TWI387850B - Radiation sensitive resin composition, projections, spacers, verticallyl aligned type liquid crystal display element, and the method for forming projections and spacers - Google Patents

Description

Radiation-sensitive resin composition, protrusion, spacer, vertical alignment type liquid crystal display element, and method for forming protrusion and/or spacer

The present invention relates to a radiation sensitive resin composition for forming protrusions and/or spacers used in a vertical alignment type liquid crystal display element, protrusions and spaces used for a vertical alignment type liquid crystal display element formed of the composition A vertical alignment type liquid crystal display element comprising the protrusions and/or spacers and a method of forming the protrusions and/or the spacers.

Liquid crystal display elements are widely used in flat panel displays. In recent years, with the promotion of OA equipment such as personal computers and word processors, and LCD TVs, the performance requirements for TFT (Thin Film Transistor) liquid crystal displays (TFT-LCDs) are becoming more and more strict. . Among TFT-LCDs, TN (Twisted Nematic) type LCDs are now the most widely used. This LCD is manufactured by disposing a polarizing film having a direction difference of 90 degrees in alignment directions on both outer sides of two substrates having transparent electrodes (hereinafter referred to as "transparent electrode substrates"), and at two transparent electrodes An alignment film is disposed inside the substrate; a nematic liquid crystal is disposed between the two alignment films, and the alignment direction of the liquid crystal is twisted from one electrode side to the other electrode side at an angle of 90 degrees. When the non-polarized light is incident in this state, the linearly polarized light that has passed through one polarizer passes through the liquid crystal, and its polarization direction is changed, so that it can pass through the other polarizer to form a bright state. Then, when a voltage is applied to both electrodes to make the liquid crystal molecules stand upright, the linearly polarized light reaching the liquid crystal directly passes through without passing through the other polarizer, forming a dark state. Thereafter, when the application of the voltage is stopped, it returns to a bright state.

Although, due to technological advances in recent years, such a TN type LCD has become comparable or superior to a cathode ray tube (CRT) in terms of front contrast and color reproducibility. However, there is still a big problem with the TN LCD that needs to be solved, that is, the viewing angle is narrow. As a method for solving such a problem, an MVA (Multi-domain Vertically Aligned) type LCD (vertical alignment type liquid crystal display) has been developed. As described in Non-Patent Document 1 and Patent Document 1, the MVA type LCD does not use the optical rotation mode of the TN type LCD, but combines a negative type liquid crystal having a negative dielectric anisotropy and a vertical alignment film, and uses In the birefringence mode LCD, even in a state where no voltage is applied, the liquid crystal alignment direction at a position close to the alignment film can be substantially maintained in the vertical direction, and therefore, the contrast, the viewing angle, and the like are excellent, and the liquid crystal alignment can be prevented. The polishing treatment and the like are also excellent in the production steps.

In the MVA type LCD, in order to allow the liquid crystal to take a plurality of alignment directions in one primitive region, the region limiting method may be to make the electrode on the display side be an electrode having a slit in one primitive region, and to be incident on the light. In the same element region on the side electrode substrate, a protrusion having a slope (for example, a triangular pyramid shape, a semi-convex lens shape, or the like) is formed at a position different from the slit of the electrode. Further, in the conventional liquid crystal display, a spherical or plate-shaped spacer such as a resin or a ceramic is generally used, and the gap (cell gap) between the two transparent electrode substrates is kept constant. When the two transparent electrode substrates are bonded, the spacers may be spread on any one of the substrates, and the cell gap is determined according to the diameter of the spacer.

Further, in order to avoid problems such as unevenness of the cell gap due to the difference in the diameter of the spacer, Patent Document 2 also discloses a method of forming a protrusion and a spacer using a photoresist material, which has the following advantages: it can be finely processed and easily Control the shape. However, Patent Document 2 does not specifically describe the composition of the photoresist material, nor does it indicate the properties of the formed protrusions and spacers.

[Non-Patent Document 1] Takeda Yusuke, Liquid Crystal, Japanese Society of Liquid Crystals, April 25, 1999, Vol. 3, No. 2, 117 [Patent Document 1] Japanese Patent Laid-Open No. Hei 11-258605 (Patent Document 2) -201750 bulletin

The performance required for the photoresist used in the formation of the protrusions and spacers used for the vertical alignment type liquid crystal display element is as follows. That is, in addition to the cross-sectional shape, the protrusions and the spacers are required to withstand the solvent used in the subsequent alignment film forming step, the heat resistance to the alignment film forming step, the transparency, the resolution, and the residue. The film rate and other properties are high. Further, the obtained vertical alignment type liquid crystal display element is required to have excellent alignment properties, voltage holding ratio, and the like. The applicant has proposed a radiation sensitive resin composition for simultaneously forming protrusions and spacers, the resin composition comprising [A] consisting of (a1) unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, (a2) a copolymer of an epoxy group-containing unsaturated compound and (a3) an unsaturated compound other than the above, [B] an unsaturated polymerizable compound and [C] a radiation-sensitive polymerization initiator; and a resin composition proposed from the resin composition The formed protrusions and spacers, and a liquid crystal display element including the protrusions and spacers (see Patent Document 3). However, only a radiation-sensitive resin composition useful for the formation of protrusions and spacers of a vertical alignment type liquid crystal display element has been developed, which has been developed to be compatible with the rapid spread of TFT-LCDs and increasingly stringent performance requirements. A novel radiation sensitive resin composition which forms protrusions and spacers having excellent properties is becoming an important technical subject.

