liquid crystal molecule.Therefore, fix for the Zone Full at substrate keeps the box gap, partition must have the film thickness uniformity of height.Particularly, in liquid crystal display cells in recent years, owing at present require also to increase to the high precision int of image quality with to the servo-actuated (high speed correspondence) of high speed animation, so also more and more higher to the requirement of film thickness uniformity.
In addition, when making liquid crystal display cells,, the size of glass substrate is maximized from improving the viewpoint of productivity, the large-scale picture of adaptation.The first generation, the second generation of 370mm * 470mm, the third generation of 620mm * 750mm, 960mm * 1 of the size process 300mm * 400mm of glass substrate, the 4th generation of 100mm, 1,100mm * 1, the 5th generation of 300mm in, just becoming main flow.In addition, more need 1 from now on, 500mm * 1, the 6th generation, 1 of 850mm, 850mm * 2, the 7th generation, 2 of 100mm, 200mm * 2, the large-scale substrate size that the 8th generation of 600mm is such.
Little in the substrate size model, for example be 370mm * 470mm when following, by the spin-coating method coating, but in the method, must a large amount of radiation sensitive resin composition solution of coating, but also can't adapt to coating to large substrate.In addition, be 960mm * 1 at substrate size, when 100mm is following,, but be difficult to adapt to substrate size after the 5th generation by the coating of slit and spin-coating method.
The application pattern that adapts to the substrate size after the 5th generation is fit to use the so-called slit coating method (patent documentation 2 and 3) that applies from slit-shaped nozzle ejection composition.This slit coating method is compared with whirl coating, has the advantage of the amount that can reduce the desired composition of coating, the manufacturing cost that helps to cut down liquid crystal display cells.Yet, this slit coating method has following problem: with the substrate vacuum suction, and then under the state of some that passes through small pin supporting substrate, from the inswept coating nozzle of certain orientation, formation is filmed, so the spots that are called " vertical bar spot " of the strip that produces the spot that is called " supporting pin spot " that the spot, the supporting pin that are called " desk-top vacuum suction spot " that the hole of vacuum suction causes cause in filming, occur in the inswept direction of coating nozzle etc. become the obstruction that realizes above-mentioned height flat type.
In addition, from the viewpoint of the manufacturing cost of further reduction liquid crystal display cells, strong request reduces the amount of liquid (saving liquid) of the composition that coating will use.
[prior art document]
[patent documentation]
[patent documentation 1] TOHKEMY 2001-261761 communique
[patent documentation 2] TOHKEMY 2006-184841 communique
[patent documentation 3] TOHKEMY 2001-25645 communique
Summary of the invention
The present invention is based on the problems referred to above proposition, when even its purpose is to adopt the slit coating method as coating method, can on filming, not produce the spot of small concavo-convex formation yet, can high speed coating during slit coating, can save the solution of radiation sensitive resin composition.
In addition; also provide and to form the partition of liquid crystal display cells or the radiation sensitive resin composition of diaphragm with high sensitivity; partition or diaphragm as liquid crystal display cells; can keep the rub resistance of requirement at present; have high response rate and flexible compression performance simultaneously concurrently, particularly have the partition of liquid crystal display cells of film thickness uniformity of height or diaphragm and forming method thereof.
According to the present invention, above-mentioned purpose of the present invention and advantage, the firstth, a kind of radiation sensitive resin composition is characterized in that, comprises:
(A) 100 mass parts alkali soluble resins, this alkali soluble resin is the multipolymer of 5～60 quality % (a1) and 40～95 quality % (a2), wherein (a1) is selected from monocarboxylic acid, the compound of dicarboxylic acids and dicarboxylic acid anhydride is to be selected from (methyl) acrylic acid hydroxyalkyl acrylate (a2), (methyl) acrylic acid dihydroxy Arrcostab or (methyl) acrylic acid (6-hydroxyl hexylyloxy) Arrcostab, unsaturated compound with epoxy radicals, (methyl) acrylic acid cycloalkyl ester, (methyl) acrylic acid aryl ester, (methyl) acrylic acid aralkyl ester, the unsaturated dicarboxylic acid dialkyl, has (methyl) acrylate that contains 5 yuan of heterocycles of oxygen or contain 6 yuan of heterocycles of oxygen, at least a kind of compound of vinyl aromatic compounds and conjugated diene compound;
(B) 30～250 mass parts polymerizable unsaturated compounds;
(C) 1～60 mass parts radiation-sensitive polymerization initiator; And
(D) R shown in the following formula (1) 1And R 2Be that carbon number is 4 or 5 straight chain shape or the solvent that props up the alkyl of chain, this solvent is 5 quality %～90 quality % with respect to the amount of the whole solvents in the radiation sensitive resin composition.
R 1——O——R 2(1)
Above-mentioned purpose of the present invention and advantage, the secondth, realize by a kind of radiation sensitive resin composition, it is characterized in that: the solvent beyond the solvent shown in the following formula (1) (below, be also referred to as (E) solvent) be more than one solvents that are selected from alcohols, glycol ethers, ethylene glycol alkyl ether acetate esters, diglycol monotertiary alkyl ether, diglycol dialkyl ether, dipropylene glycol dialkyl ether, propylene-glycol monoalky lether class, propylene glycol alkyl ether acetic acid ester class, propylene glycol alkyl ether propionic acid ester, ketone, esters solvent.
Above-mentioned purpose of the present invention and advantage, the 3rd is to be that the radiation sensitive resin composition with multipolymer of epoxy radicals or (methyl) acryloxy is realized by (A) alkali soluble resin.
Above-mentioned purpose of the present invention and advantage, the 4th is to realize by the partition or the diaphragm of the liquid crystal display cells that formed by above-mentioned radiation sensitive resin composition.
Above-mentioned purpose of the present invention and advantage, the 5th is that the spacer for liquid crystal display element of the following operation by comprising the record of following order at least or the method for diaphragm realize,
(1) the above-mentioned radiation sensitive resin composition of coating forms the operation of filming on substrate,
(2) operation that this at least a portion of filming is exposed,
(3) operation that is coated with film development after will exposing, and
(4) operation of the heating of filming after will developing.
According to the present invention, a kind of radiation sensitive resin composition is provided, when even this resin combination adopts the slit coating method as coating method, can on filming, not produce the spot of small concavo-convex formation yet, can high speed coating during slit coating, the solution of radiation sensitive resin composition can be saved, the partition or the diaphragm of liquid crystal display cells can be formed with high sensitivity; And provide the partition of liquid crystal display cells or diaphragm and forming method thereof; wherein as the partition of liquid crystal display cells; can keep the rub resistance that requires at present and have high response rate concurrently and flexible compression performance, have the film thickness uniformity of height as diaphragm.
Embodiment
Below, the present invention is specifically described.
＜(A) alkali soluble resin 〉
(A) alkali soluble resin that contains in the radiation sensitive resin composition of the present invention is so long as the developer solution to using in the developing procedure described later, the preferred bases developer solution, and the alkali soluble resin with solubility, just there is no particular limitation.As this (A) alkali soluble resin, be preferably at least a alkali soluble resin with the group that is selected from carboxyl and acid anhydride's formation, more preferably have the multipolymer of epoxy radicals or (methyl) acryloxy.
Alkali soluble resin of the present invention be preferably (a1) be selected from least a kind of group that unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides constitute (below, be called compound (a1)) with the multipolymer of (a2) (a1) in addition unsaturated compound (below, be called " compound (a2) ").
As this (A) alkali soluble resin more preferred example, can list
[A1] contain compound (a1) and in 1 molecule, have at least 1 hydroxyl unsaturated compound (below, be called " compound (a2-1) ") monomer multipolymer (below, be called " multipolymer (α) ") on, make the polymkeric substance that unsaturated isocyanate reaction obtains (below, be called " polymkeric substance (A) ")
[A2] contains compound (a 1) and has the multipolymer of the monomer of the unsaturated compound of epoxy radicals (below, be called " compound (a2-2) ") (below, be called " multipolymer (β) "),
[A3] is by the multipolymer of the monomer of in addition unsaturated compound of compound (a1) and compound (a1), compound (a2-1) and compound (a2-2) (below, be called " compound (a2-3) ") formation (below, be called " multipolymer (γ) ") etc.When making multipolymer (α), can there be compound (a2-3) simultaneously, multipolymer (α) is formed the multipolymer of compound (a1), compound (a2-1) and compound (a2-3); When making multipolymer (β), except that compound (a1) and compound (a2-2), the compound (a2-3) that can also coexist, the multipolymer of formation multipolymer (β) and compound (a1), compound (a2-2) and compound (a2-3).
The compound (a1) that uses during as manufacturing multipolymer (α), multipolymer (β) and multipolymer (γ) can list for example monocarboxylic acid, dicarboxylic acids, dicarboxylic acid anhydride etc.
