CN101622577A - Radiation sensitive resin composition, spacer for liquid crystal display element and diaphragm and their formation method - Google Patents

Abstract

For example two (the 1-oxyls-2 of multipolymer, [B] polymerizable unsaturated compound, [C] radiation-sensitive polymerization initiator and [D] nitroxyl compound that contains [A] unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides and be different from their other unsaturated compound; 2; 6,6-tetramethyl piperidine-4-yl) radiation sensitive resin composition of sebacate.The radiation sensitive resin composition that can form fine pattern, exploring excellent performance is provided.

Description

Radiation sensitive resin composition, spacer for liquid crystal display element and diaphragm and their formation method

Technical field

The present invention relates to particularly very preferred radiation sensitive resin composition, spacer and diaphragm and their formation method and liquid crystal display cells in the formation of the spacer of liquid crystal display cells and diaphragm.

Background technology

In liquid crystal display cells, keep certain in order to make the interval (box gap (セ Le ギ ヤ Star プ)) between 2 plate bases, all use spacers such as beaded glass with regulation particle diameter, plastic bead all the time.These spacers are dispersed on the transparency carriers such as glass substrate randomly, therefore, there is spacer if pixel forms the zone, the phenomenon that spacer shows (writing り こ む) then can take place, the problem that perhaps incident light is scattered, the contrast of liquid crystal display cells descends.

In order to solve this type of problem, people have adopted the method that forms spacer by photoetch method.This method is that radiation sensitive resin composition is coated on the substrate, via the mask exposure ultraviolet ray etc. of regulation, develops then, forms the spacer of point-like or striated.Because this method only assigned position beyond pixel forms the zone forms spacer, has therefore solved the problems referred to above (with reference to TOHKEMY 2001-302712 communique) substantially.

But in recent years, in order to improve image quality, liquid crystal display cells is high-definition constantly.Therefore be accompanied by the high-definition of liquid crystal display cells, the size of each pixel diminishes, and begins the radiation sensitive resin composition that requirement is used to form spacer and can form than more fine in the past pattern.To being used to form the radiation sensitive resin composition that the pixel that only is covered forms the diaphragm in zone, it can form than more fine in the past pattern equally also to begin requirement.

The problem that faces when forming fine pattern is: light diffusion and scattering that diffraction phenomena that the light of exposure partly takes place in mask open and radiation sensitive resin composition itself make exposure.Promptly; when using the radiation sensitive resin composition of so-called minus to form spacer or diaphragm; diffraction of light, diffusion and the scattering of exposure make than originally the exposure area---the wider scope of opening portion of mask is exposed; therefore the size of the pattern that forms is obviously thick than the size of mask open part, is difficult to form required fine pattern.

Photopolymerization reaction that cause for diffraction of light, diffusion and the scattering that suppresses above-mentioned exposure, the radiation sensitive resin composition outside exposure area originally all uses the compound that contains phosphorus or sulphur all the time or contains the radiation sensitive resin composition of hydroquinone derivatives etc.But though these compounds produce effect aspect the fine pattern forming, sensitivity significantly reduces, and is not suitable for requiring the radiation sensitive resin composition of highly sensitive used for liquid crystal display element.

Summary of the invention

Problem of the present invention is to provide the radiation sensitive resin composition that can form fine pattern, exploring excellent performance.

Other problem of the present invention is to provide the liquid crystal display that formed by above-mentioned radiation sensitive resin composition with spacer or diaphragm and the liquid crystal display cells that possesses them.

Another problem of the present invention is to provide the formation method of above-mentioned liquid crystal display with spacer or diaphragm.

According to the present invention, the first aspect of above-mentioned problem is solved by radiation sensitive resin composition, and this radiation sensitive resin composition is characterised in that: contain [A] and (a1) be selected from least a of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides and (a2) multipolymer of (a1) unsaturated compound in addition; [B] polymerizable unsaturated compound; [C] radiation-sensitive polymerization initiator; And [D] nitroxyl compound.

According to the present invention, the second aspect of above-mentioned problem is solved by spacer for liquid crystal display element or the diaphragm that is formed by above-mentioned each radiation sensitive resin composition.

According to the present invention, the third aspect of above-mentioned problem is solved by the formation method of spacer for liquid crystal display element or diaphragm, the method is characterized in that: comprise following at least step in the following order:

(1) on substrate, form the tunicle of above-mentioned radiation sensitive resin composition step,

(2) at least a portion of this tunicle carry out step of exposing,

(3) to the exposure after this tunicle carry out step of developing and

(4) step that this tunicle after developing is heated.

According to the present invention, the fourth aspect of above-mentioned problem is solved by liquid crystal display cells, and this liquid crystal display cells possesses above-mentioned spacer for liquid crystal display element or diaphragm or both.

The best mode that carries out an invention

＜radiation sensitive resin composition 〉

Below each composition of radiation sensitive resin composition of the present invention is elaborated.

[A] multipolymer

[A] multipolymer that contains in the radiation sensitive resin composition of the present invention is (a1) at least a (hereinafter referred to as " compound (a1) ") of being selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides and (a2) and (a1) multipolymer of different other unsaturated compounds (hereinafter referred to as " compound (a2) ").Among the present invention, [A] multipolymer is preferably selected from least a of following [A1] and [A2]: [A1] is the polymkeric substance (hereinafter referred to as " [A] polymkeric substance ") that multipolymer (hereinafter referred to as " multipolymer [α] ") reaction that has the unsaturated compound (hereinafter referred to as " compound (a2-1) ") of 1 hydroxyl in unsaturated isocyanate compound and compound (a1) and 1 molecule is at least obtained; [A2] is compound (a1) and the multipolymer (hereinafter referred to as " multipolymer [β] ") with unsaturated compound (hereinafter referred to as " compound (a2-2) ") of Oxyranyle or oxa-cyclobutyl.

Compound (a1) for example has:

Monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, succinic acid 2-acryloxy ethyl ester, succinic acid 2-methacryloxyethyl ester, hexahydrophthalic acid 2-acryloxy ethyl ester, hexahydrophthalic acid 2-methacryloxyethyl ester;

Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;

The acid anhydrides of above-mentioned dicarboxylic acids etc.

In these compounds (a1), the dissolubility of alkaline developer and the angle that obtains are easily considered preferred acrylic acid, methacrylic acid, succinic acid 2-acryloxy ethyl ester, succinic acid 2-methacryloxyethyl ester, maleic anhydride etc. from copolyreaction, resulting polymers and multipolymer.

In multipolymer [α] and the multipolymer [β], compound (a1) can use separately or with mixing more than 2 kinds.

In multipolymer [α] and the multipolymer [β], from the preferred 5-60 weight of the containing ratio % of the repetitive of compound (a1), further preferred 10-50 weight %, preferred especially 15-40 weight %.Containing ratio from the repetitive of compound (a1) is lower than 5 weight %, and then resulting polymers has the tendency of reduction to the dissolubility of alkaline developer, and surpasses 60 weight %, and then this polymkeric substance probably can be excessive to the dissolubility of alkaline developer.

Compound (a2-1) for example has:

(methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxyl butyl ester, (methyl) acrylic acid 5-hydroxyl pentyl ester, the own ester of (methyl) acrylic acid 6-hydroxyl, (methyl) acrylic acid 7-hydroxyl heptyl ester, (methyl) acrylic acid 8-hydroxyl monooctyl ester, (methyl) acrylic acid 9-hydroxyl ester in the ninth of the ten Heavenly Stems, (methyl) acrylic acid 10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) acrylic acid 11-hydroxyl undecyl ester, (methyl) acrylic acid hydroxyalkyl acrylates such as (methyl) acrylic acid 12-hydroxyl dodecyl ester;

(methyl) acrylic acid 4-hydroxyl-cyclohexyl, (methyl) acrylic acid 4-hydroxymethyl-cyclohexyl methyl esters, (methyl) acrylic acid 4-hydroxyethyl-cyclohexyl ethyl ester, (methyl) acrylic acid 3-hydroxyl-dicyclo [2.2.1] heptan-5-alkene-2-base ester, (methyl) acrylic acid 3-hydroxymethyl-dicyclo [2.2.1] heptan-5-alkene-2-base methyl esters, (methyl) acrylic acid 3-hydroxyethyl-dicyclo [2.2.1] heptan-5-alkene-2-base ethyl ester, (methyl) acrylic acid 8-hydroxyl-dicyclo [2.2.1] heptan-5-alkene-2-base ester, (methyl) acrylic acid 2-hydroxyl-octahydro-4,7-methylene-indenes-5-base ester, (methyl) acrylic acid 2-hydroxymethyl-octahydro-4,7-methylene-indenes-5-ylmethyl ester, (methyl) acrylic acid 2-hydroxyethyl-octahydro-4,7-methylene-indenes-5-base ethyl ester, (methyl) acrylic acid 3-hydroxyadamantane-1-base ester, (methyl) acrylic acid 3-hydroxymethyl-diamantane-1-base methyl esters, (methyl) acrylic acid 3-hydroxyethyl-diamantane-1-base ethyl ester etc. has (methyl) acrylic acid hydroxyalkyl acrylate of ester ring type structure;

(methyl) acrylic acid 1,2-dihydroxy ethyl ester, (methyl) acrylic acid 2,3-dihydroxy propyl ester, (methyl) acrylic acid 1,3-dihydroxy propyl ester, (methyl) acrylic acid 3,4-dihydroxy butyl ester, (methyl) acrylic acid 3-[3-(2,3-dihydroxy propoxyl group)-2-hydroxyl propoxyl group]-(methyl) acrylic acid dihydroxy Arrcostabs such as 2-hydroxy propyl ester;

Acrylic acid (6-hydroxyl hexylyloxy) Arrcostabs such as acrylic acid 2-(6-hydroxyl hexylyloxy) ethyl ester, acrylic acid 3-(6-hydroxyl hexylyloxy) propyl ester, acrylic acid 4-(6-hydroxyl hexylyloxy) butyl ester, acrylic acid 5-(6-hydroxyl hexylyloxy) pentyl ester, the own ester of acrylic acid 6-(6-hydroxyl hexylyloxy);

Methacrylic acid (6-hydroxyl hexylyloxy) Arrcostabs such as methacrylic acid 2-(6-hydroxyl hexylyloxy) ethyl ester, methacrylic acid 3-(6-hydroxyl hexylyloxy) propyl ester, methacrylic acid 4-(6-hydroxyl hexylyloxy) butyl ester, methacrylic acid 5-(6-hydroxyethyl hexylyloxy) pentyl ester, the own ester of methacrylic acid 6-(6-hydroxyl hexylyloxy) etc. (following above-mentioned (methyl) acrylic acid (6-hydroxyl hexylyloxy) Arrcostab is called " other compound (a2-1) ").