[Patent Document 3] JP-A-2003-29405

The present invention has been made in view of the above problems, and it is an object of the invention to provide a radiation-sensitive resin composition for forming protrusions and/or spacers used for a vertical alignment type liquid crystal display element, and more particularly to provide a photoresist material. It is excellent in resolution and residual film ratio, and can form protrusions and spacers excellent in pattern shape, heat resistance, solvent resistance, transparency, and the like, and can obtain a vertical alignment type liquid crystal display element excellent in alignment property, voltage holding ratio, and the like. A radiation sensitive resin composition, and a method of forming protrusions and/or spacers used in a vertical alignment type liquid crystal display element using the radiation resin composition.

According to the present invention, the above objects and advantages of the present invention are attained by a radiation sensitive resin composition for forming protrusions and/or spacers used for a vertical alignment type liquid crystal display element, which is a radiation sensitive resin. The composition is characterized by comprising [A] a copolymer obtained by copolymerizing the following (a1) to (a3) (hereinafter referred to as "copolymer [A]), wherein (a1) is an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride (hereinafter referred to as "compound (a1)"), (a2) is an unsaturated compound having an epoxy group or an oxetanyl group (hereinafter, referred to as "compound (a2)") And (a3) are olefin-based unsaturated compounds other than the above components (a1) and (a2) (hereinafter, referred to as "compound (a3)"); [B] 1,2-quinonediazide compound; [C Photocationic polymerization initiator.

The object and advantages of the present invention are the second, which is achieved by the protrusions used in the vertical alignment type liquid crystal display element formed of the above-described radiation sensitive resin composition.

The object and advantage of the present invention, the third aspect, is achieved by a spacer used in a vertical alignment type liquid crystal display element formed of the above-described radiation sensitive resin composition.

The object and advantage of the present invention, the fourth aspect, is achieved by a vertical alignment type liquid crystal display element including the above-described protrusions and/or the above spacers.

The object and advantage of the present invention, the fifth aspect is achieved by a method of forming protrusions and/or spacers, the method comprising at least the following steps: (1) forming a feeling described in item 1 of the patent application scope on a substrate a step of coating the film with the radiation composition; (2) a step of irradiating at least a portion of the film with radiation; (3) a developing step; and (4) a heating step.

Hereinafter, each component of the radiation sensitive resin composition of the present invention will be described in detail.

Copolymer (A)

The copolymer [A] is synthesized by subjecting the compound (a1), the compound (a2) and the compound (a3) to radical polymerization in the presence of a polymerization initiator in a solvent.

The copolymer [A] used in the present invention preferably contains 5 to 40% by weight of the constituent unit derived from the compound (a1), and particularly preferably contains 10 to 35% by weight. The copolymer having less than 5% by weight of the constituent unit is hardly dissolved in the alkaline aqueous solution, and the solubility of the copolymer exceeding 40% by weight in the alkaline aqueous solution tends to be excessive.

Examples of the compound (a1) include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid, and the like. An acid anhydride, a monovalent [2-(methyl) propylene methoxyethyl] succinate, a polyvalent polycarboxylic acid such as mono[2-(methyl) propylene oxyethyl] fumarate; (meth)acryloyloxyalkyl]esters, mono(meth)acrylates of polymers having a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate. Among them, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferably used from the viewpoints of copolymerization reactivity, solubility in an alkaline aqueous solution, and easy availability. They can be used alone or in combination.

The copolymer [A] used in the present invention preferably contains 5 to 60% by weight of a constituent unit derived from the compound (a2), and particularly preferably contains 10 to 50% by weight. When the constituent unit is less than 5% by weight, the heat resistance of the obtained coating film tends to be lowered. On the other hand, when it exceeds 60% by weight, the storage stability of the copolymer tends to be lowered.

The compound (a2) may, for example, be an epoxy group-containing unsaturated compound or an oxetanyl group-containing unsaturated compound.

Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, 2-methyl glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, and 3,4-butylbutyl acrylate. Acrylic epoxy (cyclo)alkyl esters such as 6,7-epoxyheptyl acrylate and 3,4-epoxycyclohexyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate , methacrylic acid epoxy (cyclo)alkyl group such as 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate Esters, α-ethyl glycidyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 6,7-epoxyheptyl α-ethyl acrylate, α-B Other α-alkyl acrylate epoxy (cyclo)alkyl esters such as 3,4-epoxycyclohexyl acrylate; o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, - glycidyl ethers such as vinylbenzyl glycidyl ether.