As above-mentioned monocarboxylic acid, can list for example acrylic acid, methacrylic acid, crotonic acid, 2-acryloxy ethyl succinic acid, 2-methacryloxyethyl succinic acid, 2-acryloxy ethyl hexahydrophthalic acid, 2-methacryloxyethyl hexahydrophthalic acid etc.; As above-mentioned dicarboxylic acids, can list for example maleic acid, fumaric acid, citraconic acid etc.; As above-mentioned dicarboxylic acid anhydride, can list the acid anhydride of above-mentioned dicarboxylic acids etc.
Among them, from the multipolymer of copolyreaction, gained deliquescent viewpoint to developer solution, preferred acrylic acid, methacrylic acid, 2-acryloxy ethyl succinic acid, 2-methacryloxyethyl succinic acid or maleic anhydride.
Compound (a1) can separately or mix use more than 2 kinds.
In multipolymer (α), multipolymer (β) and the multipolymer (γ), be preferably 5～60 quality % from the containing ratio of the repetitive of compound (a1), more preferably 7～50 quality % are preferably 8～40 quality % especially.When the containing ratio from the repetitive of compound (a1) is 5～60 quality %, can obtain the radiation sensitive resin composition of the higher equilibrium of various character grades such as radiation-sensitive, development and storage stability.
As making the compound (a2-1) that multipolymer (α) uses, can list (methyl) acrylic acid hydroxyalkyl acrylate, (methyl) acrylic acid dihydroxy Arrcostab, (methyl) acrylic acid (6-hydroxyl hexylyloxy) Arrcostab etc.
As their object lesson, can list respectively: as (methyl) acrylic acid hydroxyalkyl acrylate is for example (methyl) acrylic acid 2-hydroxyethyl ester, (methyl) acrylic acid 3-hydroxy-propyl ester, (methyl) acrylic acid 4-hydroxybutyl ester etc.; As (methyl) acrylic acid dihydroxy Arrcostab is (methyl) acrylic acid 2 for example, 3-dihydroxypropyl ester, (methyl) acrylic acid 1,3-dihydroxypropyl ester, (methyl) acrylic acid 3,4-dihydroxy butyl ester etc.; As (methyl) acrylic acid (6-hydroxyl hexylyloxy) Arrcostab is for example (methyl) acrylic acid 2-(6-hydroxyl hexylyloxy) ethyl ester, (methyl) acrylic acid 3-(6-hydroxyl hexylyloxy) propyl diester etc.
In these compounds (a2-1), from copolyreaction and with reactive viewpoint of isocyanate compound, preferred acrylic acid 2-hydroxyethyl ester, acrylic acid 3-hydroxy-propyl ester, acrylic acid 4-hydroxybutyl ester, methacrylic acid 2-hydroxyethyl ester, methacrylic acid 3-hydroxy-propyl ester, methacrylic acid 4-hydroxybutyl ester, acrylic acid 2,3-dihydroxypropyl ester, methacrylic acid 2,3-dihydroxypropyl ester, above-mentioned (methyl) acrylic acid (6-hydroxyl hexylyloxy) Arrcostab.
In compound (a2-1), above-mentioned (methyl) acrylic acid (6-hydroxyl hexylyloxy) Arrcostab and methacrylic acid 2-hydroxyethyl ester are particularly preferred from the viewpoint of compression performance that improves the development aspect and improve the partition of gained.
As the commercially available product of the potpourri of methacrylic acid 2-(6-hydroxyl hexylyloxy) ethyl ester and methacrylic acid 2-hydroxyethyl ester, can list PLACCEL FM 1D, FM2D (trade name, ダ イ セ Le chemical industry (Co., Ltd.) is made) etc. respectively.
In multipolymer (α), as above compound (a2-1) can separately or mix use more than 2 kinds.
In multipolymer (α), be preferably 1～50 quality % from the containing ratio of the repetitive of compound (a2-1), more preferably 3～40 quality % are preferably 5～30 quality % especially.When being 1～50 quality % from the containing ratio of the repetitive of compound (a2-1) and the having good stability of the multipolymer that obtains of unsaturated isocyanate compound reaction, the storage stability of the radiation sensitive resin composition of gained is good as a result.
Epoxy radicals as in the compound (a2-2) of making multipolymer (β) use can list Oxyranyle (having 1, the 2-epoxy construction), epoxypropane base (having 1, the 3-epoxy construction).
As unsaturated compound, for example can list (methyl) acrylic acid epoxy ethyl group (ring) Arrcostab, alpha-alkyl acrylic acid epoxy ethyl group (ring) Arrcostab, have the glycidyl ether compound of unsaturated link etc. with Oxyranyle; As unsaturated compound, can list (methyl) acrylate with epoxypropane base etc. with epoxypropane base.As their object lesson, can list respectively: as (methyl) acrylic acid epoxy ethyl group (ring) Arrcostab, be for example (methyl) acrylic acid glycidyl esters, (methyl) acrylic acid 2-methyl glycidyl esters, (methyl) acrylic acid 4-hydroxybutyl ester glycidol ether, (methyl) acrylic acid 3,4-epoxy butyl ester, (methyl) acrylic acid 6,7-epoxy heptyl ester, (methyl) acrylic acid 3,4-epoxycyclohexyl ester, (methyl) acrylic acid 3,4-epoxycyclohexyl methyl ester etc.; As alpha-alkyl acrylic acid epoxy ethyl group (ring) Arrcostab, be for example 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 3,4-epoxycyclohexyl ester etc.; As glycidyl ether compound, be for example adjacent vinyl benzyl glycidol ether, a vinyl benzyl glycidol ether, to vinyl benzyl glycidol ether etc. with unsaturated link; As (methyl) acrylate, be for example 3-((methyl) acryloyl-oxy ylmethyl) epoxypropane, 3-((methyl) acryloyl-oxy ylmethyl)-3-ethyl epoxypropane, 3-((methyl) acryloyl-oxy ylmethyl)-2-methyl epoxypropane, 3-((methyl) acryloxy ethyl)-3-ethyl epoxypropane, 2-ethyl-3-((methyl) acryloxy ethyl) epoxypropane, 3-methyl-3-(methyl) acryloyl-oxy ylmethyl epoxypropane, 3-ethyl-3-(methyl) acryloyl-oxy ylmethyl epoxypropane etc. with epoxypropane base.
Among them, particularly glycidyl methacrylate, methacrylic acid 2-methyl ethylene oxidic ester, methacrylic acid 3,4-epoxycyclohexyl ester, methacrylic acid 3,4-epoxycyclohexyl methyl ester, 3-methyl-3-methacryloxy methyl epoxypropane or 3-ethyl-3-methacryloxy methyl epoxypropane is preferred aspect polymerism.
When making multipolymer (β), compound (a2-2) can separately or mix use more than 2 kinds.
In multipolymer (β), be preferably 0.5～70 quality % from the containing ratio of the repetitive of compound (a2-2), more preferably 1～60 quality % is preferably 3～50 quality % especially.When being 0.5～70 quality %, can obtain harmonious higher grade the radiation sensitive resin composition of compression performance of partition of storage stability, the gained of thermotolerance, multipolymer and the radiation sensitive resin composition of multipolymer from the containing ratio of the repetitive of compound (a2-2).
That use when making multipolymer (γ) or can arbitrarily used compound (a2-3) when making multipolymer (α) and multipolymer (β), for example can list (methyl) alkyl acrylate, (methyl) acrylic acid cycloalkyl ester, (methyl) acrylic acid aryl ester, (methyl) acrylic acid aralkyl ester, unsaturated dicarboxylic acid dialkyl, have (methyl) acrylate, vinyl aromatic compounds, conjugated diene compound and other unsaturated compound that contain 5 yuan of heterocycles of oxygen or contain 6 yuan of heterocycles of oxygen.
As their object lesson, can list respectively:, be for example methyl acrylate, (methyl) acrylic acid n-pro-pyl ester, (methyl) acrylic acid isopropyl esters, (methyl) n-butylacrylate, (methyl) acrylic acid sec-butyl ester, (methyl) acrylic acid tertiary butyl ester etc. wherein as (methyl) alkyl acrylate; As (methyl) acrylic acid cycloalkyl ester, be that for example (methyl) acrylic acid cyclohexyl ester, (methyl) acrylic acid 2-methylcyclohexyl ester, (methyl) acrylic acid three encircle [5.2.1.02,6] last of the ten Heavenly stems-8-base ester, (methyl) acrylic acid 2-(three rings [5.2.1.02,6] last of the ten Heavenly stems-8-base oxygen base) ethyl ester, (methyl) acrylic acid isophorone ester etc.; As (methyl) acrylic acid aryl ester, be phenyl acrylate etc. for example; As (methyl) acrylic acid aralkyl ester, be acrylic acid benzyl ester etc. for example; As the unsaturated dicarboxylic acid dialkyl, be for example diethyl maleate, DEF etc.; As having (methyl) acrylate that contains 5 yuan of heterocycles of oxygen or contain 6 yuan of heterocycles of oxygen, be for example (methyl) acrylic acid tetrahydrofuran-2-base ester, (methyl) acrylic acid oxinane-2-base ester, (methyl) acrylic acid 2-methyl oxinane-2-base ester etc.; As vinyl aromatic compounds, be for example styrene, α-Jia Jibenyixi etc.; As conjugated diene compound, be for example 1,3-butadiene, isoprene etc.; As other unsaturated compound, be for example vinyl cyanide, methacrylonitrile, acrylamide, Methacrylamide etc.