In these compounds (a2-1), consider from copolyreaction with reactive angle of isocyanate compound, preferred acrylic acid 2-hydroxy methacrylate, acrylic acid 3-hydroxy propyl ester, acrylic acid 4-hydroxyl butyl ester, 2-hydroxyethyl methacrylate, methacrylic acid 3-hydroxy propyl ester, methacrylic acid 4-hydroxyl butyl ester, acrylic acid 4-hydroxymethyl-cyclohexyl methyl esters, methacrylic acid 4-hydroxymethyl-cyclohexyl methyl esters, acrylic acid 2,3-dihydroxy propyl ester, methacrylic acid 2,3-dihydroxy propyl ester, other compound (a2-1) etc.

In the compound (a2-1), consider preferred especially other compound (a2-1) from the angle of the raising of the compression performance of the raising of development or gained spacer.In other compound (a2-1), preferred especially acrylic acid 2-(6-hydroxyl hexylyloxy) ethyl ester, methacrylic acid 2-(6-hydroxyl hexylyloxy) ethyl ester.Commodity for example PLACCEL FM1D, FM2D's (ダ イ セ Le chemical industry (strain) system) by name can have been bought in the commercial goods of the potpourri of methacrylic acid 2-(6-hydroxyl hexylyloxy) ethyl ester and 2-hydroxyethyl methacrylate.

In the multipolymer [α], compound (a2-1) can use separately or with mixing more than 2 kinds.

In the multipolymer [α], be preferably 1-50 weight %, further preferred 3-40 weight %, preferred especially 5-30 weight % from the containing ratio of the repetitive of compound (a2-1).Containing ratio from the repetitive of compound (a2-1) is lower than 1 weight %, then the importing rate of unsaturated isocyanate compound in polymkeric substance reduces, sensitivity has the tendency of reduction, and surpass 50 weight %, then the storage stability by the polymkeric substance that obtains with the reaction of unsaturated isocyanate compound has the tendency of reduction.

Compound (a2-2) in the multipolymer [β] for example has:

(methyl) acrylic acid glycidyl esters, (methyl) acrylic acid 2-methyl glycidyl esters, 4-hydroxybutyl (methyl) acrylate glycidyl ether, (methyl) acrylic acid 3,4-epoxy radicals butyl ester, (methyl) acrylic acid 6,7-epoxy radicals heptyl ester, (methyl) acrylic acid 3,4-epoxy radicals cyclohexyl, (methyl) acrylic acid 3, (methyl) acrylic acid epoxy base (ring) Arrcostabs such as 4-epoxy radicals cyclohexyl methyl esters;

α-Yi Jibingxisuan glycidyl esters, α-n-pro-pyl acrylic acid glycidyl esters, α-normal-butyl acrylic acid glycidyl esters, α-Yi Jibingxisuan 6,7-epoxy radicals heptyl ester, α-Yi Jibingxisuan 3, other alpha-alkyl acrylic acid epoxy base (ring) Arrcostabs such as 4-epoxy radicals cyclohexyl;

Neighbour-vinyl benzyl glycidyl ether ,-vinyl benzyl glycidyl ether, right-glycidyl ethers such as vinyl benzyl glycidyl ether;

3-(methacryloxy methyl) oxetanes, 3-(methacryloxy methyl)-3-ethyl oxetanes, 3-(methacryloxy methyl)-2-methyl oxetanes, 3-(methacryloxy methyl)-2-trifluoromethyl oxetanes, 3-(methacryloxy methyl)-2-pentafluoroethyl group oxetanes, 3-(methacryloxy methyl)-2-phenyl oxetanes, 3-(methacryloxy methyl)-2,2-difluoro oxetanes, 3-(methacryloxy methyl)-2,2,4-trifluoro oxetanes, 3-(methacryloxy methyl)-2,2,4,4-tetrafluoro oxetanes, 3-(methacryloxyethyl) oxetanes, 3-(methacryloxyethyl)-3-ethyl oxetanes, 2-ethyl-3-(methacryloxyethyl) oxetanes, 3-(methacryloxyethyl)-2-trifluoromethyl oxetanes, 3-(methacryloxyethyl)-2-pentafluoroethyl group oxetanes, 3-(methacryloxyethyl)-2-phenyl oxetanes, 2,2-two fluoro-3-(methacryloxyethyl) oxetanes, 3-(methacryloxyethyl)-2,2,4-trifluoro oxetanes, 3-(methacryloxyethyl)-2,2,4, methacrylates such as 4-tetrafluoro oxetanes;

3-(acryloyl-oxy ylmethyl) oxetanes, 3-(acryloyl-oxy ylmethyl)-3-ethyl oxetanes, 3-(acryloyl-oxy ylmethyl)-2-methyl oxetanes, 3-(acryloyl-oxy ylmethyl)-2-trifluoromethyl oxetanes, 3-(acryloyl-oxy ylmethyl)-2-pentafluoroethyl group oxetanes, 3-(acryloyl-oxy ylmethyl)-2-phenyl oxetanes, 3-(acryloyl-oxy ylmethyl)-2,2-difluoro oxetanes, 3-(acryloyl-oxy ylmethyl)-2,2,4-trifluoro oxetanes, 3-(acryloyl-oxy ylmethyl)-2,2,4,4-tetrafluoro oxetanes, 3-(acryloxy ethyl) oxetanes, 3-(acryloxy ethyl)-3-ethyl oxetanes, 2-ethyl-3-(acryloxy ethyl) oxetanes, 3-(acryloxy ethyl)-2-trifluoromethyl oxetanes, 3-(acryloxy ethyl)-2-pentafluoroethyl group oxetanes, 3-(acryloxy ethyl)-2-phenyl oxetanes, 2,2-two fluoro-3-(acryloxy ethyl) oxetanes, 3-(acryloxy ethyl)-2,2,4-trifluoro oxetanes, 3-(acryloxy ethyl)-2,2,4, acrylate such as 4-tetrafluoro oxetanes.

Wherein, consider special preferable methyl acrylic acid glycidyl esters, methacrylic acid 2-methyl glycidyl esters, methacrylic acid 3 from the polymerism angle, 4-epoxy radicals cyclohexyl, methacrylic acid 3,4-epoxy radicals cyclohexyl methyl esters, 3-methyl-3-methacryloxy methyl oxetanes, 3-ethyl-3-methacryloxy methyl oxetanes etc.

In the multipolymer [β], compound (a2-2) can use separately or with mixing more than 2 kinds.

In the multipolymer [β], from the preferred 0.5-70 weight of the containing ratio % of the repetitive of compound (a2-2), further preferred 1-60 weight %, preferred especially 3-50 weight %.Containing ratio from the repetitive of compound (a2-2) is lower than 0.5 weight %, and then the thermotolerance of gained multipolymer has the tendency of reduction, and surpasses 70 weight %, and then the storage stability of multipolymer has the tendency of reduction.

In multipolymer [α] and the multipolymer [β], can use the composition of other compound (a2) different with compound (a2-2) (hereinafter referred to as " compound (a2-3) ") as multipolymer with compound (a2-1).

Its object lesson for example has:

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-BMA, the secondary butyl ester of methacrylic acid, metering system tert-butyl acrylate;

Cyclohexyl acrylate, acrylic acid 2-methyl cyclohexane ester, acrylic acid three ring [5.2.1.0 ^2,6] decane-8-base ester, acrylic acid 2-(three ring [5.2.1.0 ^2,6] decane-8-base oxygen base) acrylate ring type esters such as ethyl ester, isobornyl acrylate;

Cyclohexyl methacrylate, methacrylic acid 2-methyl cyclohexane ester, methacrylic acid three ring [5.2.1.0 ^2,6] decane-8-base ester, methacrylic acid 2-(three ring [5.2.1.0 ^2,6] decane-8-base oxygen base) methacrylic acid ester ring type esters such as ethyl ester, isobornyl methacrylate;

Acrylic acid aryl ester such as phenyl acrylate, benzyl acrylate or aralkyl ester;

The aryl ester of methacrylic acid such as phenyl methacrylate, benzyl methacrylate or aralkyl ester;

Unsaturated dicarboxylic dialkyls 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 acrylate 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 methacrylate that contains the oxygen five-ring heterocycles or contain the oxygen hexa-member heterocycle;

Styrene, α-Jia Jibenyixi, a methyl styrene, p-methylstyrene, to vinyl aromatic compounds such as methoxy styrenes;

1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene equiconjugate diene compound; And

Vinyl cyanide, methacrylonitrile, acrylamide, Methacrylamide, vinyl chloride, vinylidene chloride, vinyl acetate etc.

Wherein, consider preferable methyl n-butyl acrylate, methacrylic acid 2-methyl glycidyl esters, methacrylic acid benzyl ester, methacrylic acid three ring [5.2.1.0 from the angle of copolyreaction ^2,6] decane-8-base ester, styrene, to methoxy styrene, methacrylic acid tetrahydrofuran-2-base ester, 1,3-butadiene etc.

In multipolymer [α] and multipolymer [β], compound (a2-3) can use separately or with mixing more than 2 kinds.

In multipolymer [α] and the multipolymer [β], from the preferred 10-70 weight of the containing ratio % of the repetitive of compound (a2-3), further preferred 20-50 weight %, preferred especially 30-50 weight %.The containing ratio of the repetitive of compound (a2-3) is lower than 10 weight %, and then the molecular weight of multipolymer has the tendency of reduction, and surpasses 70 weight %, and then compound (a1), compound (a2-1) and compound (a2-2) become the effect of branch performance to reduce.

Multipolymer [α] and multipolymer [β] can be by in appropriate solvent, polymerization prepare in the presence of radical polymerization initiator.