Examples of the oxetane-containing unsaturated compound include 3-(methacryloxymethyl)oxetane and 3-(methacryloxymethyl)-3-B. Oxycyclobutane, 3-(methacryloxymethyl)-3-methyloxetane, 3-(methacryloxymethyl)-2-methyloxane Butane, 3-(methacryloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxymethyl)-2-pentafluoroethyloxycyclohexane Butane, 3-(methacryloxymethyl)-2-phenyloxetane, 3-(methacryloxymethyl)-2,2-difluorooxetane Alkane, 3-(methacryloxymethyl)-2,2,4-trifluorooxetane, 3-(methacryloxymethyl)-2,2,4,4 -tetrafluorooxetane, 3-(methacryloxyethyl)oxetane, 3-(methacryloxyethyl)-3-ethyloxetane 2-ethyl-3-(methacryloxyethyl)oxetane, 3-(methacryloxyethyl)-2-trifluoromethyloxetane, 3 -(methacryl Oxyethyl)-2-pentafluoroethyl oxetane, 3-(methacryloxyethyl)-2-phenyl-oxetane, 2,2-difluoro- 3-(methacryloxyethyl)oxetane, 3-(methacryloxyethyl)-2,2,4-trifluorooxetane, 3-(A Acryloxyethyl)-2,2,4,4-tetrafluorooxetane, 2-(methacryloxymethyl)oxetane, 2-methyl-2 -(methacryloxymethyl)oxetane, 3-methyl-2-(methacryloxymethyl)oxetane, 4-methyl-2-(methyl Propylene methoxymethyl)oxetane, 2-(methacryloxymethyl)-2-trifluoromethyloxetane, 2-(methacryloxymethyl) 3-trifluoromethyloxetane, 2-(methacryloxymethyl)-4-trifluoromethyloxetane, 2-(methacryloxymethyl) -2-pentafluoroethyl oxetane, 2-(methacryloxymethyl)-3-pentafluoroethyl oxetane, 2-(methacryloxymethyl) -4-pentafluoroethyl oxetane, 2-( Acryloxymethyl)-2-phenyloxetane, 2-(methacryloxymethyl)-3-phenyloxetane, 2-(methacryloxyl) Methyl)-4-phenyloxetane, 2,3-difluoro-2-(methacryloxymethyl)oxetane, 2,4-difluoro-2 -(methacryloxymethyl)oxetane, 3,3-difluoro-2-(methacryloxymethyl)oxetane, 3,4-difluoro -2-(methacryloxymethyl)oxetane, 4,4-difluoro-2-(methacryloxymethyl)oxetane, 2-(methyl Propylene methoxymethyl)-3,3,4-trifluorooxetane, 2-(methacryloxymethyl)-3,4,4-trifluorooxetane , 2-(methacryloxymethyl)-3,3,4,4-tetrafluorooxetane, 2-(methacryloxyethyl)oxetane, A 2-(2-(2-methyloxetanyl))ethyl acrylate, 2-(2-(3-methyloxetanyl))ethyl methacrylate, 2-( Methacryloxyethyl)-2-methyloxetane, 2-(methyl Propylene methoxyethyl)-4-methyloxetane, 2-(methacryloxyethyl)-2-trifluoromethyloxetane, 2-(methacryl oxime Oxyethyl)-3-trifluoromethyloxetane, 2-(methacryloxyethyl)-4-trifluoromethyloxetane, 2-(methacryl oxime Oxyethyl)-2-pentafluoroethyl oxetane, 2-(methacryloxyethyl)-3-pentafluoroethyl oxetane, 2-(methacryl oxime Oxyethyl)-4-pentafluoroethyloxetane, 2-(methacryloxyethyl)-2-phenyloxetane, 2-(methacryloxyloxy) Ethyl)-3-phenyloxetane, 2-(methacryloxyethyl)-4-phenyloxetane, 2,3-difluoro-2-(methyl Propylene oxiranyl ethyl) oxetane, 2,4-difluoro-2-(methacryloxyethyl)oxetane, 3,3-difluoro-2-( Methyl propylene oxiranyl ethyl oxetane, 3,4-difluoro-2-(methacryl oxiranyloxy) oxetane, 4,4-difluoro-2 -(methacryloxyethyl)oxy Butane, 2-(methacryloxyethyl)-3,3,4-trifluorooxetane, 2-(methacryloxyethyl)-3,4,4- a methacrylate such as a trifluorooxetane or a 2-(methacryloxyethyl)-3,3,4,4-tetrafluorooxetane; 3-(polypropylene oxide) Oxymethyl)oxetane, 3-(acryloxymethyl)-3-ethyloxetane, 3-(acryloxymethyl)-3-methyloxocycle Butane, 3-(acryloxymethyl)-2-methyloxetane, 3-(acryloxymethyl)-2-trifluoromethyloxetane, 3-( Propylene methoxymethyl)-2-pentafluoroethyl oxetane, 3-(acryloxymethyl)-2-phenyl oxetane, 3-(acryloxymethyl) )-2,2-difluorooxetane, 3-(acryloxymethyl)-2,2,4-trifluorooxetane, 3-(acryloxymethyl) -2,2,4,4-tetrafluorooxetane, 3-(acryloxyethyl)oxetane, 3-(acryloxyethyl)-3-ethyl Oxetane, 2-ethyl-3-(acryloxyethyl) oxalate Butane, 3-(acryloxyethyl)-2-trifluoromethyloxetane, 3-(acryloxyethyl)-2-pentafluoroethyloxetane, 3 -(propylene methoxyethyl)-2-phenyl oxetane, 2,2-difluoro-3-(propylene oxiranyloxy) oxetane, 3-(propylene oxime Benzyl)-2,2,4-trifluorooxetane, 3-(acryloxyethyl)-2,2,4,4-tetrafluorooxetane, 2- (propylene methoxymethyl) oxetane, 2-methyl-2-(acryloxymethyl)oxetane, 3-methyl-2-(acryloxymethyl) Oxetane, 4-methyl-2-(acryloxymethyl)oxetane, 2-(acryloxymethyl)-2-trifluoromethyloxetane, 2-(Propyloxymethyl)-3-trifluoromethyloxetane, 2-(acryloxymethyl)-4-trifluoromethyloxetane, 2-(propylene醯oxymethyl)-2-pentafluoroethyl oxetane, 2-(acryloxymethyl)-3-pentafluoroethyl oxetane, 2-(propylene oxyalkylene) Base)-4-pentafluoroethyl oxetane, 2-( Enoxamethoxymethyl)-2-phenyloxetane, 2-(acryloxymethyl)-3-phenyloxetane, 2-(acryloxymethyl)- 4-phenyloxetane, 2,3-difluoro-2-(acryloxymethyl)oxetane, 2,4-difluoro-2-(propyleneoxymethyl) Oxetane, 3,3-difluoro-2-(acryloxymethyl)oxetane, 3,4-difluoro-2-(acryloxymethyl)oxyl Heterocyclic butane, 4,4-difluoro-2-(acryloxymethyl)oxetane, 2-(acryloxymethyl)-3,3,4-trifluorooxyl Heterocyclic butane, 2-(acryloxymethyl)-3,4,4-trifluorooxetane, 2-(acryloxymethyl)-3,3,4,4- Tetrafluorooxetane, 2-(acryloxyethyl)oxetane, 2-(2-(2-methyloxetanyl)ethyl methacrylate, methyl 2-(2-(3-methyloxetanyl)ethyl acrylate, 2-(acryloxyethyl)-2-methyloxetane, 2-(acryloxy) 4-methyloxetane, 2-(acryloxyethyl)-2- Fluoromethyl oxetane, 2-(acryloxyethyl)-3-trifluoromethyloxetane, 2-(acryloxyethyl)-4-trifluoromethyloxy Heterocyclic butane, 2-(acryloxyethyl)-2-pentafluoroethyl oxetane, 2-(acryloxyethyl)-3-pentafluoroethyl oxetane , 2-(propylene methoxyethyl)-4-pentafluoroethyl oxetane, 2-(acryloxyethyl)-2-phenyl oxetane, 2-(acrylofluorene Oxyethyl)-3-phenyloxetane, 2-(acryloxyethyl)-4-phenyloxetane, 2,3-difluoro-2-(acrylofluorene) Oxyethyl)oxetane, 2,4-difluoro-2-(propyleneoxyethyl)oxetane, 3,3-difluoro-2-(propyleneoxyloxy) Ethyl)oxetane, 3,4-difluoro-2-(acryloxyethyl)oxetane, 4,4-difluoro-2-(acryloxyethyl) Oxetane, 2-(acryloxyethyl)-3,3,4-trifluorooxetane, 2-(acryloxyethyl)-3,4,4- Trifluorooxetane, 2-(acryloxyethyl)-3,3 An acrylate such as 4,4-tetrafluorooxetane.