In these compounds (a2-3), from the copolyreaction aspect, preferable methyl n-butyl acrylate, methacrylic acid 2-methyl ethylene oxidic ester, methacrylic acid benzyl ester, methacrylic acid three ring [5.2.1.0 2,6] last of the ten Heavenly stems-8-base ester, styrene, to methoxy styrene, methacrylic acid tetrahydrofuran-2-base ester, 1,3-butadiene etc.
When making multipolymer (α), multipolymer (β) and multipolymer (γ), compound (a2-3) can separately or mix use more than 2 kinds.
In multipolymer (α) and multipolymer (β), the containing ratio from the repetitive of compound (a2-3) is preferably 10～70 quality %, and more preferably 20～50 quality % are preferably 30～50 quality % especially.When the containing ratio of the repetitive of compound (a2-3) is 10～70 quality %, control the molecular weight of multipolymer easily, can obtain harmonious higher grade the radiation sensitive resin composition of development property, radioactive ray sensitivity etc.
Multipolymer (α), multipolymer (β) and multipolymer (γ) preferably in appropriate solvent, preferably in the presence of radical polymerization initiator, make the polymerization of mixtures manufacturing of aforesaid monomer.Solvent as aforementioned polymerization is used can list for example diglycol alkyl ether, propylene-glycol monoalky lether acetic acid esters, alkoxypropan acid alkyl ester, acetic acid esters etc.These solvents can separately or mix use more than 2 kinds.
As above-mentioned radical polymerization initiator, there is no particular limitation, for example can list 2,2 '-azoisobutyronitrile, 2,2 '-azo two-(2, the 4-methyl pentane nitrile), 2,2 '-azo two-azo-compounds such as (4-methoxyl-2,4-methyl pentane nitriles).These radical polymerization initiators can separately or mix use more than 2 kinds.
The weight-average molecular weight of the polystyrene conversion that multipolymer (α), multipolymer (β) and multipolymer (γ) are measured by gel permeation chromatography (GPC) (below, be called " Mw ") is preferably 2,000～100,000, and more preferably 5,000～50,000.The Mw of multipolymer (α), multipolymer (β) and multipolymer (γ) is 2,000～100,000 o'clock, can obtain balanced higher grade radiation sensitive resin composition of thermotolerance, development, radioactive ray sensitivity etc.
Polymkeric substance (A) can obtain by making the reaction of multipolymer (α) and unsaturated isocyanate compound.The multipolymer that as above obtains (α) can be directly used in polymeric reaction solution makes polymkeric substance (A), after perhaps also multipolymer (α) temporarily can being separated from solution, is used to make polymkeric substance (A).
As the unsaturated isocyanate compound, can list for example (methyl) acrylic acid derivative etc., as its object lesson, can list 2-(methyl) acryloxy ethyl isocyanate, 4-(methyl) acryloxy butyl isocyanate, (methyl) acrylic acid 2-(2-isocyanates ethoxy) ethyl ester etc.
Commercially available product as them can list respectively: wherein the commercially available product as 2-acryloxy ethyl isocyanate is カ レ Application ズ AOI (clear and electrician (Co., Ltd.) makes), as the commercially available product of 2-methacryloxyethyl isocyanates is カ レ Application ズ MOI (clear and electrician (Co., Ltd.) makes), is カ レ Application ズ MOI-EG (clear and electrician (Co., Ltd.) manufacturing) as the commodity of methacrylic acid 2-(2-isocyanates ethoxy) ethyl ester.
In these unsaturated isocyanate compounds, from and the reactive aspect of multipolymer (α), preferred 2-acryloxy ethyl isocyanate, 2-methacryloxyethyl isocyanates, 4-methacryloxy butyl isocyanate or methacrylic acid 2-(2-isocyanates ethoxy) ethyl ester.
When making polymkeric substance (A), the unsaturated isocyanate compound can separately or mix use more than 2 kinds.
The reaction of multipolymer (α) and unsaturated isocyanate compound, as required in the presence of suitable catalyzer, preferably in the solution that contains the multipolymer of polymerization inhibitor (α), under room temperature or heating, add the unsaturated isocyanate compound while stirring and carry out.As above-mentioned catalyzer, can list for example di-n-butyltin dilaurate (IV) etc.; As above-mentioned polymerization inhibitor, can list for example p methoxy phenol etc.
The usage ratio of the unsaturated isocyanate compound when making polymkeric substance (A), the hydroxyl with respect to from the compound (a2-1) in the multipolymer (α) is preferably 0.1～95mol%, and more preferably 1.0～80mol% is preferably 5.0～75mol% especially.When the usage ratio of unsaturated isocyanate compound is 0.1～95mol%, can further improve and the reactivity of multipolymer (α), the thermotolerance and the elastic property of radiation sensitive resin composition, so preferred.
In radiation sensitive resin composition of the present invention, polymkeric substance (A), multipolymer (β) and multipolymer (γ) can be distinguished use separately, but preferably polymkeric substance (A) and multipolymer (β) are used together, perhaps multipolymer (β) and multipolymer (γ) are used together.
By polymkeric substance (A) and multipolymer (β) are used together, can further improve the intensity and the thermotolerance of the partition of the storage stability of radiation sensitive resin composition of gained and gained, so preferred.Polymkeric substance (A) and multipolymer (β) when using together, as the usage ratio of polymkeric substance (A), with respect to 100 mass parts multipolymers (β), are being preferably 0.5～50 mass parts, and more preferably 1～30 mass parts is preferably 3～20 mass parts especially.When the usage ratio of polymkeric substance (A) is 0.5～50 mass parts, can obtain storage stability and the partition of gained or stable on heating harmonious higher grade the radiation sensitive resin composition of diaphragm of radiation sensitive resin composition.
On the other hand,, can obtain to improve the advantage of the storage stability of radiation-ray sensitive composition, so preferred by multipolymer (β) and multipolymer (γ) are used together.
With multipolymer (β) and multipolymer (γ) when using together, with respect to 100 mass parts multipolymers (γ), the usage ratio of multipolymer (β) is preferably 10～150 mass parts, and more preferably 20～130 mass parts are preferably 30～100 mass parts especially.
＜(B) polymerizable unsaturated compound 〉
(B) polymerizable unsaturated compound that contains in the radiation sensitive resin composition of the present invention is in the presence of (C) described later radiation-sensitive polymerization initiator, the unsaturated compound of irradiation radioactive ray polymerization.As this polymerism unsaturated monomer, there is no particular limitation, good from polymerism, as can to improve the partition of gained intensity aspect, preferred simple function, 2 officials can or 3 officials can above (methyl) acrylate.
As above-mentioned simple function (methyl) acrylate, can list for example acrylic acid 2-hydroxyethyl ester, methacrylic acid 2-hydroxyethyl ester, carbiphene acrylate, carbiphene methacrylate, (2-acryloxy ethyl) (2-hydroxypropyl) phthalic ester, (2-methacryloxyethyl) (2-hydroxypropyl) phthalic ester, ω-carboxyl polycaprolactone single-acrylate etc.As their commodity, represent with trade name, can list for example ア ロ ニ Star Network ス M-101, same M-111, same M-114, same M-5300 (above, East Asia synthetic (Co., Ltd.) makes); KAYARAD TC-110S, same TC-120S (above, Japanese chemical drug (Co., Ltd.) manufacturing); PVC ス コ one ト 158, with 2311 (more than, Osaka organic chemistry industry (Co., Ltd.) is made) etc.
As above-mentioned 2 officials energy (methyl) acrylate, can list glycol diacrylate, propylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediyl ester, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethylacrylate etc.As their commodity, represent with trade name, can list for example ア ロ ニ Star Network ス M-210, same M-240, same M-6200 (above, East Asia synthetic (Co., Ltd.) makes), KAYARADHDDA, same HX-220, same R-604 (above, Japanese chemical drug (Co., Ltd.) manufacturing), PVC ス コ one ト 260, with 312, same 335HP (above, Osaka organic chemistry industry (Co., Ltd.) is made), ラ イ ト ア Network リ レ one ト 1,9-NDA (Sakae society chemistry (Co., Ltd.) is made altogether) etc.
As above (methyl) acrylate of above-mentioned 3 officials energy, can list trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylate, dipentaerythritol five acrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol acrylate, the potpourri of dipentaerythritol five acrylate and dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylate, the dipentaerythritol acrylate of oxirane modification, three (2-acryloxy ethyl) phosphate, three (2-methacryloxyethyl) phosphate, pentaerythrite six acrylate of succinic acid modification; And have straight chain shape alkylidene and alicyclic structure and have the compound of the isocyanate group more than 2 and in molecule, have the hydroxyl more than 1 and have multifunctional urethanes acrylic ester compound that the compound reaction of 3,4 or 5 (methyl) acryloxies obtains etc.