The solvent that uses in the above-mentioned polymerization for example has:

Alcohol such as methyl alcohol, ethanol, n-propanol, isopropyl alcohol;

Ethers such as tetrahydrofuran, diox;

Ethylene glycol one alkyl ethers such as glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol one positive propyl ether, ethylene glycol one n-butyl ether;

Ethylene glycol one alkyl ether acetic acid esters such as methyl glycol acetate, ethoxyethyl acetate(EA), ethylene glycol one positive propyl ether acetic acid esters, ethylene glycol one n-butyl ether acetic acid esters;

Ethylene glycol one alkyl ether propionic esters such as glycol monomethyl ether propionic ester, ethylene glycol monoethyl ether propionic ester, ethylene glycol one positive propyl ether propionic ester, glycol monomethyl n-butyl ether propionic ester;

Diglycol alkyl ethers such as diethylene glycol monomethyl ether, carbitol, diethylene glycol dimethyl ether, diethyl carbitol, diglycol methyl ethyl ether;

Propylene glycol one alkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol one positive propyl ether, propylene glycol one n-butyl ether;

Dipropylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol one ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether;

Propylene glycol one alkyl ether acetic acid esters such as propylene glycol monomethyl ether acetic acid esters, ethoxy propyl acetate, propylene glycol one positive propyl ether acetic acid esters, propylene glycol one n-butyl ether acetic acid esters;

Propylene glycol one alkyl ether propionic esters such as propylene glycol monomethyl ether propionic ester, propylene glycol monoethyl ether propionic ester, propylene glycol one positive propyl ether propionic ester, propylene glycol one n-butyl ether propionic ester;

Aromatic hydrocarbon such as toluene, dimethylbenzene;

Ketone such as methyl ethyl ketone, 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 esters such as 3-n-butoxy n-butyl propionate;

Methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, hydroxy methyl acetate, hydroxyl ethyl acetate, the glycolic acid n-propyl, the positive butyl ester of glycolic acid, acetate 4-methoxyl butyl ester, acetate 3-methoxyl butyl ester, acetate 2-methoxyl butyl ester, acetate 3-ethoxy butyl ester, acetate 3-propoxyl group butyl ester, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, the 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-hydracrylic acid n-propyl, the positive butyl ester of 3-hydracrylic acid, 2-hydroxy-3-methyl methyl butyrate, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid n-propyl, the positive butyl ester of methoxyacetic acid, ethoxy acetate, ethoxy ethyl acetate, the ethoxyacetic acid n-propyl, the positive butyl ester of ethoxyacetic acid, the positive propoxy methyl acetate, positive propoxy ethyl acetate, the positive propoxy n-propyl acetate, the positive propoxy n-butyl acetate, the n-butoxy methyl acetate, n-butoxy ethyl acetate, the n-butoxy n-propyl acetate, other ester etc. such as n-butoxy n-butyl acetate.

In these solvents, preferred diglycol alkyl ether, propylene glycol one alkyl ether acetic acid esters, alkoxypropan acid alkyl ester, acetic acid esters etc.

Above-mentioned solvent can use separately or with mixing more than 2 kinds.

Above-mentioned radical polymerization initiator is not particularly limited, for example can be: 2,2 '-azoisobutyronitrile, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (4-methoxyl-2, the 4-methyl pentane nitrile), 4,4 '-azo two (4-cyanopentanoic acid), dimethyl-2,2 '-azo two (2 Methylpropionic acid ester), 2,2 '-azo two azo-compounds such as (4-methoxyl-2,4-methyl pentane nitriles); Benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivarate, 1, organic peroxides such as two (t-butyl peroxy) cyclohexanes of 1-; Hydrogen peroxide etc.

When using superoxide, it can be used in combination with reductive agent, make the oxidation-reduction type initiating agent as radical polymerization initiator.

These radical polymerization initiators can use separately or with mixing more than 2 kinds.

Above-mentioned multipolymer that obtains [α] and multipolymer [β] can be directly be used for preparation [A] polymkeric substance with the form of solution, be used for preparing [A] polymkeric substance after can also separating from solution earlier.

The weight-average molecular weight through polystyrene conversion (hereinafter referred to as " Mw ") that gel permeation chromatography (GPC) by multipolymer [α] and multipolymer [β] carries out is preferably 2,000-100,000, more preferably 5,000-50,000.Mw is lower than 2,000, then probably reductions such as the alkali-developable of gained tunicle, residual film ratio, and pattern form, thermotolerance etc. are impaired, and surpass 100,000, and then probably resolution reduces, and pattern form is impaired.

[A] polymkeric substance among the present invention obtains by making unsaturated isocyanate compound and multipolymer [α] reaction.

The unsaturated isocyanate compound for example has:

2-acryloxy ethyl isocyanate, 3-acryloxy propyl group isocyanates, 4-acryloxy butyl isocyanate, 6-acryloxy hexyl isocyanates, 8-acryloxy octyl group isocyanates, 10-acryloxy decyl isocyanates, acrylic acid 2-(2-isocyanates base oxethyl) ethyl ester, acrylic acid 2-[2-(2-isocyanates base oxethyl) ethoxy] ethyl ester, acrylic acid 2-{2-[2-(2-isocyanates base oxethyl) ethoxy] ethoxy } ethyl ester, acrylic acid 2-(2-isocyanate group propoxyl group) ethyl ester, acrylic acid 2-[2-(2-isocyanate group propoxyl group) propoxyl group] acrylic acid derivative such as ethyl ester;

2-methacryloxyethyl isocyanates, 3-methacryloxypropyl isocyanates, 4-methacryloxy butyl isocyanate, 6-methacryloxy hexyl isocyanates, 8-methacryloxy octyl group isocyanates, 10-methacryloxy decyl isocyanates, methacrylic acid 2-(2-isocyanates base oxethyl) ethyl ester, methacrylic acid 2-[2-(2-isocyanates base oxethyl) ethoxy] ethyl ester, methacrylic acid 2-{2-[2-(2-isocyanates base oxethyl) ethoxy] ethoxy } ethyl ester, methacrylic acid 2-(2-isocyanate group propoxyl group) ethyl ester, methacrylic acid 2-[2-(2-isocyanate group propoxyl group) propoxyl group] methacrylic acid derivative such as ethyl ester.

It is カ レ Application ズ AOI (clear and electrician's (strain) system) that there is trade name the commercial goods of 2-acryloxy ethyl isocyanate, it is カ レ Application ズ MOI (clear and electrician's (strain) system) that there is trade name the commercial goods of 2-methacryloxyethyl isocyanates, and it is カ レ Application ズ MOI-EG (clear and electrician's (strain) system) that there is trade name the commercial goods of methacrylic acid 2-(2-isocyanates base oxethyl) ethyl ester.

In these unsaturated isocyanate compounds, from consider preferred 2-acryloxy ethyl isocyanate, 2-methacryloxyethyl isocyanates, 4-methacryloxy butyl isocyanate, methacrylic acid 2-(2-isocyanates base oxethyl) ethyl ester etc. with reactive angle of multipolymer [α].

In [A] polymkeric substance, the unsaturated isocyanate compound can use separately or with mixing more than 2 kinds.

Among the present invention, multipolymer [α] for example can followingly be implemented with the reaction of unsaturated isocyanate compound: at the room temperature or multipolymer [α] solution following, that the limit stirring contains polymerization inhibitors such as di-n-butyltin dilaurate catalyzer such as (IV) or p methoxy phenol of heating, the limit is to wherein adding the unsaturated isocyanate compound.

Preparation is during [A] polymkeric substance, and the consumption of unsaturated isocyanate compound is with respect to the hydroxyl of the compound (a2-1) in the 1 equivalent multipolymer [α], preferred 0.1-95 mole %, further preferred 1-80 mole %, preferred especially 5-75 mole %.The use amount of unsaturated isocyanate compound is lower than 0.1 mole of %, the effect that then sensitivity, thermotolerance raising and elastic property improve is little, and above 95 moles of %, then unreacted unsaturated isocyanate compound is residual, and the storage stability of resulting polymers solution or radiation sensitive resin composition has the tendency of reduction.

[A] polymkeric substance and multipolymer [β] all can use separately, but, further preferably [A] polymkeric substance and multipolymer [β] are used in combination from the storage stability of gained radiation sensitive resin composition and intensity and the consideration of stable on heating angle that can further improve spacer.

Among the present invention, when being used in combination, the consumption of multipolymer [β] is preferably the 0.5-50 weight portion with respect to 100 weight portions [A] polymkeric substance with [A] polymkeric substance and multipolymer [β], further preferred 1-40 weight portion, preferred especially 3-30 weight portion.The consumption of multipolymer [β] is lower than 0.5 weight portion, and then the intensity of spacer or thermotolerance raising effect is little, and surpasses 50 weight portions, and the tendency of the storage stability reduction that makes radiation sensitive resin composition is then arranged.

-[B] polymerizable unsaturated compound-

[B] polymerizable unsaturated compound is included in the existence of radiation-sensitive polymerization initiator and descends the unsaturated compound of polymerization by the exposure of radioactive ray.

Above-mentioned [B] polymerizable unsaturated compound is not particularly limited, and preferably contains the compound (hereinafter referred to as " polymerizable unsaturated compound [B2] ") that has 1-3 polymerism unsaturated link in the compound (hereinafter referred to as " polymerizable unsaturated compound [B1] ") that has 4 above polymerism unsaturated links in each a kind of 1 molecule and 1 molecule at least.

Described polymerizable unsaturated compound [B1] for example has pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, three (2-(methyl) acryloxy ethyl) phosphate etc., in addition also has: make to have the hydroxyl more than 1 in the compound that has straight-chain alkyl-sub-and ester ring type structure and have 2 above isocyanate group and the molecule and have polyurethane (methyl) acrylate compounds that the compound reaction of 3-5 (methyl) acryloxy obtains etc.