Among them, from the viewpoint that the obtained photosensitive resin composition has a wide processing range and the chemical resistance of the obtained protrusions and spacers can be improved, as the epoxy group-containing unsaturated compound, glycidyl methacrylate is preferably used. Ester, 2-methylglycidyl methacrylate, 6,7-epoxyheptyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, o-vinylbenzyl glycidyl ether, m-ethylene Glycidyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc.; as the oxetanyl group-containing unsaturated compound, 3-(methacryloxymethyl)oxetane is preferably used. , 3-(methacryloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxymethyl)-2-phenyloxetane, 2 -(methacryloxymethyl)oxetane, 2-(methacryloxymethyl)-4-trifluoromethyloxetane, 3-(methacryloxyl) Methyl)-3-ethyloxetane, 3-(methacryloxymethyl)-3-methyloxetane, 3-(propylene oxyalkylene) ) -3-ethyl oxetane, 3- (Bing Xixi yloxy) -3-methyl oxetane. They can be used alone or in combination.

The copolymer [A] used in the present invention preferably contains 10 to 80% by weight of a constituent unit derived from the compound (a3), and particularly preferably contains 20 to 70% by weight. When the structural unit is less than 10% by weight, the storage stability of the copolymer [A] tends to be lowered. On the other hand, when it exceeds 80% by weight, the copolymer [A] is hardly soluble in an aqueous alkaline solution.

Examples of the compound (a3) include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate, and acrylic acid. Alkyl acrylates such as methyl ester and isopropyl acrylate; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, trimethyl methacrylate [5.2.1.0 ^{2 . 6} ] 癸-8-yl Ester (as a commonly used name in the art, also known as dicyclopentanyl methacrylate), dimethyl pentaneoxyethyl methacrylate, isophorone methacrylate, etc. Alkyl esters, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.0 ^{2 . 6} ] 癸-8-yl acrylate (also known as acrylic acid in the field) Acrylic cyclic alkyl esters such as cyclopentyl ester), dicyclopentanyloxyethyl acrylate, isophorone acrylate, aryl methacrylate such as phenyl methacrylate or benzyl methacrylate Classes, aryl acrylates such as phenyl acrylate and benzyl acrylate, diethyl maleate, rich Dicarboxylic acid diesters such as diethyl acid and diethyl itaconate, hydroxyalkyl esters such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; bicyclo [2.2. 1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2. 1]hept-2-ene, 5-carboxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl Bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene , 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)di Ring [2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2 .1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene , 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-B Bicyclo[2.2.1]hept-2-ene, 5 Hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethyl Bicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (norbornene dianhydride), 5-tert-butoxycarbonylbicyclo[ 2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5 , 6-di(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene, etc. a cyclic unsaturated compound; phenyl maleimide, cyclohexylmaleimide, benzyl maleimide, N-succinimide-3-maleimide benzoate, N-Amber succinimide-4-maleimide butyrate, N-succinimide-6-maleimide caproate, N-amber quinone imine-3-malay Dicarbonyl quinone imine derivatives such as quinone imine ester, N-(9-acridinyl) maleimide; styrene, α-methylstyrene, m-methylstyrene, p- Methylstyrene, vinyl toluene p-Methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene , 2,3-dimethyl-1,3-butadiene, glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, glycidyl α-n-propyl acrylate, α- Glycidyl butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, methacrylic acid- 6,7-epoxyheptyl ester, α-ethyl acrylate 6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinyl benzyl Glycidyl ether and the like.