Commodity as above (methyl) acrylate of 3 officials energy, represent with trade name, can list for example 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 (more than, make in East Asia synthetic (Co., Ltd.)), KAYARAD TMPTA, same DPHA, same DPCA-20, same DPCA-30, same DPCA-60, same DPCA-120, same DPEA-12 (more than, Japan's chemical drug (Co., Ltd.) is made), PVC ス コ one ト 295, with 300, with 360, same GPT, same 3PA, with 400 (more than, Osaka organic chemistry industry (Co., Ltd.) is made), and, can list ニ ユ one Off ロ Application テ イ ア R-1150 (the first industrial pharmacy (Co., Ltd.) manufacturing) as the commercially available product that contains multifunctional urethanes acrylic ester compound, KAYARAD DPHA-40H (Japanese chemical drug (Co., Ltd.) manufacturing) etc.
Among them, particularly preferably contain ω-carboxyl polycaprolactone single-acrylate, 1,9-nonanediol dimethylacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol five acrylate, dipentaerythritol acrylate, and the potpourri of dipentaerythritol five acrylate and dipentaerythritol acrylate, the dipentaerythritol acrylate of oxirane modification, pentaerythrite six acrylate of succinic acid modification, the commercially available product of multifunctional urethanes acrylic ester compound etc.
Aforesaid (B) polymerizable unsaturated compound can separately or mix use more than 2 kinds.
The usage ratio of (B) polymerism unsaturated monomer in the radiation sensitive resin composition of the present invention with respect to 100 mass parts (A) alkali soluble resin, is preferably 30～250 mass parts, more preferably 50～200 mass parts.When (B) consumption of polymerism unsaturated monomer was 30～250 mass parts, the thermotolerance and the elastic property of the sensitivity of radiation sensitive resin composition, the partition of gained were better.
＜(C) radiation-sensitive polymerization initiator 〉
[C] radiation-sensitive polymerization initiator that contains in the radiation sensitive resin composition of the present invention is to respond to radioactive ray, produces the composition of the spike that causes the polymerization of [B] polymerizable unsaturated compound.As this [C] radiation-sensitive polymerization initiator, can list O-acyl group oxime compound, acetophenone compound, united imidazole, benzophenone cpd etc.Object lesson as above-mentioned O-acyl group oxime compound; can list ethyl ketone-1-(9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl)-1-(O-acetyl group oxime); 1-(9-ethyl-6-benzoyl-9.H.-carbazole-3-yl) suffering-1-ketoxime-O-acetic acid esters; 1-(9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl)-second-1-ketoxime-O-benzoic ether; 1-(9-normal-butyl-6-(2-ethylamino benzonitrile acyl group)-9.H.-carbazole-3-yl)-second-1-ketoxime-O-benzoic ether; ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl group oxime); ethyl ketone-1-(9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl benzoyl)-9.H.-carbazole-3-yl)-1-(O-acetyl group oxime); ethyl ketone-1-(9-ethyl-6-(2-methyl-5-tetrahydrofuran base benzoyl)-9.H.-carbazole-3-yl)-1-(O-acetyl group oxime); ethyl ketone-1-(9-ethyl-6-{2-methyl-4-(2; 2-dimethyl-1,3-dioxolane base) the methoxybenzoyl base }-9.H.-carbazole-3-yl)-1-(O-acetyl group oxime) etc.
Among them; as preferred O-acyl group oxime compound; can list ethyl ketone-1-(9-ethyl-6-(2-methyl benzoyl)-9H-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) or ethyl ketone-1-(9-ethyl-6-{2-methyl-4-(2; 2-dimethyl-1,3-dioxolane base) the methoxybenzoyl base }-9.H.-carbazole-3-yl)-1-(O-acetyl group oxime).
These O-acyl group oxime compounds can separately or mix use more than 2 kinds.
As above-mentioned acetophenone compound, can list for example alpha-amido ketonic compound, alpha-hydroxyacetone compounds.
As the object lesson of alpha-amido ketonic compound, can list 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-Ding-1-ketone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholine-4-base-phenyl)-Ding-1-ketone, 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino third-1-ketone etc.;
As the object lesson of alpha-hydroxyacetone compounds, 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.
In these acetophenone compounds, preferred alpha-amido ketonic compound, preferred especially 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-Ding-1-ketone or 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholine-4-base-phenyl)-Ding-1-ketone.
As the object lesson of above-mentioned united imidazole, can list 2,2 '-two (2-chlorophenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline, 2,2 '-two (2-chlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4-dichloro-phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4,6-trichlorobenzene base)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc.
In these united imidazoles, preferred 2,2 '-two (2-chlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4-dichloro-phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline or 2,2 '-two (2,4,6-trichlorobenzene base)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, preferred especially 2,2 '-two (2,4-dichloro-phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline.
In radiation sensitive resin composition of the present invention, when using united imidazole as (C) radiation-sensitive polymerization initiator, can add at least a kind that is selected from aliphatics with dialkyl amido or aromatics (below, be called " amino class sensitizer ") and mercaptan compound.
Above-mentioned amino class sensitizer is to have the radioactive ray sensitivity that increases united imidazole; the compound of the function of the generation efficient of raising imidazole radical; based on the sensitivity and the resolution that improve radiation sensitive resin composition, further improve the partition that forms or diaphragm the purpose of the adaptation of substrate is added.As this amino class sensitizer, can list for example N methyldiethanol amine, 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, ESCAROL 507 ethyl ester, ESCAROL 507 isopentyl ester etc.In these amino class sensitizers, preferred especially 4,4 '-two (diethylamino) benzophenone.These amino class sensitizers can separately or mix use more than 2 kinds.
With respect to 100 mass parts united imidazoles, the addition of amino class sensitizer is preferably 0.1～50 mass parts, more preferably 1～20 mass parts.When the addition of amino class sensitizer is 0.1～50 mass parts, the effect of can improve sensitivity, resolution and adaptation.
As above-mentioned mercaptan compound is to have to provide hydroperoxyl radical to imidazole radical, thereby produces the compound of the function of the composition with sulphur free radical.United imidazole is subjected to radiation exposure, the polymerization energy of initiation of the imidazole radical that cracking produces is moderate, because the polymerization energy of initiation is not very high, if so it is directly used in the partition that forms liquid crystal display cells, then the section shape of partition might be the bad like this shape of back taper.But, by adding mercaptan compound therein, provide hydroperoxyl radical by mercaptan compound to imidazole radical, thereby change imidazole radical into neutral imidazole radicals, produce composition simultaneously with the higher sulphur free radical of polymerization energy of initiation, thus, can make the shape of partition be better suitable taper exactly.As this mercaptan compound, can list for example 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-sulfydryl-5-methoxyl benzo thiazole, 2-sulfydryl-aromatic mercaptans compounds such as 5-methoxyl benzo imidazoles; The single mercaptan compound of aliphatics such as 3-mercaptopropionic acid, 3-mercapto-propionate, 3-mercaptopropionic acid ethyl ester, 3-mercaptopropionic acid monooctyl ester; 3,6-two oxa-s-1, hot two mercaptan of 8-, pentaerythrite four (mercaptoacetate), the analiphatic sulphur alcoholic compound more than pentaerythrite four 2 officials such as (3-mercaptopropionic acid esters) energy etc.In these mercaptan compounds, preferred especially 2-mercaptobenzothiazole.
With respect to 100 mass parts united imidazoles, be preferably 0.1～50 mass parts as the addition of mercaptan compound, more preferably 1～20 mass parts.When the addition of mercaptan compound is 0.1～50 mass parts, can improve the adaptation of the partition of gained to base material, shape is good.
In radiation sensitive resin composition of the present invention, when using united imidazole, preferably add above-mentioned amino class sensitizer and mercaptan compound simultaneously as (C) radiation-sensitive polymerization initiator.
Usage ratio as (C) radiation-sensitive polymerization initiator among the present invention with respect to 100 weight portions (A) alkali soluble resin, is preferably 1～60 mass parts, more preferably 2～50 mass parts, more preferably 5～40 mass parts.
By in the scope of 1～60 mass parts, using (C) radiation-sensitive polymerization initiator, even under low exposure, also can form partition with high rigidity and adaptation.
＜(D) solvent 〉
The feature of radiation sensitive resin composition of the present invention is to contain the solvent shown in the following formula (1).
R 1——O——R 2(1)
(in the formula (1), R 1And R 2Be that carbon number is 4 or 5 straight chain shape or the alkyl that props up chain.)