The commercial goods of polymerizable unsaturated compound [B1] for example has: ア ロ ニ Star Network ス M-400, ア ロ ニ Star Network ス M-402, ア ロ ニ Star Network ス M-405, ア ロ ニ Star Network ス M-450, ア ロ ニ Star Network ス M-1310, ア ロ ニ Star Network ス M-1600, ア ロ ニ Star Network ス M-1960, 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 M-8100, ア ロ ニ Star Network ス M-8530, ア ロ ニ Star Network ス M-8560, ア ロ ニ Star Network ス M-9050, ア ロ ニ Star Network ス TO-1450, ア ロ ニ Star Network ス TO-1382 (above) by East Asia synthetic (strain) system, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD MAX-3510 (above) by Japanese 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 (above) by Osaka organic chemistry industry (strain) system, the urethane acrylate based compound has: ニ ユ one Off ロ Application テ イ ア R-1150 (the first industrial pharmacy (strain) system), KAYARAD DPHA-40H, UX-5000 (Japanese chemical drug (strain) system), UN-9000H (industry (strain) system on the root) etc.

Above-mentioned polymerizable unsaturated compound [B2] for example has: one (methyl) acrylic acid ω-carboxyl polycaprolactone, (methyl) acrylic acid glycol ester, two (methyl) acrylic acid 1,6-hexane diol ester, two (methyl) acrylic acid 1,9-nonane diol ester, two (methyl) acrylic acid tetraethylene glycol ester, two (methyl) polyalkylene glycol acrylate ester, two (methyl) acrylic acid polypropylene glycol ester, two phenoxetol fluorenes two (methyl) acrylate, dihydroxymethyl tristane two (methyl) acrylate, 2-hydroxyl-3-(methyl) acryloxy propyl methyl acid esters, 2-(2 '-vinyl oxygen base oxethyl) ethyl (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate etc.

The commercial goods of polymerizable unsaturated compound [B2] for example has: ア ロ ニ Star Network ス M-5300, ア ロ ニ Star Network ス M-5600, ア ロ ニ Star Network ス M-5700, ア ロ ニ Star Network ス M-210, ア ロ ニ Star Network ス M-220, ア ロ ニ Star Network ス M-240, ア ロ ニ Star Network ス M-270, ア ロ ニ Star Network ス M-6200, ア ロ ニ Star Network ス M-305, ア ロ ニ Star Network ス M-309, ア ロ ニ Star Network ス M-310, ア ロ ニ Star Network ス M-315 (above) by East Asia synthetic (strain) system, KAYARAD HDDA, KAYARAD HX-220, KAYARADHX-620, KAYARAD R-526, KAYARAD R-167, KAYARAD R-604, KAYARAD R-684, KAYARAD R-551, KAYARAD R-712, UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU-4001 (above) by Japanese chemical drug (strain) system, ア one ト レ ジ Application UN-9000PEP, ア one ト レ ジ Application UN-9200A, ア one ト レ ジ Application UN-7600, ア one ト レ ジ Application UN-333, ア one ト レ ジ Application UN-1003, ア one ト レ ジ Application UN-1255, ア one ト レ ジ Application UN-6060PTM, ア one ト レ ジ Application UN-6060P (above) by industry (strain) system on the root, with SH-500B PVC ス コ one ト 260, PVC ス コ one ト 312, PVC ス コ one ト 335HP (above) etc. by Osaka organic chemistry industry (strain) system.

Among the present invention, [B] polymerizable unsaturated compound can use separately or with mixing more than 2 kinds.

The usage ratio of [B] polymerizable unsaturated compound is preferably the 40-250 weight portion, more preferably the 60-180 weight portion with respect to 100 weight portions [A] multipolymer in the radiation sensitive resin composition of the present invention.

When being used in combination, polymerizable unsaturated compound [B1] shared ratio in both total amounts is preferably 40-99 weight %, more preferably 60-95 weight % with polymerizable unsaturated compound [B1] and polymerizable unsaturated compound [B2].

By contain [B] polymerizable unsaturated compound with aforementioned proportion, radiation sensitive resin composition of the present invention can form the approaching fine pattern of size with the mask open part, even also obtain enough curable easily under low exposure.

-[C] radiation-sensitive polymerization initiator-

[C] radiation-sensitive polymerization initiator comprises the exposure by visible light, ultraviolet ray, far ultraviolet, charged particle ray, X ray isoradial, and generation can cause the composition of spike of the polymerization of [B] polymerizable unsaturated compound.

Above-mentioned [C] radiation-sensitive polymerization initiator for example has: O-acyl group oxime compound, acetophenone based compound, bisglyoxaline based compound, benzoin based compound, benzophenone based compound, α-diketone based compound, encircle quinone based compound, xanthone based compound, phosphine based compound, triazine based compound etc. more.Radiation sensitive resin composition of the present invention preferably contains O-acyl group oxime compound as [C] radiation-sensitive polymerization initiator.

In the radiation sensitive resin composition of the present invention, the consumption of [C] radiation-sensitive polymerization initiator is preferably the 0.01-120 weight portion, more preferably the 1-100 weight portion with respect to 100 weight portions [B] polymerizable unsaturated compound.When the consumption of radiation-sensitive polymerization initiator was lower than 0.01 weight portion, the residual film ratio when then developing had the tendency of reduction, and surpassed 120 weight portions, and unexposed portion has the tendency of reduction to the dissolubility of alkaline developer when then developing.

Above-mentioned O-acyl group oxime compound for example has: 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-nonane-1; 2-nonane-2-oxime-O-benzoic ether; 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-nonane-1; 2-nonane-2-oxime-O-acetic acid esters; 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-pentane-1; 2-pentane-2-oxime-O-acetic acid esters; 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-octane-1-ketoxime-O-acetic acid esters; 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-benzoic ether; 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-acetic acid esters; 1-[9-ethyl-6-(1; 3; the 5-trimethylbenzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-benzoic ether; 1-[9-butyl-6-(2-ethylamino benzonitrile acyl group)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-benzoic ether; 1-[9-ethyl-6-[2-methyl-4-(2; 2-dimethyl-1; 3-dioxane amyl group) methoxybenzoyl base]-9.H.-carbazole-3-yl]-1-(O-acetyl group) ethyl ketone oxime; 1; 2-octane diketone-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oxime); 1; 2-butane diketone-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oxime); 1; 2-butane diketone-1-[4-(thiophenyl) phenyl]-2-(O-acetyl oxime); 1; 2-octane diketone-1-[4-(methyl mercapto) phenyl]-2-(O-benzoyl oxime); 1; 2-octane diketone-1-[4-(thiophenyl) phenyl]-2-(O-(4-toluyl oxime)); 1; 2-octane diketone; 1-[4-(thiophenyl)-, 2-(O-benzoyl oxime)] etc.

In these O-acyl group oxime compounds; preferred especially 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-acetic acid esters, 1-[9-ethyl-6-[2-methyl-4-(2; 2-dimethyl-1; 3-dioxane amyl group) methoxybenzoyl base]-9.H.-carbazole-3-yl]-1-(O-acetyl group) ethyl ketone oxime, 1; 2-octane diketone-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oxime), 1; 2-octane diketone; 1-[4-(thiophenyl)-, 2-(O-benzoyl oxime)].

Above-mentioned O-acyl group oxime compound can use separately or with mixing more than 2 kinds.

Among the present invention,, can obtain highly sensitive radiation sensitive resin composition, and can obtain to have the spacer or the diaphragm of good fit by using O-acyl group oxime compound.

In radiation sensitive resin composition of the present invention,, be the radiation-sensitive polymerization initiator that polymerization initiator is used in combination more than a kind other further preferably with O-acyl group oxime as [C] radiation-sensitive polymerization initiator.

Above-mentioned other radiation-sensitive polymerization initiator preference such as acetophenone based compound, bisglyoxaline based compound etc.

Above-mentioned acetophenone based compound for example has: alpha-alcohol ketone based compound, alpha-amido ketone based compound etc.

Above-mentioned alpha-alcohol ketone based compound for example has: 1-phenyl-2-hydroxy-2-methyl propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 1-hydroxycyclohexylphenylketone etc.Above-mentioned alpha-amido ketone based compound for example has: 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholinyl propane-1-ketone, 2-methyl isophthalic acid-[4-(hydroxyl ethylmercapto group) phenyl]-2-morpholinyl propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone, 2-(4-methyl benzoyl)-2-(dimethylamino)-1-(4-morpholino phenyl)-butane-1-ketone etc.Acetophenone based compound in addition for example has: 2, and 2-dimethoxy-acetophenone, 2,2-diethoxy acetophenone, 2,2-dimethoxy-2-phenyl acetophenone etc.

In these acetophenone based compounds, preferred especially 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholinyl propane-1-ketone, 2-methyl isophthalic acid-[4-(hydroxyl ethylmercapto group) phenyl]-2-morpholinyl propane-1-ketone, 2-(4-methyl benzoyl)-2-(dimethylamino)-1-(4-morpholino phenyl)-butane-1-ketone.

Above-mentioned acetophenone based compound can use separately or with mixing more than 2 kinds.Among the present invention,, can further improve sensitivity, spacer shape and compression strenght by being used in combination the acetophenone based compound.

Above-mentioned bisglyoxaline based compound for example has: 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline, 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc.

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

Above-mentioned bisglyoxaline based compound can use separately or with mixing more than 2 kinds.Among the present invention,, can further improve sensitivity, resolution and stickiness by being used in combination the bisglyoxaline based compound.

When being used in combination the bisglyoxaline based compound,, can add aliphatic series or aromatics based compound (hereinafter referred to as " amino is sensitizer ") with dialkyl amido for its sensitization.

Amino is that sensitizer for example has: N methyldiethanol amine, 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, ESCAROL 507 ethyl ester, ESCAROL 507 isopentyl ester etc.

These amino are in the sensitizer, preferred especially 4,4 '-two (diethylamino) benzophenone.

Above-mentioned amino is that sensitizer can use separately or with mixing more than 2 kinds.

When being used in combination bisglyoxaline based compound and amino and being sensitizer, can add the mercaptan based compound as the hydrogen supply compound.The bisglyoxaline based compound is sensitizer sensitization and ftractureing by above-mentioned amino, produce imidazole radical, but this state does not show high polymerization initiating power, and the gained spacer forms preferred reverse tapered shapes mostly.But, by to bisglyoxaline based compound and amino being interpolation mercaptan based compound in the system of sensitizer coexistence, then supply with hydroperoxyl radical to imidazole radical by the mercaptan based compound, imidazole radical becomes neutral imidazoles as a result, produce the composition of sulphur free radical simultaneously, can make the shape of spacer become preferred positive taper thus with high polymerization initiating power.