Among them, styrene, tert-butyl methacrylate, dicyclopentanyl methacrylate, p-methoxystyrene, acrylic acid 2 are preferred from the viewpoints of copolymerization reactivity and solubility in an aqueous alkaline solution. -Methylcyclohexyl ester, 1,3-butadiene, glycidyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidol Ether, phenylmaleimide, cyclohexylmaleimide, bicyclo[2.2.1]hept-2-ene, and the like. They can be used singly or in combination.

As described above, the copolymer [A] used in the present invention has a carboxyl group and/or an acid anhydride group and an oxetanyl group, and has an appropriate solubility to an alkaline aqueous solution, and can also be used without being used together with a specific curing agent. Heating is easily cured.

The radiation-sensitive resin composition containing the copolymer [A] described above does not cause development residue during development, and does not cause film reduction, and it is easy to form a coating film having a predetermined pattern.

Specific examples of the solvent used in the synthesis of the copolymer [A] include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; and glycols such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether. Ethers; ethylene cellosolve acetate, ethyl cellosolve acetate, etc., ethylene glycol alkyl ether acetate; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Diethylene glycol such as dimethyl ether, diethylene glycol diethyl ether or diethylene glycol ethyl methyl ether; propylene glycol monoether such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether or propylene glycol butyl ether Alkyl ethers; propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc.; propylene glycol methyl ether propionate; propylene glycol methyl ether propionic acid Propylene glycol alkyl ether propionate such as ester, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone, Ketones such as 4-hydroxy-4-methyl-2-pentanone; methyl acetate, ethyl acetate, propyl acetate, butyl acetate Ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, lactic acid Methyl ester, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxyl Methyl 3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyacetic acid Ester, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate , ethyl butoxylate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, sodium 2-methoxypropionate Ester, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate Ester, methyl 2-butoxypropionate, Ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3-butyl ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, Esters such as methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

Further, as the polymerization initiator used in the production of the copolymer [A], a known radical polymerization initiator can be used, and examples thereof include 2,2'-azobisisobutyronitrile and 2,2'-couple. An azo compound such as nitrogen di-(2,4-dimethylvaleronitrile) or 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), benzamidine Organic peroxides such as peroxide, lauryl peroxide, t-butyl peroxypivalate, 1,1'-di-(tert-butylperoxy)cyclohexane, and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, a peroxide and a reducing agent can also be used together as an oxidation-reduction type initiator.

In the production of the copolymer [A], a molecular weight modifier for adjusting the molecular weight can be used. Specific examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrabromide, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and thioglycolic acid. Such as thiol, dimethyl keogen sulfide, diisopropyl xanthogen disulfide and other xanthogen, terpinolene, α-methyl styrene dimer and the like.

The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the copolymer [A] used in the present invention is usually 2 × 10 ³ to 5 × 10 ⁵ , preferably 5 × 10 ³ to 1 ×10 ⁵ . If Mw is less than 2 × 10 ³ , the residual film ratio after development tends to decrease, and if it exceeds 5 × 10 ⁵ , development residue remains.

1,2-quinonediazide compound [B]

Examples of the [B] 1,2-quinonediazide compound include 1,2-benzoquinonediazidesulfonate, 1,2-naphthoquinonediazidesulfonate, and 1,2-benzoquinone. Amidoxidinium diazidosulfonate and decylamine 1,2-naphthoquinonediazidesulfonate.