Compound as formula (1) expression, can list for example two (normal-butyl) ether, two (isobutyl) ether, two (tert-butyl group) ether, (normal-butyl) isobutyl ether, normal-butyl-tertbutyl ether, isobutyl-tertbutyl ether, two (n-pentyl) ether, n-pentyl-3-methyl butyl ether, n-pentyl-2-methyl butyl ether, n-pentyl-1-methyl butyl ether, n-pentyl-2,2-dimethyl propyl ether, n-pentyl-1,2-dimethyl propyl ether, n-pentyl-1,1-dimethyl propyl ether, two (3-methyl butyl) ether, 3-methyl butyl-2-methyl butyl ether, 3-methyl butyl-1-methyl butyl ether, 3-methyl butyl-2,2-dimethyl propyl ether, 3-methyl butyl-1,2-dimethyl propyl ether, 3-methyl butyl-1,1-dimethyl propyl ether, two (2-methyl butyl) ether, 2-methyl butyl-1-methyl butyl ether, 2-methyl butyl-2,2-dimethyl propyl ether, 2-methyl butyl-1,2-dimethyl propyl ether, 2-methyl butyl-1,1-dimethyl propyl ether, two (1-methyl butyl) ether, 1-methyl butyl-2,2-dimethyl propyl ether, 1-methyl butyl-1,2-dimethyl propyl ether, 1-methyl butyl-1,1-dimethyl propyl ether, two (2, the 2-dimethyl propyl) ether, 2,2-dimethyl propyl-1,2-dimethyl propyl ether, 2,2-dimethyl propyl-1,2-dimethyl propyl ether, two (1, the 2-dimethyl propyl) ether, 1,2-dimethyl propyl-1,1-dimethyl propyl ether, two (1, the 1-dimethyl propyl) ether, normal-butyl-n-pentyl ether, normal-butyl-3-methyl butyl ether, normal-butyl-2-methyl butyl ether, normal-butyl-1-methyl butyl ether, normal-butyl-2,2-dimethyl propyl ether, normal-butyl-1,2-dimethyl propyl ether, normal-butyl-1,1-dimethyl propyl ether, isobutyl-n-pentyl ether, isobutyl-3-methyl butyl ether, isobutyl-2-methyl butyl ether, isobutyl-1-methyl butyl ether, isobutyl-2,2-dimethyl propyl ether, isobutyl-1,2-dimethyl propyl ether, isobutyl-1,1-dimethyl propyl ether, the tert-butyl group-n-pentyl ether, the tert-butyl group-3-methyl butyl ether, the tert-butyl group-2-methyl butyl ether, the tert-butyl group-1-methyl butyl ether, the tert-butyl group-2,2-dimethyl propyl ether, the tert-butyl group-1,2-dimethyl propyl ether, the tert-butyl group-1,1-dimethyl propyl ether etc.
Among them, particularly, preferably use two (normal-butyl) ether, two (isobutyl) ether, two (tert-butyl group) ether, normal-butyl-isobutyl ether, normal-butyl-tertbutyl ether, isobutyl-tertbutyl ether, two (n-pentyl) ether, n-pentyl-isoamyl ether, diisoamyl ether, two (tertiary pentyl) ether from improving the viewpoint of slit coating.
With respect to the amount of the whole solvents in the radiation sensitive resin composition, (D) content of solvent is preferably 5 quality %～40 quality %, the more preferably scope of 5 quality %～30 quality %.
When (D) solvent is 5 quality %～40 quality % with respect to the content of the amount of the whole solvents in the radiation sensitive resin composition, the viscosity of radiation sensitive resin composition and the harmony of solid component concentration be for more high-grade, and then can obtain the filming of excellent in uniformity of thickness.
In the present invention, can with the solvent beyond (D) solvent (below, be also referred to as (E) solvent) and (D) solvent use together.As this (E) solvent, can list alcohol, glycol ethers, ethylene glycol alkyl ether acetic acid esters, diglycol monotertiary alkyl ether, diglycol dialkyl ether, dipropylene glycol dialkyl ether, propylene-glycol monoalky lether, propylene glycol alkyl ether acetic acid ester, propylene glycol alkyl ether propionic ester, ketone, ester etc.
As the object lesson of these other solvents, can for example list respectively:, be phenmethylol etc. wherein as alcohol; As glycol ethers, be glycol monomethyl methyl ether, ethylene glycol monomethyl ether etc.;
As ethylene glycol alkyl ether acetic acid esters, be ethylene glycol monobutyl ether acetic acid esters, diethylene glycol monoethyl ether acetate etc.; As the diglycol monotertiary alkyl ether, be diglycol monotertiary methyl ether, carbiphene etc.;
As the diglycol dialkyl ether, be diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diglycol ethyl-methyl ether etc.;
As the dipropylene glycol dialkyl ether, be dipropylene glycol dimethyl ether, dipropylene glycol Anaesthetie Ether, dipropylene glycol ethyl-methyl ether etc.;
As propylene-glycol monoalky lether, be methyl proxitol, propylene glycol ethylether, propylene glycol propyl ether, propylene glycol butyl ether etc.;
As propylene glycol alkyl ether acetic acid ester, be methyl proxitol acetate, propylene glycol ethylether acetic acid esters etc.;
As propylene glycol alkyl ether propionic ester, be methyl proxitol propionic ester, propylene glycol ethylether propionic ester, propylene glycol propyl ether propionic ester etc.;
As ketone, be methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2 pentanone, methyl isoamyl ketone etc.;
As ester, be ethyl acetate, butyl acetate, the 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, the glycolic acid butyl ester, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, the 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c acid butyl ester, 2-butoxy methyl propionate, 2-butoxy ethyl propionate base, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-ethoxy-c propyl propionate, 3-ethoxy-c acid butyl ester, 3-propoxyl group methyl propionate etc.
Among them, preferred especially phenmethylol, diglycol ethyl-methyl ether, methyl proxitol acetate, propylene glycol ethylether acetic acid esters, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetic acid esters, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, 3-methoxypropionic acid methyl esters, 3-ethoxyl ethyl propionate, cyclohexanone, dipropylene glycol dimethyl ether, methyl proxitol propionic ester etc.
With respect to the amount of the whole solvent in the radiation sensitive resin composition, (E) content of solvent is preferably 60 quality %～95 quality %, the more preferably scope of 70 quality %～95 quality %.When (E) solvent is 60 quality %～95 quality % with respect to the content of the amount of the whole solvent in the radiation sensitive resin composition, the balanced higher grade of the viscosity of radiation sensitive resin composition and solid concentration, can obtain the more excellent radiation sensitive resin composition of high speed coating.
＜surfactant 〉
Radiation sensitive resin composition of the present invention preferably contains surfactant.Be preferably fluorochemical surfactant, silicone based surfactant as surfactant.
Be preferably endways as above-mentioned fluorochemical surfactant, at least arbitrarily the position of main chain and side chain has the compound of fluoro-alkyl and/or fluoro alkylidene, as its example, can list 1,1,2,2-tetrafluoro generation-n-octyl (1,1,2,2-tetrafluoro generation-n-pro-pyl) ether, 1,1,2,2-tetrafluoro generation-n-octyl (n-hexyl) ether, six ethylene glycol bisthioglycolates (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, eight ethylene glycol bisthioglycolates (1,1,2,2-tetrafluoro generation-normal-butyl) ether, six propylene glycol two (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, eight propylene glycol two (1,1,2,2-tetrafluoro generation-normal-butyl) ether, perfluoro-dodecyl sodium sulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-ten fluoro-n-dodecane, and fluoro-alkyl benzene sulfonic acid sodium salt, the fluoro-alkyl sodium phosphate, the fluoro-alkyl carboxylic acid sodium, two glycerine four (fluoro-alkyl polyoxyethylene ether), iodate fluoro-alkyl ammonium, the fluoro-alkyl betaine, other fluoro-alkyl polyoxyethylene ether, perfluoroalkyl polyoxy ethanol, the perfluoroalkyl alkoxide, carboxylic acid fluoroalkyl etc.
In addition, commercially available product as above-mentioned fluorochemical surfactant, can list for example BM-1000, BM-1100 (more than, BM CHEMIE company makes), メ ガ Off ア Star Network F142D, same F172, same F173, same F183, same F178, same F191, same F471, same F476 (more than, big Japanese イ Application キ chemical industry (Co., Ltd.) is made), Off タ one ジ エ Application ト FT-100, with-110, with-140A, with-150, with-250, with-251, with-300, with-310, with-400S, Off タ one ジ エ Application ト FTX-218, with-251 (more than, (Co., Ltd.) ネ オ ス makes) etc.
As above-mentioned silicone based surfactant, the surfactant that can list ト one レ シ リ コ one Application DC3PA, same DC7PA, sell with SH 11PA, 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 trade names such as (above ， East レ ダ ウ コ one ニ Application グ シ リ コ one Application (Co., Ltd.) are made).These surfactants can separately or mix use more than 2 kinds.
These surfactants can separately or mix use more than 2 kinds.With respect to 100 mass parts (A) alkali soluble resin, dosage of surfactant is 0.1～5 mass parts, more preferably 0.15～3 mass parts.When the consumption of surfactant is 0.1～5 mass parts, can reduce the inequality of filming.
＜other any adjuvant 〉
In radiation sensitive resin composition of the present invention, as required, in the scope of not damaging effect of the present invention, can also mix above-mentioned any adjuvant in addition, for example bonding agent, preserving stabilizer etc.
Above-mentioned bonding agent is to be used to improve the partition of formation and the fusible composition of substrate.