Above-mentioned mercaptan based compound for example has: 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-sulfydryl-5-methoxyl benzo thiazole, 2-sulfydryl-aromatic compounds such as 5-methoxyl benzo imidazoles; Aliphatic monobasic mercaptan such as 3-mercaptopropionic acid, 3-mercapto-propionate, 3-mercaptopropionic acid ethyl ester, 3-mercaptopropionic acid monooctyl ester; 3,6-two oxa-s-1,8-octane two mercaptan, pentaerythrite four (mercaptoacetate), the above aliphatic mercaptan of pentaerythrite four difunctionalitys such as (3-mercaptopropionic acid esters).

In these mercaptan based compounds, preferred especially 2-mercaptobenzothiazole.

Above-mentioned mercaptan based compound can use separately or with mixing more than 2 kinds.

In the radiation sensitive resin composition of the present invention; when O-acyl group oxime compound and other radiation-sensitive polymerization initiator are used in combination; the usage ratio of other radiation-sensitive polymerization initiator is preferred 30-98 weight % in whole radiation-sensitive polymerization initiators, further preferred 40-95 weight %.When the usage ratio of other radiation-sensitive polymerization initiator is lower than 30 weight %, probably can't form fine pattern, and surpass 98 weight %, probably the sensitivity meeting reduces.

Bisglyoxaline based compound and amino are sensitizer when being used in combination, amino be the addition of sensitizer with respect to the preferred 0.1-150 weight portion of 100 weight portion bisglyoxaline based compounds, further preferred 1-120 weight portion.Amino is that the addition of sensitizer is lower than 0.1 weight portion, and the effect of improving of then sensitivity, resolution and stickiness has the tendency of reduction, and surpasses 150 weight portions, and then the shape of gained spacer has impaired tendency.

When the bisglyoxaline based compound was used in combination with the mercaptan based compound, the addition of mercaptan based compound was with respect to the preferred 1-80 weight portion of 100 weight portion bisglyoxaline based compounds, further preferred 5-60 weight portion.The addition of mercaptan based compound is lower than 1 weight portion, then has the shape of gained spacer to improve the tendency that effect is low, residual film ratio is low, and surpasses 80 weight portions, and then the shape of gained spacer has impaired tendency.

-[D] nitroxyl compound-

[D] nitroxyl compound contains the composition of the photopolymerization reaction that suppresses the outer radiation sensitive resin composition in exposure area originally, and this photopolymerization reaction is because the light that exposes causes in mask open diffraction phenomena and the radiation sensitive resin composition light diffusion and the scattering that make exposure itself partly.By containing described composition, can under the situation of the shape of not damaging sensitivity or gained spacer, form fine pattern near the mask open portion size.

The compound that above-mentioned [D] nitroxyl compound for example has following formula (1-1), (1-2) and (1-3) represents respectively.

(in the formula, each R is separate, and the alkyl of expression carbon number 1-12, Z and T represent to finish five or the necessary group of hexatomic ring, and E represents two or trivalent organic group, and n represents 2 or 3 integer).

Preferred R for example has in the formula (1-1): methyl, ethyl etc.In addition, in the compound shown in the formula (1-2), the following formula (1-2-1) and (1-2-2) compound etc. of expression are respectively for example arranged preferably.

(in the formula, X represents hydrogen atom, hydroxyl, acyloxy, amide group or imide).

In the compound shown in the formula (1-3), the compound that following formula (1-3-1) is preferably for example arranged and (1-3-2) represent respectively.

(in the formula, Y represents the alkylidene of methylene, carbon number 2-12 or the arlydene of alkenylene, cyclohexane two bases, cyclohexene two bases or carbon number 6-12).

(in the formula, R ¹The alkyl of expression carbon number 1-12).

The object lesson of above-mentioned nitroxyl compound has following compound.The structural formula of each compound after by the compound title with letter representation.Two-tert-butyl group nitroxyl (a); 1-oxyl-2; 2; 6; 6-tetramethyl piperidine (b); 1-oxyl-2; 2; 6; 6-tetramethyl piperidine-4-alcohol (c); 1-oxyl-2; 2; 6; 6-tetramethyl piperidine-4-ketone (d); 1-oxyl-2,2,6; 6-tetramethyl piperidine-4-yl acetate (e); 1-oxyl-2; 2,6,6-tetramethyl piperidine-4-base-2 ethyl hexanoic acid ester (f); 1-oxyl-2; 2; 6,6-tetramethyl piperidine-4-base stearate (g); 1-oxyl-2,2; 6; 6-tetramethyl piperidine-4-yl benzoic acid ester (h); 1-oxyl-2,2,6; 6-tetramethyl piperidine-4-base-4-p t butylbenzoic acid ester (i); two (1-oxyls-2; 2,6,6-tetramethyl piperidine-4-yl) succinate (j); two (1-oxyls-2; 2; 6,6-tetramethyl piperidine-4-yl) adipate (k); two (1-oxyls-2,2; 6; 6-tetramethyl piperidine-4-yl) sebacate (l); two (1-oxyl-2,2,6; 6-tetramethyl piperidine-4-yl) n-butylmalonic acid ester (m); two (1-oxyls-2; 2,6,6-tetramethyl piperidine-4-yl) phthalic ester (n); two (1-oxyls-2; 2; 6,6-tetramethyl piperidine-4-yl) isophthalic acid ester (o); two (1-oxyls-2,2; 6; 6-tetramethyl piperidine-4-yl) terephthalate (p); two (1-oxyl-2,2,6; 6-tetramethyl piperidine-4-yl) six hydrogen terephthalate (q); N; N '-two (1-oxyl-2,2,6; 6-tetramethyl piperidine-4-yl) adipamide (r); N-(1-oxyl-2; 2,6,6-tetramethyl piperidine-4-yl) caprolactam (s); N-(1-oxyl-2; 2; 6,6-tetramethyl piperidine-4-yl) dodecyl succinimide (t); 2,4; 6-three-[N-butyl-N-(1-oxyl-2; 2,6,6-tetramethyl piperidine-4-yl)-the s-triazine] (u).

In these nitroxyl compounds, preferred especially two (1-oxyls-2,2; 6,6-tetramethyl piperidine-4-yl) sebacate, 2,4; 6-three-[N-butyl-N-(1-oxyl-2; 2,6,6-tetramethyl piperidine-4-yl)-the s-triazine] or 4; 4 '-ethylenebis (1-oxyl-2; 2,6,6-tetramethyl piperazine-3-ketone).

There is trade name the commercial goods of above-mentioned nitroxyl compound for example for IRGASTAB UV10, IRGASTAB UV22 (above by チ バ ス ペ シ ヤ リ テ イ one ケ ミ カ Le ズ system) etc.

In the radiation sensitive resin composition of the present invention, the consumption of [D] nitroxyl compound is with respect to the preferred 0.001-2 weight portion of 100 weight portions [A] multipolymer, further preferred 0.01-1 weight portion.The consumption of [D] nitroxyl compound is lower than 0.001 weight portion, then probably can't obtain required effect, and surpasses 2 weight portions, and then probably sensitivity reduces, and pattern form is impaired.

-[E] chain-transferring agent-

Further contain [E] chain-transferring agent in the preferred radiation sensitive resin composition of the present invention.By [E] chain-transferring agent is used in combination with [D] nitroxyl compound, can further form the approaching fine pattern of size with the mask open part.

[E] chain-transferring agent is not particularly limited so long as can bring into play the compound of chain-transferring agent function get final product in Raolical polymerizable, and compound shown in the following formula (2) or thio-alcohol etc. are for example arranged.

(in the formula, each R ²Independent mutually, expression hydrogen or the alkyl of carbon number below 3).

R in the formula (2) ²For example have: methyl, ethyl, n-pro-pyl, isopropyl.

The object lesson of chain-transferring agent for example has: 2, and the compound shown in the following formulas (2) such as 4-diphenyl-4-methyl-1-pentene; Aliphatic series monobasic mercaptan such as 1-butane mercaptan, 3-mercaptopropionic acid butyl ester, 3-mercaptopropionic acid, 3-mercapto-propionate, 3-mercaptopropionic acid ethyl ester, 3-mercaptopropionic acid monooctyl ester, the different monooctyl ester of 3-mercaptopropionic acid; 3,6-two oxa-s-1,8-octane two mercaptan; Pentaerythrite four (mercaptoacetate), the above aliphatic series mercaptan of pentaerythrite four difunctionalitys such as (3-mercaptopropionic acid esters).

In these chain-transferring agents, the compound shown in the preferred following formula (2), preferred especially 2,4-diphenyl-4-methyl-1-pentene.

In the radiation sensitive resin composition of the present invention, the consumption of [E] chain-transferring agent is with respect to below preferred 3 weight portions of 100 weight portions [A] multipolymer, further preferred 0.5-2 weight portion.The consumption of [E] chain-transferring agent surpasses 3 weight portions, and then probably sensitivity reduces, and pattern form is impaired.

-adjuvant-

In the scope of not damaging the desired effect of the present invention, except that mentioned component, adjuvants such as matching surface activating agent, bonding agent, preserving stabilizer, thermotolerance improving agent as required in the radiation sensitive resin composition of the present invention.

Above-mentioned surfactant is the composition with the effect that improves coating, and preferred fluorine is surfactant and silicon-type surfactant.

Above-mentioned fluorine is that surfactant is preferred endways, any part at least of main chain and side chain has the compound of fluoroalkyl or fluorine alkylidene.Its object lesson has: 1,1,2,2-tetrafluoro octyl group (1,1,2,2-tetrafluoro-n-pro-pyl) ether, 1,1,2,2-tetrafluoro 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 fluoro-n-dodecanes, perfluor dodecyl sodium sulfonate or fluoroalkyl benzene sodium sulfonate, the fluoroalkyl Alendronate, the fluoroalkyl carboxylic acid sodium, the fluoroalkyl polyoxyethylene ether, diglycerol four (fluoroalkyl polyoxyethylene ether), the fluoroalkyl ammonium iodide, the fluoroalkyl betaine, the fluoroalkyl polyoxyethylene ether, the perfluoroalkyl poly oxyethanol, the perfluoroalkyl alcoxylates, fluorine is an Arrcostab etc.