Specific examples thereof include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate and 2,3,4-trihydroxybenzophenone-1. , 2-naphthoquinonediazide-5-sulfonate, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonate, 2,3,4 -Trihydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonate, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonate Acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone Diazido-5-sulfonate, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonate, 2,4,6-trihydroxydiphenyl Trihydroxyl of keto-1,2-naphthoquinonediazide-7-sulfonate, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonate 1,2-naphthoquinonediazidesulfonate of benzophenone; 2,2',4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid Ester, 2,2',4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,2',4,4'-four Dibenzophenone-1,2-naphthoquinonediazide-6-sulfonate, 2,2',4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-7 -sulfonate, 2,2',4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonate, 2,3'4,3'-tetrahydroxy Phenylketone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid Ester, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonate, 2,3,4,3'-tetrahydroxybenzophenone-1 , 2-naphthoquinonediazide-7-sulfonate, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonate, 2, 3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthalene Bis-azido-5-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonate, 2,3,4, 4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide Base-8-sulfonate, 2,3,4,2 -tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone -1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide- 6-sulfonate, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-7-sulfonate, 2,3,4, 2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-8-sulfonate, 2,3,4,4'-tetrahydroxy-3'-methoxy Benzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinone Azido-5-sulfonate, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-6-sulfonate, 2 ,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-7-sulfonate, 2,3,4,4'-tetrahydroxy- 1,2-naphthoquinonediazidesulfonate of tetrahydroxybenzophenone such as 3'-methoxybenzophenone-1,2-naphthoquinonediazide-8-sulfonate; 3, 4,2',6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,2',6'-pentahydroxybenzophenone-1 , 2-naphthoquinonediazide-5-sulfonate, 2,3,4,2',6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonate , 2,3,4,2',6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonate, 2,3,4,2',6'-pentahydroxy 1,2-naphthoquinonediazidesulfonate of pentahydroxybenzophenone such as benzophenone-1,2-naphthoquinonediazide-8-sulfonate; 2,4,6,3' , 4',5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,4,6,3',4',5'-hexahydroxybenzophenone -1,2-naphthoquinonediazide-5-sulfonate, 2,4,6,3',4',5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide- 6-sulfonate, 2,4,6,3',4',5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonate, 2,4,6, 3',4',5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonate, 3,4,5,3',4',5'-hexahydroxydi Phenylketone-1,2-naphthoquinonediazide-4-sulfonate, 3,4,5,3',4 ',5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 3,4,5,3',4',5'-hexahydroxybenzophenone-1 , 2-naphthoquinonediazide-6-sulfonate, 3,4,5,3',4',5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-7- a sulfonic acid ester, a hexahydroxybenzophenone such as 3,4,5,3',4',5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonate, 2-naphthoquinonediazidesulfonate; bis(2,4-dihydroxyphenyl)methane-1,2-naphthoquinonediazide-4-sulfonate, bis(2,4-di Hydroxyphenyl)methane-1,2-naphthoquinonediazide-5-sulfonate, bis(2,4-dihydroxyphenyl)methane-1,2-naphthoquinonediazide-6-sulfonate Acid ester, bis(2,4-dihydroxyphenyl)methane-1,2-naphthoquinonediazide-7-sulfonate, bis(2,4-dihydroxyphenyl)methane-1,2- Naphthoquinonediazide-8-sulfonate, bis(p-hydroxyphenyl)methane-1,2-naphthoquinonediazide-4-sulfonate, bis(p-hydroxyphenyl)methane-1, 2-naphthoquinonediazide-5-sulfonate, bis(p-hydroxyphenyl)methane-1,2-naphthoquinonediazide-6-sulfonate Bis(p-hydroxyphenyl)methane-1,2-naphthoquinonediazide-7-sulfonate, bis(p-hydroxyphenyl)methane-1,2-naphthoquinonediazide-8-sulfonic acid Ester, tris(p-hydroxyphenyl)methane-1,2-naphthoquinonediazide-4-sulfonate, tris(p-hydroxyphenyl)methane-1,2-naphthoquinonediazide-5- Sulfonate, tris(p-hydroxyphenyl)methane-1,2-naphthoquinonediazide-6-sulfonate, tris(p-hydroxyphenyl)methane-1,2-naphthoquinonediazide- 7-sulfonate, tris(p-hydroxyphenyl)methane-1,2-naphthoquinonediazide-8-sulfonate, 1,1,1-tris(p-hydroxyphenyl)ethane-1, 2-naphthoquinonediazide-4-sulfonate, 1,1,1-tris(p-hydroxyphenyl)ethane-1,2-naphthoquinonediazide-5-sulfonate, 1, 1,1-tris(p-hydroxyphenyl)ethane-1,2-naphthoquinonediazide-6-sulfonate, 1,1,1-tris(p-hydroxyphenyl)ethane-1,2 -naphthoquinonediazide-7-sulfonate, 1,1,1-tris(p-hydroxyphenyl)ethane-1,2-naphthoquinonediazide-8-sulfonate, double (2 ,3,4-trihydroxyphenyl)methane-1,2-naphthoquinonediazide-4-sulfonate, bis(2,3,4- Hydroxyphenyl)methane-1,2-naphthoquinonediazide-5-sulfonate, bis(2,3,4-trihydroxyphenyl)methane-1,2-naphthoquinonediazide-6 -sulfonate, bis(2,3,4-trihydroxyphenyl)methane-1,2-naphthoquinonediazide-7-sulfonate, bis(2,3,4-trihydroxyphenyl) Methane-1,2-naphthoquinonediazide-8-sulfonate, 2,2-bis(2,3,4-trihydroxyphenyl)propane-1,2-naphthoquinonediazide-4 -sulfonate, 2,2-bis(2,3,4-trihydroxyphenyl)propane-1,2-naphthoquinonediazide-5-sulfonate, 2,2-bis (2,3 ,4-trihydroxyphenyl)propane-1,2-naphthoquinonediazide-6-sulfonate, 2,2-bis(2,3,4-trihydroxyphenyl)propane-1,2- Naphthoquinonediazide-7-sulfonate, 2,2-bis(2,3,4-trihydroxyphenyl)propane-1,2-naphthoquinonediazide-8-sulfonate, 1 , 1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonate, 1,1,3- Tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonate, 1,1,3-tri(2, 5-dimethyl-4-hydroxybenzene 3-phenylpropane-1,2-naphthoquinonediazide-6-sulfonate, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3 -Phenylpropane-1,2-naphthoquinonediazide-7-sulfonate, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane -1,2-naphthoquinonediazide-8-sulfonate, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl] Ethylene]bisphenol-1,2-naphthoquinonediazide-4-sulfonate, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methyl Ethyl]phenyl]ethylidene]bisphenol-1,2-naphthoquinonediazide-5-sulfonate, 4,4'-[1-[4-[1-[4-hydroxyphenyl ]-1-methylethyl]phenyl]ethylidene]bisphenol-1,2-naphthoquinonediazide-6-sulfonate, 4,4'-[1-[4-[1- [4-Hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol-1,2-naphthoquinonediazide-7-sulfonate, 4,4'-[1- [4-[1-[4-Hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol-1,2-naphthoquinonediazide-8-sulfonate, double 2,5-dimethyl-4-hydroxyphenyl) 2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonate, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane-1 , 2-naphthoquinonediazide-5-sulfonate, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane-1,2-naphthoquinonediazide -6-sulfonate, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane-1,2-naphthoquinonediazide-7-sulfonate, double 2,5-Dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane-1,2-naphthoquinonediazide-8-sulfonate, 3,3,3',3'-four Methyl-1,1'-spiro-di-indol-5,6,7,5',6',7'-hexanol-1,2-naphthoquinonediazide-4-sulfonate, 3 ,3,3',3'-tetramethyl-1,1'-spiro-di-indol-5,6,7,5',6',7'-hexanol-1,2-naphthoquinone Nitro-5-sulfonate, 3,3,3',3'-tetramethyl-1,1'-spiro-di-indol-5,6,7,5',6',7'-hexyl Alcohol-1,2-naphthoquinonediazide-6-sulfonate, 3,3,3',3'-tetramethyl-1,1'-spiro-di-indol-5,6,7, 5',6',7'-hexanol-1,2-naphthoquinone Diazido-7-sulfonate, 3,3,3',3'-tetramethyl-1,1'-spiro-di-anthracene-5,6,7,5',6',7' -hexanol-1,2-naphthoquinonediazide-8-sulfonate, 2,2,4-trimethyl-7,2',4'-trihydroxyflavan-1,2-naphthoquinone Diazido-4-sulfonate, 2,2,4-trimethyl-7,2',4'-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonate 2,2,4-Trimethyl-7,2',4'-trihydroxyflavan-1,2-naphthoquinonediazide-6-sulfonate, 2,2,4-trimethyl -7,2',4'-trihydroxyflavan-1,2-naphthoquinonediazide-7-sulfonate, 2,2,4-trimethyl-7,2',4'-three 1,2-naphthoquinonediazide sulfonate of (polyhydroxyphenyl)alkane such as hydroxyflavan-1,2-naphthoquinonediazide-8-sulfonate.