As this bonding agent, be preferably have carboxyl, the functional silanes coupling agent of methacryloxy, vinyl, isocyanate group, epoxy radicals isoreactivity functional group, as its example, can list trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-isocyanate group propyl-triethoxysilicane, γ-glycidoxypropyltrimewasxysilane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane etc.
These bonding agents can separately or mix use more than 2 kinds.With respect to 100 mass parts (A) alkali soluble resin, the consumption of bonding agent preferably with the scope of 1～20 mass parts, more preferably uses with the scope of 2～15 mass parts.When the consumption of bonding agent is the scope of 1～20 mass parts, can produce at developing procedure and to develop residually, can improve the adaptation of pattern.
As above-mentioned preserving stabilizer, can list for example sulphur, quinones, hydroquinones, polyoxygenated compound, amine, nitro nitroso compound etc.Example more specifically can list, 4-metoxyphenol, N-nitroso--N-phenyl hydramine aluminium etc.
These preserving stabilizers can separately or mix use more than 2 kinds.
With respect to 100 mass parts (A) alkali soluble resin, the preserving stabilizer consumption preferably with the scope of 0.01～10 mass parts, more preferably uses with the scope of 0.1～5 mass parts.When the consumption of preserving stabilizer was the scope of 0.01～10 mass parts, the storage stability of radiation sensitive resin composition was good.
The preparation of＜radiation sensitive resin composition 〉
Radiation sensitive resin composition of the present invention can be by at above-mentioned (A) alkali soluble resin, (B) polymerizable unsaturated compound, (C) radiation-sensitive polymerization initiator, (D) solvent and (E) in the solvent, evenly mixes other composition that as above adds arbitrarily respectively and prepares with the ratio of regulation.This radiation sensitive resin composition preferred dissolution is in appropriate solvent, with the state use of solution.
The composition solution of preparation uses filtration back uses such as the such millipore filter of aperture 0.5 μ m like this.
When radiation sensitive resin composition of the present invention is prepared as solution state, solid component concentration (composition beyond the solvent composition that occupies in the composition), just above-mentioned (A) alkali soluble resin, (B) polymerizable unsaturated compound, (C) radiation-sensitive polymerization initiator, in the ratio of the total amount of (D) solvent and other composition of (E) adding arbitrarily in the solvent, can be according to value of application target and desirable thickness etc., be set at concentration (for example, 5～50 quality %) arbitrarily.Further preferred solid component concentration is different according to form the method for filming on substrate.When adopting spin-coating method as coating method, solid component concentration is 20～50 quality % more preferably, are preferably 30～40 quality % especially.When adopting the slit coating method, solid component concentration is 10～35 quality % more preferably, are preferably 15～30 quality % especially.
The formation method of＜partition or diaphragm 〉
Then, to using radiation sensitive resin composition of the present invention, the method that forms partition or diaphragm describes.
The formation method of partition of the present invention or diaphragm can be undertaken by the following operation of carrying out following order record.
(1) operation of filming of formation radiation sensitive resin composition of the present invention on substrate,
(2) to the operation of this at least a portion of filming irradiation radioactive ray,
(3) will shine the operation that is coated with film development behind the radioactive ray, and
(4) operation of the heating of filming after will developing.
Below, these each operations are described successively.
(1) operation of filming of formation radiation sensitive resin composition of the present invention on substrate
One side at transparency carrier forms nesa coating, forms filming of radiation sensitive resin composition of the present invention on this nesa coating.
As transparency carrier used herein, can list for example glass substrate, resin substrate etc.; More specifically, can list glass substrates such as soda-lime glass, alkali-free glass; The resin substrate that forms by plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide.Nesa coating as the one side at transparency carrier is provided with can list for example by tin oxide (SnO 2) form NESA film (registered trademark of U.S. PPG company), by indium oxide-tin oxide (In 2O 3-SnO 2) the ITO film that forms etc.
When forming overlay film, can behind the solution of coating radiation sensitive resin composition of the present invention on the above-mentioned nesa coating,, form overlay film to applicator surface heating (prebake) by coating process.As the coating method of composition solution, can adopt suitable methods such as spray-on process, rolling method, method of spin coating (spin-coating method), slot coated method, scraping article rubbing method, ink-jet application method, preferred especially spin-coating method or slot coated method.Particularly when adopting the slot coated method, owing to having given play to advantageous effects of the present invention to greatest extent, so preferred.
After the coating, preferably carry out prebake and after cure.Prebake and after the condition of curing should be respectively suitably set according to the kind of the composition that contains in the radiation sensitive resin composition of the present invention, usage ratio etc.Prebake for example under 70～100 ℃, was for example carried out under such condition at 1～10 minute.After cure and can be undertaken by hot plate, suitable heating arrangement such as cleaning baking oven etc.As after the temperature of curing be preferably 180～240 ℃, more preferably 200～230 ℃.After time of curing according to the kind of the heating arrangement that uses and different.Use hot plate as after cure heating arrangement the time, after time of curing be preferably 10～60 minutes, more preferably 15～40 minutes.When using the cleaning baking oven, after the time of curing be preferably 20～120 minutes, more preferably 30～90 minutes.
The thickness of filming of Xing Chenging is preferably 0.1～8 μ m like this, more preferably 0.1～6 μ m, more preferably 0.1～5 μ m.
(2) to the operation of this at least a portion of filming irradiation radioactive ray
Then, at least a portion of the filming irradiation radioactive ray to forming.At this moment, only to the part irradiation radioactive ray of filming the time, method that can be by for example getting involved the mask irradiation with predetermined pattern etc. is carried out.
Partition or diaphragm vary in size according to the peristome of the photomask that uses, and the formation method is also different.For example, if when using the photomask of pattern mask of point-like, can form partition with 5 μ m～30 μ m.If according to pixel size, use to have the photomask that 1 limit is the above quadrangle patterns of 50 μ m, then form diaphragm.
Radioactive ray as irradiation is used can list visible rays, ultraviolet ray, far ultraviolet etc.Wherein, optimal wavelength is the interior radioactive ray of scope of 250～550nm, particularly contains the ultraviolet radioactive ray of 365nm.
The exposure of radioactive ray (exposure) is by the value of the intensity of the wavelength 365nm of the radioactive ray of illuminometer (OAI model 365, Optical Associates Inc. makes) mensuration irradiation, is preferably 100～5,000J/m 2, more preferably 200～3,000J/m 2
Radiation sensitive resin composition of the present invention is compared with at present known composition, and radioactive ray sensitivity is higher, even above-mentioned radiation exposure amount is 800J/m 2Below, also can obtain desirable thickness, excellent in shape, the adaptation of excellence and the partition or the diaphragm of high rigidity.
(3) will shine the operation that is coated with film development behind the radioactive ray
Then,, remove part (non-exposed portion) not, form the pattern of regulation the film development that is coated with behind the irradiation radioactive ray.
Developer solution as developing and using can use for example inorganic alkaline compounds such as NaOH, potassium hydroxide, sodium carbonate; The aqueous solution of organic basic compounds such as quaternary ammonium salt such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide.In the aqueous solution of above-mentioned alkali compounds, can add at least a kind of use of the group of water-miscible organic solvents such as being selected from methyl alcohol, ethanol and surfactant formation in right amount.
As developing method, can be arbitrary method such as liquid buildup method, infusion process, shower method; Development time was preferably for 10～180 seconds.Development temperature can be a normal temperature.After the development treatment, then preference such as flowing water washed after 30～90 seconds, and is air-dry by pressurized air or compressed nitrogen, can obtain desirable pattern.
(4) add the operation of filming after the thermal development
Then, with pattern-like film by suitable heating arrangements such as hot plate, baking ovens, in set point of temperature, for example 100～250 ℃ are heated the stipulated time down, for example on hot plate, heated 5～30 minutes, in baking oven, heated 30～180 minutes, can obtain having the partition of desired pattern.
Through as above operation, can be formed on the spacer for liquid crystal display element of various character excellences such as the spot that do not have small concavo-convex formation in filming, film thickness uniformity.
[embodiment]
Below, expression synthesis example and embodiment the present invention is described more specifically, but the present invention are not subjected to the qualification of these synthesis examples and embodiment.
In addition, below, weight-average molecular weight of polymkeric substance (Mw) and number-average molecular weight (Mn) are measured by the gel permeation chromatography (GPC) of following condition.
Determinator: East ソ one (Co., Ltd.) makes, " HLC 8220 シ ス テ system "
Separating column: East ソ one (Co., Ltd.) makes, 4 of the TSK gel GMHHR-N use that is connected in series
Column temperature: 40 ℃
Eluting solvent: tetrahydrofuran (making) with light Pure pharmaceutical worker industry (Co., Ltd.)
Flow velocity: 1.0mL/ branch
Sample solution concentration: 1.0 quality %
Sample injection rate IR: 100 μ m
Detecting device: differential refractometer
Standard substance: monodisperse polystyrene
In addition, the E type viscosity Meter that the solution viscosity of radiation sensitive resin composition uses Tokyo gauge (Co., Ltd.) to make measures down at 30 ℃.