Fluorine is that the commercial goods of surfactant has trade name for example to be BM-1000, BM-1100 (above) by BM CHEMIE 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 side Off ア Star Network F476 (above) by 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 (above) by Sumitomo 3M (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 (above) by Asahi Glass (strain) system, エ Off ト Star プ EF301, エ Off ト Star プ EF303, エ Off ト Star プ EF352 (above by new autumn fields change into (strain) system), Off タ one ジ エ Application ト FT-100, Off タ one ジ エ Application ト FT-110, Off タ one ジ エ Application ト FT-140A, Off タ one ジ エ Application ト FT-150, Off タ one ジ エ Application ト FT-250, Off タ one ジ エ Application ト FT-251, Off タ one ジ エ Application ト FTX-251, Off タ one ジ エ Application ト FTX-218, Off タ one ジ エ Application ト FT-300, Off タ one ジ エ Application ト FT-310, Off タ one ジ エ Application ト FT-400S's (above) etc. by (strain) ネ オ ス system.

The commercial goods of above-mentioned silicon-type surfactant has trade name for example to be ト one レ シ リ コ one Application DC3PA, 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 (the Shang You East of Yi 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, TSF-4452's (above) etc. by GE East sesame シ リ コ one Application (strain) system.

Surfactant beyond the above-mentioned substance for example has: polyoxyethylene alkyl ether classes such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-nonyl phenyl ether; Nonionics such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate, polyoxyethylene distearate are surfactant, and there is trade name the commercial goods for example for KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), Port リ Off ロ one No.57, Port リ Off ロ one No.95 (common prosperity society chemistry (strain) system) etc.

Above-mentioned surfactant can use separately or with mixing more than 2 kinds.

The use level of above-mentioned surfactant is with respect to below preferred 5 weight portions of 100 weight portions [A] polymkeric substance, further below preferred 2 weight portions.The use level of surfactant surpasses 5 weight portions, and film is coarse easily when then being coated with.

Above-mentioned bonding agent is the composition with effect of the further stickiness of improving spacer and matrix, preferred functional silanes coupling agent.

Above-mentioned functional silanes coupling agent for example has: the compound with carboxyl, methacryl, vinyl, isocyanate group, epoxy radicals isoreactivity functional group.More particularly have: trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-isocyanate group propyl-triethoxysilicane, γ-glycidoxypropyltrime,hoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane etc.

These bonding agents can use separately or with mixing more than 2 kinds.

The use level of bonding agent is with respect to below preferred 20 weight portions of 100 weight portions [A] polymkeric substance, further below preferred 10 weight portions.The use level of bonding agent surpasses 20 weight portions, and it is residual then to take place easily to develop.

Above-mentioned preserving stabilizer for example has sulphur, quinones, hydroquinones, polyoxy compound, amine, nitroso compound etc., more particularly has: 4-metoxyphenol, N-nitroso--N-Phenylhydroxylamine aluminium etc.

These preserving stabilizers can use separately or with mixing more than 2 kinds.

The use level of preserving stabilizer is preferably below 3 weight portions with respect to 100 weight portions [A] polymkeric substance, further preferred 0.001-0.5 weight portion.The use level of preserving stabilizer surpasses 3 weight portions, and then probably sensitivity reduces, and pattern form is impaired.

Above-mentioned thermotolerance improving agent for example have N-(alkoxy methyl)-imidazolidine also [4,5-d] imidazoles-2,5 (1H, 3H)-diketone (グ リ コ one Le ウ リ Le) compound, N-(alkoxy methyl) melamine compound etc.

Above-mentioned N-(alkoxy methyl)-imidazolidine is [4,5-d] imidazoles-2,5 (1H also, 3H)-dione compounds for example has: N ', N ", N " ', N " "-four (methoxy)-imidazolidine is [4,5-d] imidazoles-2,5 (1H also, 3H)-diketone, N ', N ", N " ', N " "-four (ethoxyl methyl)-imidazolidine is [4,5-d] imidazoles-2,5 (1H also, 3H)-diketone, N ', N ", N " ', N " "-four (n-propoxymethyl)-imidazolidine is [4,5-d] imidazoles-2,5 (1H also, 3H)-diketone, N ', N ", N " ', N " "-four (isopropoxy methyl)-imidazolidine is [4,5-d] imidazoles-2,5 (1H also, 3H)-diketone, N ', N ", N " ', N " "-four (n-butoxy methyl)-imidazolidine is [4,5-d] imidazoles-2,5 (1H also, 3H)-diketone, N ', N ", N " ', N " "-four (tert-butoxy methyl)-imidazolidine also [4,5-d] imidazoles-2,5 (1H, 3H)-diketone etc.

These N-(alkoxy methyl)-imidazolidine also [4,5-d] imidazoles-2,5 (1H, 3H)-dione compounds in, preferred especially N ', N ", N " ', N " "-four (methoxy)-imidazolidine also [4,5-d] imidazoles-2,5 (1H, 3H)-diketone.

Above-mentioned N-(alkoxy methyl) melamine compound for example has: 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, preferred especially N, N, N ', N ', N "; N "-six (methoxy) melamine, its commercial goods have trade name for example for ニ カ ラ Star Network N-2702, ニ カ ラ Star Network MW-30M (above by three and ケ ミ カ Le (strain) system) etc.

Above-mentioned thermotolerance improving agent can use separately or with mixing more than 2 kinds.

The use level of thermotolerance improving agent is preferably below 30 weight portions with respect to 100 weight portions [A] polymkeric substance, further below preferred 20 weight portions.The use level of thermotolerance improving agent surpasses 30 weight portions, and then the storage stability of radiation sensitive resin composition has the tendency of reduction.

Radiation sensitive resin composition of the present invention preferably uses with the form that is dissolved in the composition solution in the appropriate solvent.

Above-mentioned solvent uses each composition uniform dissolution that will constitute radiation sensitive resin composition, not with each composition reaction, has appropriate volatile solvent, dissolving power from each composition, consider with the angle that forms the easiness of filming with the reactivity of each composition, preferred alcohols, ethylene glycol one alkyl ether acetic acid esters, diglycol one alkyl ether acetic acid esters, the diglycol alkyl ether, propylene glycol one alkyl ether acetic acid esters, the dipropylene glycol alkyl ether, the alkoxypropan acid alkyl ester, acetic acid esters etc., preferred especially benzylalcohol, the 2-phenylethanol, 3-phenyl-1-propyl alcohol, ethylene glycol one n-butyl ether acetic acid esters, diglycol monoethyl ether acetic acid esters, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diglycol ethyl-methyl ether, propylene glycol monomethyl ether acetic acid esters, ethoxy propyl acetate, the dipropylene glycol dimethyl ether, acetate 3-methoxyl butyl ester, acetate 2-methoxyl ethyl ester etc.

Above-mentioned solvent can use separately or with mixing more than 2 kinds.

Among the present invention, can further be used in combination high boiling solvent with above-mentioned solvent.

Above-mentioned high boiling solvent for example has: 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, benzylalcohol, acetate benzyl ester, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propylene carbonate, ethylene glycol one phenyl ether acetic acid esters etc.

These high boiling solvents can use separately or with mixing more than 2 kinds.

Zhi Bei composition solution can use the filtration backs such as Millipore filter about the 0.5 μ m of aperture to use as mentioned above.

The radiation sensitive resin composition utmost point of the present invention is suitable for forming the spacer or the diaphragm of used for liquid crystal display element.

The formation method of spacer or diaphragm

Below, the method for using radiation sensitive resin composition of the present invention to form spacer of the present invention or diaphragm is described.

The formation of spacer of the present invention or diaphragm comprises following steps at least in the following order.

(1) step of the tunicle of formation radiation sensitive resin composition of the present invention on substrate;

(2) at least a portion of this tunicle is carried out step of exposing;

(3) tunicle after the exposure is carried out step of developing; And

(4) step that the tunicle after developing is heated.

Below describe for each steps in sequence.

-(1) step-

When forming diaphragm, form the pixel that contains the red, green, blue dyed layer on transparency carrier, preferably the form with composition solution is coated with radiation sensitive resin composition on this dyed layer, and heating (preliminary drying) coated face forms tunicle then.In addition; when forming spacer; above-mentioned formed the transparency carrier of pixel or formed thereon again on the face of transparency carrier of diaphragm form nesa coating; preferably the form with composition solution is coated with radiation sensitive resin composition on this nesa coating; the preliminary drying coated face forms tunicle then.

Here employed transparency carrier for example has glass substrate, resin substrate etc., more particularly has: glass substrates such as soda-lime glass, alkali-free glass; The resin substrate that contains plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide.

Being located at nesa coating on the face of transparency carrier for example can use and contain tin oxide (SnO ₂) NESA film (registered trademark of U.S. PPG company), contain indium oxide-tin oxide (In ₂O ₃-SnO ₂) ITO film etc.

The coating process of composition solution and the method that forms the tunicle of radiation sensitive resin composition of the present invention for example can adopt (1) rubbing method, (2) dry film method.

The rubbing method of composition solution for example can adopt spray-on process, rolling method, spin-coating method, slot die rubbing method, rod to be coated with suitable methods such as method, ink-jet application method, preferred especially spin-coating method, slot die rubbing method.

When forming the tunicle of radiation sensitive resin composition of the present invention, during (2) the dry film method of employing, this dry film is (hereinafter referred to as " photosensitive dry film ") that the stacked radiation-sensitive layer that contains radiation sensitive resin composition of the present invention forms on the basement membrane of basement membrane, preferred coating character.

Above-mentioned photosensitive dry film can followingly form: preferably the form with liquid composition is coated with radiation sensitive resin composition of the present invention on basement membrane, and is dry then, stacked thus radiation-sensitive layer.The basement membrane of photosensitive dry film for example can use the film of synthetic resin such as polyethylene terephthalate (PET), tygon, polypropylene, polycarbonate, Polyvinylchloride.The thickness of basement membrane is comparatively suitable in the scope of 15-125 μ m.About the preferred 1-30 μ of the thickness m of gained radiation-sensitive layer.

Photosensitive dry film can further stackedly on its radiation-sensitive layer not preserved by overlay film when using yet.This, so that do not peel off when using and can easily be peeled off in use by the demoulding that overlay film must have appropriateness.As satisfy above-mentioned condition by overlay film, for example can use and carry out the coating of silicon-type remover or the film of roasting gained on the surface of synthetic resin films such as PET film, polypropylene screen, polyethylene film, polychloroethylene film.Promptly enough about 25 μ m usually by the thickness of overlay film.