These 1,2-quinonediazide compounds may be used singly or in combination of two or more.

The component [B] is used in a proportion of 5 to 100 parts by weight, preferably 10 to 50 parts by weight, per 100 parts by weight of the copolymer [A].

When the ratio is less than 5 parts by weight, the amount of acid generated by radiation irradiation is small. Therefore, the difference in solubility between the portion irradiated with radiation and the portion not irradiated with the alkaline aqueous solution as the developer is small, and it tends to be difficult to pattern. Further, the amount of the acid associated with the reaction of the copolymer [A] becomes small, and sufficient heat resistance and solvent resistance may not be obtained. On the other hand, when the ratio exceeds 100 parts by weight, when the radiation is irradiated for a short period of time, the unreacted [B] component remains in a large amount, and the effect of being insoluble in the alkaline aqueous solution is too high, and it tends to be difficult to develop.

Photocationic polymerization initiator [C]

As the photocationic polymerization initiator [C], a phosphonium salt can be mentioned. The onium salt is composed of a phosphonium cation and an anion derived from Lewis acid.

Specific examples of the phosphonium cation include diphenyl iodonium, di(p-tolyl) iodonium, di(p-tert-butylphenyl) iodonium, and di(p-octylphenyl) iodonium. Bis(p-octadecylphenyl)iodonium, bis(p-octyloxyphenyl)iodonium, bis(p-octadecyloxyphenyl)iodonium, phenyl(p-octadecane) Oxyphenyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, methylnaphthyl iodonium, ethylnaphthyl iodonium, triphenylphosphonium, tris(p-toluene) , 三, tris(p-isopropylphenyl) fluorene, tris(2,6-dimethylphenyl)anthracene, tris(p-tert-butylphenyl)anthracene, tris(p-cyanophenyl) ) anthracene, tris(p-chlorophenyl)anthracene, dimethylnaphthyl anthracene, diethylnaphthyl anthracene, dimethyl(methoxy)anthracene, dimethyl(ethoxy)anthracene, dimethyl (propoxy) hydrazine, dimethyl (butoxy) hydrazine, dimethyl (octyloxy) hydrazine, dimethyl (octadecyloxy) hydrazine, dimethyl (isopropoxy) hydrazine , dimethyl (tert-butoxy) hydrazine, dimethyl (cyclopentyloxy) hydrazine, dimethyl (cyclohexyloxy) fluorene, dimethyl (fluoromethoxy) hydrazine, dimethyl ( 2-chloroethoxy)anthracene, dimethyl (3-bromopropoxy) hydrazine, dimethyl (4-cyanobutoxy) hydrazine, dimethyl (8-nitrooctyloxy) hydrazine, dimethyl (18-trifluoromethyl) Octadecyloxy)anthracene, dimethyl(2-hydroxyisopropoxy)anthracene, dimethyl(tris(trichloromethyl)methyl)anthracene, and the like. Preferred are bis(p-tolyl)iodonium, (p-tolyl)(p-isopropylphenyl)iodonium, di(p-tert-butylphenyl)iodonium, triphenylphosphonium, Tris(p-tert-butylphenyl) hydrazine and the like.

Specific examples of the anion derived from the Lewis acid include hexafluorophosphate, hexafluoroaluminate, hexafluoroantimonate, tetrakis(pentafluorophenyl)borate, and the like, and hexafluoroantimonic acid is preferred. Salt, tetrakis(pentafluorophenyl)borate.

The foregoing phosphonium cation and an anion derived from Lewis acid can be arbitrarily combined.