＜(A) alkali soluble resin is synthetic 〉
Synthesis example 1
In the flask that has condenser pipe and stirrer, add 6 mass parts 2,2 '-azo two (2, the 4-methyl pentane nitrile), 3 parts of pentaerythrites four (3-mercaptopropionic acid ester), 250 mass parts 3-methoxypropionic acid methyl esters, and then add 14 mass parts methacrylic acids, 40 mass parts glycidyl methacrylate, 6 mass parts styrene and 35 mass parts methacrylic acids, three ring [5.2.1.0 2,6] last of the ten Heavenly stems-8-base ester, behind the nitrogen replacement, add 5 mass parts 1,3-butadienes again, slowly stir on the limit, and the limit rises to 70 ℃ with solution temperature, keeps this temperature to carry out polymerization in 4 hours, obtains the copolymer solution of solid component concentration 28.1%.With it as multipolymer (A-1).The Mw of the multipolymer of gained (A-1) is 10,500.
Synthesis example 2
In the flask that has condenser pipe, stirrer, add 5 mass parts 2,2 '-azoisobutyronitrile, 250 mass parts propylene glycol monomethyl ether, and then add 18 mass parts methacrylic acids, 25 mass parts methacrylic acids, three ring [5.2.1.0 2,6] last of the ten Heavenly stems-8-base ester, 5 mass parts styrene, 30 mass parts methacrylic acid 2-hydroxyethyl esters, 22 mass parts methacrylic acid benzyl esters, behind the nitrogen replacement, slowly stir on the limit, the limit rises to 70 ℃ with solution temperature, keep this temperature to carry out polymerization in 5 hours, obtain the solution of the multipolymer (α-1) of solid component concentration 28.8%.
When using GPC to measure the Mw of multipolymer (α-1) of gained, be 13,000.
Then, in aforementioned multipolymer (α-1) solution, add 12 mass parts 3-methacryloxyethyl isocyanates (trade name カ レ Application ズ MOI, clear and electrician (Co., Ltd.) makes), behind the 0.1 mass parts 4-metoxyphenol, 40 ℃ of down reactions 1 hour, then 60 ℃ of following stirring reactions 2 hours.Can confirm to react by IR (infrared ray absorbing) spectrum from the isocyanate group of 3-methacryloxyethyl isocyanates and the hydroxyl of multipolymer (α-1).40 ℃ of down reactions after 1 hour, again 60 ℃ of reactions after 2 hours down, the IR spectrum of assaying reaction solution is from the 2270cm of the isocyanate group of 3-methacryloxyethyl isocyanates -1Near peak reduces, and carries out thereby can confirm to react.Obtain polymkeric substance (A-1) solution of solid component concentration 31.0%.With it as polymkeric substance (A-1).
Synthesis example 3
In the flask that has condenser pipe and stirrer, add 6 mass parts 2,2 '-azo two (isobutyronotrile), 250 mass parts 3-methoxypropionic acid methyl esters, and then add 14 mass parts methacrylic acids, 20 mass parts methacrylic acid tetrahydro furfuryl esters, 5 mass parts styrene and 56 mass parts methacrylic acid benzyl esters, behind the nitrogen replacement, add 5 mass parts 1 again, the 3-butadiene, slowly stir on the limit, the limit rises to 70 ℃ with solution temperature, keep this temperature to carry out polymerization in 5 hours, obtain (A) copolymer solution of solid component concentration 27.9%.With it as multipolymer (A-2).The Mw of the multipolymer of gained (A-2) is 11,400.
Synthesis example 4
In the flask that has condenser pipe and stirrer, add 6 mass parts 2,2 '-azo two (isobutyronotrile) and 250 mass parts 3-methoxypropionic acid methyl esters, and then add 5 mass parts styrene, 14 mass parts methacrylic acids, 33 mass parts methacrylic acid benzyl esters and 23 mass parts methacrylic acid n-butyl, 20 mass parts 3-(methacryloxy methyl)-3-ethyl epoxypropane, behind the nitrogen replacement, add 5 mass parts 1 again, the 3-butadiene, slowly stir on the limit, the limit rises to 80 ℃ with solution temperature, keep this temperature to carry out polymerization in 4 hours, obtain (A) copolymer solution of solid component concentration 27.9%.With it as multipolymer (A-3).
When measuring the Mw of multipolymer (A-3) of gained with GPC, be 11,200.
Embodiment 1～19 and comparative example 1～3
(I) preparation of radiation sensitive resin composition
Add the solution that is scaled the multipolymer (A-1) that above-mentioned synthesis example 1 that multipolymer (A-1) is equivalent to the amount of 100 mass parts (solid constituent) obtains as (A) alkali soluble resin; as the 150 mass parts dipentaerythritol acrylates of (B) polymerizable unsaturated compound and potpourri (the trade name KAYARAD DPHA of dipentaerythritol five acrylate; Japan's chemical drug (Co., Ltd.) is made); 40 mass parts succinic acid modification pentaerythrites, six acrylate; 10 mass parts ω-carboxyl polycaprolactone single-acrylate (trade name ア ロ ニ Star Network ス M-5300 (East Asia synthetic (Co., Ltd.) makes); 10 mass parts ethyl ketone-1-(9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl)-1-(O-acetyl group oxime) (" イ Le ガ キ ユ ア OXE02 " that チ バ ス ペ シ ヤ Le テ イ one ケ ミ カ Le ズ company makes) as (C) radiation-sensitive polymerization initiator; 3 mass parts 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholino 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 company makes); 3 mass parts 2; 2 '-two (2-chlorophenyls)-4; 4 '; 5; 5 '-tetraphenyl-1; 2 '-bisglyoxaline; 185 mass parts diisoamyl ethers as (D) solvent; 500 mass parts 3-methoxypropionic acid methyl esters as (E) solvent; 5 mass parts γ-glycidoxypropyltrimewasxysilane; 0.2 mass parts Off タ, one ジ エ Application ト FTX-218 ((Co., Ltd.) ネ オ ス manufacturing) as surfactant; dissolving is so that after solid component concentration is 23.5 quality %; millipore filter by aperture 0.5 μ m filters, the preparation radiation sensitive resin composition.The viscosity of the radiation sensitive resin composition after the preparation is 3.0 (mPas).
The radiation sensitive resin composition of above-mentioned preparation is estimated according to following order.The result as shown in Table 1 and Table 2.
(1) mensuration of the viscosity of composition solution
(eastern machine industry (Co., Ltd.) is made, and VISCONICELD.R), measures down at 25 ℃ to use E type viscosity meter.The result as shown in Table 1 and Table 2.
(2) mensuration of the solid component concentration in the composition solution
Precision weighing 0.3g composition solution in the aluminium oxide vessel, add about 1g diethylene glycol dimethyl ether after, under 175 ℃, on hot plate dry 60 minutes, try to achieve solid component concentration by the weight before and after dry.
Here, owing to be the ratio of the nonrecoverable amount of liquid of slot coated, so when composition viscosity was consistent with 3.0mPas, under the lower situation of solid component concentration, the liquid quantitative change of use was many with respect to solid component concentration.Therefore, when the viscosity of composition was consistent with 3.0mPas, solid component concentration was under the situation below 23%, can judge that the nonrecoverable amount of liquid of slot coated is more, can't realize solving the effect of solution.The result as shown in Table 1 and Table 2.
(3) evaluation of coating (spot of vertical bar spot, smog spot, pin vestige)
On glass at the formation chromium film of 550mm * 650mm, use the composition solution of squash type spreader (slit die coater) (chemical industry (Co., Ltd.) manufacturing is answered in TR632105-CL, Tokyo) coating preparation, drying under reduced pressure is behind 0.5Torr, on hot plate, under 100 ℃, prebake 2 minutes, formation is filmed, then 2,000J/m 2Exposure under expose, form the film of the thickness 4 μ m above the glass that forms the chromium film.
By sodium vapor lamp irradiation film surface, the film surface of Visual Confirmation coating.Confirm that clearly the vertical bar spot is arranged (the coating direction or and the direction of its intersection on 1 or the spot of many straight lines), during the spot (spot of the point-like that on the base plate supports pin, forms) of smog spot (cloud form spot), pin vestige, note does *; Only confirm to have when a small amount of note to make △; When almost not finding, note does zero; When not having discovery that the spot of vertical bar spot, smog spot, pin vestige is arranged, note is made ◎.The result as shown in Table 1 and Table 2.
(4) evaluation of coating (homogeneity)
The thickness of filming in the formation on glass that forms the chromium film of above-mentioned manufacturing, (KLA Tencor company makes, and AS200) measures to use the probe-type analyzer.
Film thickness gauge by 9 measuring points is calculated homogeneity.Suppose that the short-axis direction with substrate is that X, long axis direction are Y, described 9 measuring points are that (X[mm], Y[mm]) is (275,20), (275,30), (275,60), (275,100), (275,325), (275,550), (275,590), (275,620), (275,630).Be shown below as inhomogeneity computing formula.The FT of following formula (X, Y) max is the maximal value in the thickness of 9 measuring points, the minimum value in the thickness that FT (X, Y) min is 9 measuring points, and FT (X, Y) avg. is the mean value in the thickness of 9 measuring points.Homogeneity is 2% when following, can judge that film thickness uniformity is good.The result as shown in Table 1 and Table 2.