The condition of preliminary drying is different and different according to the kind of each composition, cooperation ratio etc., is normally carrying out about 1-15 minute under 70-120 ℃.

-(2) step-

Then, at least a portion of the tunicle that forms is exposed.At this moment, when the part of tunicle is exposed, normally expose via mask with predetermined pattern.

The radioactive ray that use in the exposure for example can use visible light, ultraviolet ray, far ultraviolet, electron ray, X ray etc., and optimal wavelength especially preferably contains the ultraviolet radioactive ray of 365nm at the radioactive ray of 190-450nm scope.

Exposure is the value of the intensity of radioactive ray when wavelength is 365nm of exposure being measured with illuminometer (OAI, model 356, OAI Optical Associates Inc. system), is generally 100-10,000J/m ², preferred 500-3000J/m ²

-(3) step-

Then,, remove unwanted part, form the pattern of regulation by the tunicle after the exposure is developed.

The developer solution preferred bases developer solution that uses in the development, its example has: inorganic bases such as NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonium, aliphatic primary amines such as ethamine, n-propylamine; Aliphatic secondary amine such as diethylamine, di-n-propylamine; Aliphatic tertiary amines such as trimethylamine, methyl diethylamide, dimethylethyl amine, triethylamine; Pyrroles, piperidines, N-methyl piperidine, N-crassitude, 1,8-diazabicyclo [5.4.0]-7-undecylene, 1,5-diazabicyclo [4.3.0]-alicyclic tertiary amines such as 5-nonene; Aromatic uncle amines such as pyridine, trimethylpyridine, lutidines, quinoline; Alkanolamines such as dimethylamino ethanol amine, methyldiethanolamine, triethanolamine; The aqueous solution of alkali compounds such as quaternary ammonium salt such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide.

Can add water-miscible organic solvent or surfactant uses such as methyl alcohol, ethanol in the aqueous solution of above-mentioned alkali compounds in right amount.

Developing method can be to soak any means such as the method for putting (liquid is contained the り method), infusion process (デ イ Star ピ Application グ method), spray process, and development time is generally 10-180 about second.

For example use flowing water rinsing 30-90 second after the development, for example carry out air-dryly then, form required pattern thus with pressurized air or compressed nitrogen.

-(4) step-

Then; the gained pattern is for example used heating arrangements such as hot plate, baking oven heat (back baking), spacer that can obtain to stipulate or diaphragm thus in baking oven with set point of temperature (for example 100-230 ℃), stipulated time (for example be 5-30 minute on the hot plate, be 30-180 minute).

Liquid crystal display cells

Liquid crystal display cells of the present invention for example can be by following method (a) or (b) making.

(a) at first prepare 1 (2) had the transparency carrier of nesa coating (electrode) on a face; use radiation sensitive resin composition of the present invention; according to the method described above, form spacer or diaphragm or both therein on the nesa coating of 1 plate base.Then, on the nesa coating of two substrates and spacer or diaphragm, form alignment films with liquid crystal aligning ability.Facing to the inside of alignment films one side will have been formed, Jie is disposed two substrates relatively by certain clearance (box gap), make the vertical or antiparallel of liquid crystal aligning direction of each alignment films, liquid crystal is filled in the box gap that surface (alignment films) and spacer by substrate come zoning, mouth is filled in sealing, constitutes liquid crystal cell.The Polarizer of fitting on two outside surfaces of liquid crystal cell then makes its polarization direction consistent or vertical with the liquid crystal aligning direction of the alignment films that forms on the one side of this substrate, can obtain liquid crystal display cells of the present invention thus.

(b) at first same with above-mentioned first method, prepare a pair of transparency carrier that is formed with nesa coating, spacer or diaphragm or both and alignment films.Use dispersion machine then, the end coating ultraviolet hardening sealant along a substrate then uses the dispersed liquid crystal machine to be the fine droplet shape and drips liquid crystal, two substrates of fitting under vacuum.Use high-pressure sodium lamp to above-mentioned sealant part irradiation ultraviolet radiation then, seal two substrates.At two outside surface applying Polarizers of liquid crystal cell, can obtain liquid crystal display cells of the present invention thus at last.

The liquid crystal that uses in above-mentioned each method has for example nematic crystal, smectic crystal.Wherein, preferred nematic crystal, it is that liquid crystal, azoxy are that liquid crystal, biphenyl are that liquid crystal, cyclohexylbenzene are that liquid crystal, ester are that liquid crystal, terphenyl are that liquid crystal, cyclohexyl biphenyl hexane are that liquid crystal, pyrimidine are that liquid crystal, diox are that liquid crystal, double-octane are liquid crystal, cube methane series liquid crystal etc. that schiff bases is for example arranged.The uses such as chiral reagent that also can add cholesteric crystal such as for example cholesteric chloride, cholesteryl nonanoate, cholesteryl carbonate in these liquid crystal or sell with trade name " C-15 ", " CB-15 " (above) by メ Le Network corporate system.Also can use oxygen base benzal-in the last of the ten Heavenly stems strong dielectricity liquid crystal such as amino-2-methyl butyl cinnamate.

The Polarizer that use in the outside of liquid crystal cell has: Polarizer that the light polarizing film that will be called as the H film obtains with the clamping of cellulose acetate diaphragm or the Polarizer that contains H film itself etc., wherein, described H film is to make the polyvinyl alcohol (PVA) stretch orientation, absorbed the film of iodine simultaneously.

As mentioned above, radiation sensitive resin composition of the present invention has high degree of resolution, can form fine pattern in the liquid crystal display cells of high-resolution.

Embodiment

Below provide embodiment, further specify embodiment of the present invention.But the present invention is not subjected to the qualification of following embodiment.Here, part and % are weight basis.

In the following synthesis example, the mensuration of the weight-average molecular weight Mw of multipolymer is under following apparatus and condition, undertaken by gel permeation chromatography (GPC).

Device: GPC-101 (clear and electrician's (strain) system)

Post: with GPC-KF-801, GPC-KF-802, GPC-KF-803, GPC-KF-804

Be used in combination

Moving phase: the tetrahydrofuran that contains 0.5 weight % phosphoric acid

Synthesis example 1

In the flask of band condenser pipe and stirring machine, add 5 weight portions 2,2 '-azo two (2, the 4-methyl pentane nitrile), 200 weight portion diglycol methyl ethyl ethers, then add 18 weight portion methacrylic acids, 40 weight portion methyl propenoic acid glycidyl base esters, 5 parts by weight of styrene and 32 weight portion methacrylic acids, three ring [5.2.1.0 ^2,6] decane-8-base ester, carry out nitrogen displacement back and further add 5 weight portion 1,3-butadienes, slowly stir, make the temperature of solution be increased to 70 ℃ simultaneously, this temperature is kept carrying out polymerization in 5 hours, obtain the solution of multipolymer [A-1].

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

Synthesis example 2

In the flask of band condenser pipe and stirring machine, add 5 weight portions 2,2 '-azoisobutyronitrile, 250 weight portion diglycol methyl ethyl ethers, then add 35 weight portion succinic acid 2-methacryloxy ethyl esters, 25 weight portion n-BMAs and 35 weight portion methacrylic acid benzyl esters, carry out nitrogen displacement back and further add 5 weight portions 1, the 3-butadiene, slowly stir, make the temperature of solution be increased to 90 ℃ simultaneously, this temperature is kept carrying out in 5 hours polymerization, [A] copolymer solution that to obtain solid formation branch concentration be 28.0 weight %, with it as multipolymer [A-2].

Measuring the Mw of gained multipolymer [A-2], is 12,000.

Synthesis example 3

Add 5 weight portions 2 in the flask of band condenser pipe and stirring machine, 2 '-azoisobutyronitrile, 250 weight portion acetate trimethoxy butyl esters then add 18 weight portion methacrylic acids, 25 weight portion methacrylic acids, three ring [5.2.1.0 ^2,6] decane-8-base ester, 5 parts by weight of styrene, 30 weight portion 2-hydroxyethyl methacrylates and 22 weight portion methacrylic acid benzyl esters, carrying out nitrogen displacement back slowly stirs, make the temperature of solution be increased to 80 ℃ simultaneously, this temperature is kept carrying out polymerization in 5 hours multipolymer [α-1] solution that to obtain solid formation branch concentration be 28.8 weight %.

Measuring the Mw of gained multipolymer [α-1], is 13,000.

Then, in the above-mentioned multipolymer of 100 weight portions [α-1] solution, add 12 weight portion 3-methacryloxyethyl isocyanates (trade name カ レ Application ズ MOI, clear and electrician's (strain) system), 0.1 weight portion 4-metoxyphenol, then 40 ℃ stir down 1 hour, stirred 2 hours down at 60 ℃ again, react.Confirm between the isocyanate group of 3-methacryloxyethyl isocyanates and the hydroxyl reaction having taken place by IR (infrared absorption) spectrum from multipolymer [α-1].For 40 ℃ down reaction after 1 hour solution and further at 60 ℃ of reaction solution after 2 hours down, confirm from 2 of the isocyanate group of 3-methacryloxyethyl isocyanates, 270cm by the IR spectrum respectively ^-1Near peak reduces.[A] copolymer solution that to obtain solid formation branch concentration be 31.0 weight %.With it as multipolymer [A-3].

Synthesis example 4

In the flask of band condenser pipe and stirring machine, add 5 weight portions 2,2 '-azoisobutyronitrile and 220 weight portion acetate 3-methoxyl butyl esters.Then add 5 parts by weight of styrene, 15 parts by weight of acrylic acid, 15 weight portion n-BMAs, 20 weight portion methacrylic acid benzyl esters and 40 weight portion 3-(methacryloxy methyl)-3-ethyl oxetanes, carry out nitrogen displacement back and further add 5 weight portions 1, the 3-butadiene, slowly stir, make the temperature of solution be increased to 80 ℃ simultaneously, this temperature is kept carrying out polymerization in 5 hours, obtain the solution of multipolymer [A-4].The solid formation branch concentration of gained copolymer solution is 30.5 weight %, and the Mw of multipolymer [A-4] is 10,700.

Synthesis example 5

In the flask of band condenser pipe and stirring machine, add 4 weight portions 2,2 '-azo two (2, the 4-methyl pentane nitrile), 250 weight portion diglycol methyl ethyl ethers.Then add 5 parts by weight of styrene, 20 parts by weight of acrylic acid, 15 weight portion methacrylic acid tetrahydro furfuryl esters, 30 weight portion methyl propenoic acid glycidyl base esters and 25 weight portion 3-(methacryloxy methyl)-3-ethyl oxetanes, carry out nitrogen displacement back and further add 5 weight portions 1, the 3-butadiene, slowly stir, make the temperature of solution be increased to 70 ℃ simultaneously, this temperature is kept carrying out polymerization in 5 hours, obtain the solution of multipolymer [A-5].The solid formation branch concentration of gained copolymer solution is 28.3 weight %, and the Mw of multipolymer [A-5] is 11,000.

Embodiment 1-23 and comparative example 1-2

The preparation of＜radiation sensitive resin composition 〉

With (A)-(E) composition shown in the table 1 and 2.5 weight portions as the γ-glycidoxypropyltrime,hoxysilane of bonding agent, 0.5 weight portion FTX-218 (trade name as surfactant, (strain) ネ オ ス system), 0.5 weight portion mixes as the 4-metoxyphenol of preserving stabilizer, be dissolved in the propylene glycol monomethyl ether acetic acid esters, making solid formation branch concentration is 20 weight %, Millipore filter with aperture 0.5 μ m filters then, the preparation composition solution.About comparative example 2, further cooperate phenothiazine as polymerization inhibitor.

(B) composition

B-1: dipentaerythritol acrylate (trade name KAYARAD DPHA, Japanese chemical drug (strain) system)

B-2: the polymerism unsaturated monomer (trade name KAYARAD DPHA-40H, Japanese chemical drug (strain) system) that contains multifunctional polyurethane acrylate based compound

B-3:1,9-nonane diacrylate (trade name ラ イ ト ア Network リ レ one ト 1,9-NDA, common prosperity society (strain) system)

B-4: ω-carboxyl polycaprolactone one acrylate (trade name ア ロ ニ Star Network ス M-5300, East Asia synthetic (strain) system)

(C) composition

C-1:1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-acetic acid esters (trade name イ Le ガ キ ユ ア OXE02, チ バ ス ペ シ ヤ Le テ イ one ケ ミ カ Le ズ system)

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

C-3:4,4 '-two (diethylamino) benzophenone

The C-4:2-mercaptobenzothiazoler

C-5:1,2-octane diketone, 1-[4-(thiophenyl)-, 2-(O-benzoyl oxime)] (trade name イ Le ガ キ ユ ア OXE01, チ バ ス ペ シ ヤ Le テ イ one ケ ミ カ Le ズ system)

C-6:2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl propane-1-ketone (trade name イ Le ガ キ ユ ア 907, チ バ ス ペ シ ヤ リ テ イ one ケ ミ カ Le ズ system)

C-7:2-methyl isophthalic acid-[4-(hydroxyl ethylmercapto group) phenyl]-2-morpholinyl propane-1-ketone

C-8:2,4-diethyl thioxanthone (trade name KAYACURE DETX-S, Japanese chemical drug (strain) system)

(D) composition

D-1: two (1-oxyl-2,2,6,6-tetramethyl piperidine-4-yl) sebacate

(E) composition

E-1:2,4-diphenyl-4-methyl-1-pentene

Other composition

F-1: phenothiazine

This composition is not used in "-" expression in the column.

＜estimate

The radiation sensitive resin composition of the above-mentioned preparation of following evaluation.Evaluation result is as shown in table 2.

(1) evaluation of sensitivity

Use the spin coating instrument on alkali-free glass substrate, be coated with the solution of the radiation sensitive resin composition of above-mentioned preparation, preliminary drying 3 minutes on 80 ℃ hot plate then, the tunicle of formation thickness 4.0 μ m.

Then, be 250W/m via having diameter 14 μ m circular patterns as the mask of opening portion, with the intensity under the 365nm ²Ultraviolet ray, change the time shutter gained tunicle exposed.With 0.05% weight potassium hydroxide aqueous solution, developed 60 seconds down at 25 ℃, used the pure water rinsing then 1 minute then, further back baking 20 minutes in 230 ℃ baking oven forms spacer.

At this moment, the residual film ratio after the baking later on (thickness after the baking of back * 100/ exposure back thickness) is that 90% minimum exposure amount when above is as sensitivity.Sensitivity is 1,000J/m ²When following, it is good to can be described as sensitivity.

(2) development evaluation

Making exposure is 1,000J/m ², development time is 40 seconds, and is in addition same with the evaluation of (1) sensitivity, forms spacer on substrate.If form pattern this moment under the situation that does not produce residue, then be evaluated as zero, be evaluated as when producing residue *.

(3) evaluation of resolution

Making exposure is 1,000J/m ², in addition same with the evaluation of (1) sensitivity, on substrate, form spacer.The diameter of gained pattern is measured with laser microscope (VK-8500, キ one エ Application ス system).At this moment, when the diameter of pattern was lower than 25 μ m, it was good to be called resolution, and it is good especially then to can be described as resolution when being lower than 20 μ m.

(4) observation of separator surface state

Exposure is set to be equivalent to by definite sensitivity in (1) sensitivity evaluation, and is in addition same with the evaluation of (1) sensitivity, forms spacer on substrate.Use scanning electron-microscopic observation gained pattern,, then be evaluated as good (zero), then be evaluated as when confirming rough surface bad (*) if separator surface is level and smooth.

(5) evaluation of compression displacement amount

Same with the observation of (4) separator surface state, on substrate, form spacer.For the gained pattern, use the minute-pressure experimental machine (DUH-201, (strain) Shimadzu Seisakusho Ltd. system) that contracts, press son to apply 50mN load with the plane of diameter 50 μ m, measure deflections at this moment down for 23 ℃ measuring temperature.This value is 0.45 when above, and it is good then to can be described as the compression displacement amount.

(6) stickiness evaluation

Do not use the photoengraving mask, make exposure be equivalent to the sensitivity of in (1) sensitivity is estimated, determining, same with the evaluation of (1) sensitivity, on substrate, form cured film.In the tack experiment of JISK-5400 (1900) 8.5, estimate then by 8.5.2 gridiron pattern adhesive tape method.At this moment, residual gridiron pattern number is as shown in table 2 in 100 gridiron patterns.

(7) evaluation of voltage retention

Formed the SiO that prevents the sodion stripping from the teeth outwards ₂Film, and further evaporation the solution of the radiation sensitive resin composition of the above-mentioned preparation of spin coating on the soda-lime glass substrate of ITO (indium-tin oxide alloy) electrode of regulation shape, preliminary drying 10 minutes in 90 ℃ cleaning oven forms filming of thickness 2.0 μ m then.

Then, use high-pressure sodium lamp, not via the photoengraving mask, with 1,000J/m ²Exposure comprise the exposure of the radioactive ray of 365nm, 405nm and each wavelength of 436nm to filming.Then this substrate was soaked 1 minute in 23 ℃ the developer solution that contains 0.04 weight % potassium hydroxide aqueous solution, develop, use super pure water rinse and air-dry then, further dried by the fire 30 minutes the back under 230 ℃, makes curing of coating, forms permanent cured film.

Then, with the gained substrate and only evaporation the substrate of ITO electrode of regulation shape fit with the sealant that is mixed with the 0.8mm beaded glass, inject the liquid crystal MLC6608 (trade name) of メ Le Network system then, make liquid crystal cell.

Then, liquid crystal cell is put into 60 ℃ calibration cell, measure the voltage retention that the VHR-1A of system type (trade name) is measured liquid crystal cell by the liquid crystal voltage conservation rate that Dongyang テ Network ニ カ makes.The impressed voltage of this moment is the rectangular wave of 5.5V, and the mensuration frequency is 60Hz.Here, voltage retention is the value of when liquid crystal cell potential difference (PD)/0 millisecond (after 16.7 milliseconds impressed voltage).The voltage retention of liquid crystal cell is below 90%, and then liquid crystal cell can't be with the time of impressed voltage with 16.7 milliseconds of prescribed level maintenances, and this just means can't make liquid crystal aligning fully, and the possibility height of " image retention " takes place.

Claims (8)

1. radiation sensitive resin composition is characterized in that containing:

[A] (a1) be selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides at least a, with (a2) be different from the multipolymer of other unsaturated compound of (a1);

[B] polymerizable unsaturated compound;

[C] radiation-sensitive polymerization initiator; And

[D] nitroxyl compound.

2. the described radiation sensitive resin composition of claim 1, wherein, [D] nitroxyl compound is following formula (1-1), (1-2) or (1-3) any one of the compound of expression respectively,

In the formula, each R is separate, and the alkyl of expression carbon number 1-12, Z and T represent to finish five or the necessary group of hexatomic ring, and E represents divalence or trivalent organic group, and n represents 2 or 3 integer.

3. the described radiation sensitive resin composition of claim 1, wherein, [D] nitroxyl compound is following formula (1-2-1), (1-2-2), (1-3-1) or (1-3-2) any one of the compound of expression respectively,

In the formula, X represents hydrogen atom, hydroxyl, acyloxy, amide group or imide, and Y represents the alkylidene of methylene, carbon number 2-12 or the arlydene of alkenylene, cyclohexane two bases, cyclohexene two bases or carbon number 6-12, R ¹The alkyl of expression carbon number 1-12.

4. each described radiation sensitive resin composition among the claim 1-3, said composition further contains [E] chain-transferring agent.

5. each described radiation sensitive resin composition among the claim 1-4, said composition is used to form the spacer or the diaphragm of used for liquid crystal display element.

6. spacer for liquid crystal display element or the diaphragm that forms by the described radiation sensitive resin composition of claim 5.

7. the formation method of spacer for liquid crystal display element or diaphragm is characterized in that: comprise following at least step in the following order:

(1) on substrate, form the tunicle of the described radiation sensitive resin composition of claim 5 step,

(2) at least a portion of this tunicle carry out step of exposing,

(3) to the exposure after tunicle carry out step of developing and

(4) step that the tunicle after developing is heated.

8. possess described spacer of claim 6 or diaphragm or both liquid crystal display cells.