(inhomogeneity computing formula)
Homogeneity (%)={ FT (X, Y) max-FT (X, Y) min} * 100/{2 * FT (X, Y) avg.}
(5) evaluation of high-speed coating
Use the slot coated device on the alkali-free glass substrate of 550mm * 650mm, to apply, as the coating condition is that the distance (GAP) of base material and nozzle is 150 μ m, in order to make the thickness after the exposure is 2.5 μ m, from nozzle ejection coating liquid, the translational speed of nozzle changes in the scope of 120mm/sec.～220mm/sec., tries to achieve the maximal rate that does not have to produce the strip spot that disconnected liquid causes.At this moment, even the above speed of 200mm/sec. when also not producing the strip spot, is judged as and can adapts to high-speed coating.The result as shown in Table 1 and Table 2.
(6) evaluation of sensitivity
On the alkali-free glass substrate of 95mm * 95mm, use spin-coating method, behind the coating radiation sensitive resin composition, on 90 ℃ hot plate, prebake 3 minutes forms filming of thickness 3.5 μ m.
Then, on the filming of gained, the circular pattern by forming diameter 12 μ m is as the photomask of peristome, and the intensity by 365nm is 250W/m 2Ultraviolet ray, change time shutter, exposure, afterwards, the potassium hydroxide aqueous solution by 0.05%, 25 ℃ developed 60 seconds down after, with pure water washing 1 minute, then in 230 ℃ baking oven, after cured 30 minutes, form partition.At this moment, with after residual film ratio (thickness after the thickness after afterwards curing * 100/ exposure) after curing be the minimum exposure amount more than 90%, as sensitivity.The exposure of this moment is 800J/m 2Below, think that then sensitivity is good.The result as shown in Table 1 and Table 2.
(7) evaluation of wearing quality
Except exposure for be equivalent to the exposure of " evaluation of (6) sensitivity " definite sensitivity and " evaluation of (6) sensitivity " similarly, on substrate, form partition.On the substrate of gained, be coated with the application printing machine by liquid crystal orientation film, behind the coated with liquid crystal alignment agent AL3046 (trade name, JSR (Co., Ltd.) make), 180 ℃ dry 1 hour down, form the filming of aligning agent for liquid crystal of thickness 0.05 μ m.
Then, the rubbing machine of the roller of the cloth by having the polyamide system of having reeled is under the condition of 1cm/sec. at roller revolution 500rpm, moving speed of table, this is filmed carry out friction treatment.At this moment, the affirmation pattern has or not wearing and tearing or peels off.The result as shown in Table 1 and Table 2.
(8) evaluation of compression performance
With above-mentioned " evaluation of (6) sensitivity " similarly, be exposure more than 90% with residual film ratio, on substrate, form the circular pattern of residue.This pattern is in slight compression testing machine (Off イ Star シ ヤ one ス コ one プ H100C (manufacturing of Off イ Star シ ヤ one イ Application ス ト Le メ Application Star)), use the plane pressure head of the length of side 50 μ m, by the heavy burden of 40mN, carry out compression test, measure the compression displacement amount with respect to the variation of bearing a heavy burden.At this moment, the displacement when displacement during by load 40mN and the load of removing 40mN is calculated response rate (%).At this moment, response rate is more than 90%, and the displacement during heavy burden 40mN is 0.15 μ m when above, thinks to have to have the high response rate and the partition of flexible compression performance concurrently.The result as shown in Table 1 and Table 2.
Figure GSA00000102604300341
Figure GSA00000102604300351
(B) composition
B-1: the potpourri of dipentaerythritol acrylate and dipentaerythritol five acrylate (trade name KAYARAD DPHA, Japanese chemical drug (Co., Ltd.) are made)
B-2: polyfunctional acrylic ester based compound (trade name KAYARADDPHA-40H, Japanese chemical drug (Co., Ltd.) is made)
B-3: succinic acid modification pentaerythrite six acrylate
B-4: ω-carboxyl polycaprolactone single-acrylate (trade name ア ロ ニ Star Network ス M-5300 (East Asia synthetic (Co., Ltd.) makes)
(C) composition
C-1: ethyl ketone, 1-(9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl)-, 1-(O-acetyl group oxime) (trade name イ Le ガ キ ユ ア OXE02, チ バ ス ペ シ ヤ Le テ イ one ケ ミ カ Le ズ company makes)
C-2:2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholino 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 company make)
C-3:2,2 '-two (2-chlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline
C-4:4,4 '-two (diethylamino) benzophenone
The C-5:2-mercaptobenzothiazoler
(D) composition
D-1: diisoamyl ether
D-2: two (n-pentyl) ether
D-3: two (normal-butyl) ether
(E) composition
E-1:3-methoxypropionic acid methyl esters
E-2: propylene glycol monomethyl ether
E-3: diglycol ethyl-methyl ether
E-4: cyclohexanone
E-5: dipropylene glycol dimethyl ether
E-6: phenmethylol
E-7: the ethylene glycol monobutyl ether acetic acid esters,
E-8: methyl proxitol propionic ester

Claims (10)

1. a radiation sensitive resin composition is characterized in that, comprises:
(A) 100 mass parts alkali soluble resins, this alkali soluble resin is the multipolymer of 5～60 quality % (a1) and 40～95 quality % (a2), wherein (a1) is selected from acrylic acid, methacrylic acid, crotonic acid, 2-acryloxy ethyl succinic acid, 2-methacryloxyethyl succinic acid, 2-acryloxy ethyl hexahydrophthalic acid, 2-methacryloxyethyl hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, or at least a kind of compound of the acid anhydride of above-mentioned dicarboxylic acids, be to be selected from (methyl) acrylic acid hydroxyalkyl acrylate (a2), (methyl) acrylic acid dihydroxy Arrcostab or (methyl) acrylic acid (6-hydroxyl hexylyloxy) Arrcostab, unsaturated compound with epoxy radicals, (methyl) acrylic acid cycloalkyl ester, (methyl) acrylic acid aralkyl ester, has (methyl) acrylate that contains 5 yuan of heterocycles of oxygen or contain 6 yuan of heterocycles of oxygen, at least a kind of compound of vinyl aromatic compounds and conjugated diene compound;
(B) 30～250 mass parts polymerizable unsaturated compounds;
(C) 1～60 mass parts radiation-sensitive polymerization initiator; And
(D) R shown in the following formula (1) 1And R 2Be that carbon number is 4 or 5 straight chain shape or the solvent that props up the alkyl of chain, this solvent is 5 quality %～90 quality % with respect to the amount of the whole solvents in the radiation sensitive resin composition;
R 1-O-R 2(1)。
2. the radiation sensitive resin composition of putting down in writing according to claim 1, it is characterized in that: comprise at least a above (E-1) solvent that is selected from diglycol dialkyl ether, propylene glycol alkyl ether acetic acid ester class, ketone, esters solvent, and the solvent of following formula (1).
3. the radiation sensitive resin composition of putting down in writing according to claim 1, it is characterized in that: comprise (E-2) solvent more than a kind that is selected from alcohols, glycol ethers, ethylene glycol alkyl ether acetate esters, diglycol monotertiary alkyl ether, dipropylene glycol dialkyl ether, propylene-glycol monoalky lether class, propylene glycol alkyl ether propionic acid ester, and the solvent of following formula (1).
4. the radiation sensitive resin composition of putting down in writing according to claim 2 is characterized in that: (E-1) solvent is more than one the solvent that is selected from diglycol ethyl-methyl ether, diethylene glycol dimethyl ether, methyl proxitol acetate, propylene glycol ethylether acetic acid esters, 3-methoxypropionic acid methyl esters, 3-ethoxyl ethyl propionate, cyclohexanone.
5. the radiation sensitive resin composition of putting down in writing according to claim 3 is characterized in that: (E-2) solvent is more than one the solvent that is selected from phenmethylol, ethylene glycol monobutyl ether acetic acid esters, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, methyl proxitol propionic ester.
6. the radiation sensitive resin composition of putting down in writing according to claim 1, it is characterized in that: (A) alkali soluble resin is the multipolymer with epoxy radicals or (methyl) acryloxy.
7. the radiation sensitive resin composition of putting down in writing according to claim 6 is characterized in that: (C) a kind of O-of being acyl group oxime compound of radiation-sensitive polymerization initiator.
8. according to each radiation sensitive resin composition of being put down in writing of claim 1～7, it is used to form the partition or the diaphragm of liquid crystal display cells.
9. the partition or the diaphragm of the liquid crystal display cells that forms of the radiation sensitive resin composition of putting down in writing by claim 8.
10. the formation method of spacer for liquid crystal display element or diaphragm is characterized in that: comprise the following operation of following order record at least,
(1) radiation sensitive resin composition of coating claim 8 record forms the operation of filming on substrate,
(2) operation that this at least a portion of filming is exposed,
(3) operation that is coated with film development after will exposing, and
(4) operation of the heating of filming after will developing.
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