Specifically, examples of the [C] photocationic polymerization initiator include diphenyliodonium hexafluorophosphate, bis(p-tolyl)iodonium hexafluorophosphate, and di(p-tert-butylphenyl)iodonium. Hexafluorophosphate, bis(p-octylphenyl)iodonium hexafluorophosphate, di(p-octadecylphenyl)iodonium hexafluorophosphate, di(p-octyloxyphenyl)iodine Hexafluorophosphate, bis(p-octadecyloxyphenyl)iodonium hexafluorophosphate, phenyl (p-octadecyloxyphenyl) iodonium hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, methylnaphthyl iodonium hexafluorophosphate, ethylnaphthyl iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, three ( P-tolyl)phosphonium hexafluorophosphate, tris(p-isopropylphenyl)phosphonium hexafluorophosphate, tris(2,6-dimethylphenyl)phosphonium hexafluorophosphate, three (p-terr Butylphenyl)phosphonium hexafluorophosphate, tris(p-cyanophenyl)phosphonium hexafluorophosphate, tris(p-chlorophenyl)phosphonium hexafluorophosphate, dimethylnaphthylphosphonium hexafluorophosphate Salt, diethylnaphthylphosphonium hexafluorophosphate, dimethyl(methoxy)phosphonium hexafluorophosphate Dimethyl(ethoxy)phosphonium hexafluorophosphate, dimethyl(propoxy)phosphonium hexafluorophosphate, dimethyl(butoxy)phosphonium hexafluorophosphate, dimethyl (octyloxy) Hexafluorophosphate, dimethyl(octadecyloxy)phosphonium hexafluorophosphate, dimethyl(isopropoxy)phosphonium hexafluorophosphate, dimethyl(tert-butoxy)phosphonium hexafluorophosphate Salt, dimethyl(cyclopentyloxy)phosphonium hexafluorophosphate, dimethyl(cyclohexyloxy)phosphonium hexafluorophosphate, dimethyl(fluoromethoxy)phosphonium hexafluorophosphate, dimethyl (2-chloroethoxy)phosphonium hexafluorophosphate, dimethyl(3-bromopropoxy)phosphonium hexafluorophosphate, dimethyl(4-cyanobutoxy)phosphonium hexafluorophosphate Salt, dimethyl(8-nitrooctyloxy)phosphonium hexafluorophosphate, dimethyl (18-trifluoromethyloctadecyloxy)phosphonium hexafluorophosphate, dimethyl (2-hydroxyiso) Propoxy)phosphonium hexafluorophosphate, dimethyl(tris(trichloromethyl)methyl)phosphonium hexafluorophosphate; diphenyliodonium hexafluoroaluminate, bis(p-tolyl)iodonium Fluoroaluminate, di(p-tert-butylphenyl)iodonium hexafluoroaluminate, bis(p-octylphenyl)iodonium hexafluoroaluminate, two (p-eighteen Phenylphenyl)iodonium hexafluoroaluminate, bis(p-octyloxyphenyl)iodonium hexafluoroaluminate, di(p-octadecyloxyphenyl)iodonium hexafluoroaluminate, Phenyl (p-octadecyloxyphenyl) iodonium hexafluoroaluminate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroaluminate, methylnaphthyl iodonium Hexafluoroaluminate, ethylnaphthyl iodonium hexafluoroaluminate, triphenylsulfonium hexafluoroaluminate, tris(p-tolyl)phosphonium hexafluoroaluminate, tris(p-isopropylbenzene) Hexafluoroaluminate, tris(2,6-dimethylphenyl)phosphonium hexafluoroaluminate, tris(p-tert-butylphenyl)phosphonium hexafluoroaluminate, tris(p-cyanide) Phenyl phenyl) hexafluoroaluminate, tris(p-chlorophenyl) sulfonium hexafluoroaluminate, dimethylnaphthyl fluorene hexafluoroaluminate, diethyl naphthyl fluorene hexafluoroaluminate , dimethyl(methoxy)phosphonium hexafluoroaluminate, dimethyl(ethoxy)phosphonium hexafluoroaluminate, dimethyl(propoxy)phosphonium hexafluoroaluminate, dimethyl ( Butoxy) hexafluoroaluminate, dimethyl(octyloxy)phosphonium hexafluoroaluminate, dimethyl(octadecyloxy)phosphonium hexafluoroaluminate, dimethyl (isopropoxy) Hexafluoroaluminate , dimethyl (tert-butoxy) sulfonium hexafluoroaluminate, dimethyl (cyclopentyloxy) ruthenium hexafluoroaluminate, dimethyl (cyclohexyloxy) ruthenium hexafluoroaluminate, two Methyl(fluoromethoxy)phosphonium hexafluoroaluminate, dimethyl(2-chloroethoxy)phosphonium hexafluoroaluminate, dimethyl(3-bromopropoxy)phosphonium hexafluorophosphate Aluminate, dimethyl(4-cyanobutoxy)phosphonium hexafluoroaluminate, dimethyl(8-nitrooctyloxy)phosphonium hexafluoroaluminate, dimethyl (18-trifluoro) Methyloctadecyloxy)phosphonium hexafluoroaluminate, dimethyl(2-hydroxyisopropoxy)phosphonium hexafluoroaluminate, dimethyl(tris(trichloromethyl)methyl)phosphonium Fluoroaluminate; diphenyliodonium hexafluoroantimonate, bis(p-tolyl)iodonium hexafluoroantimonate, di(p-tert-butylphenyl)iodonium hexafluoroantimonate, two ( p-Octylphenyl)iodonium hexafluoroantimonate, di(p-octadecylphenyl)iodonium hexafluoroantimonate, di(p-octyloxyphenyl)iodonium hexafluoroantimonate Salt, di(p-octadecyloxyphenyl)iodonium hexafluoroantimonate, phenyl(p-octadecyloxyphenyl)iodonium hexafluoroantimonate, (p-tolyl) ( P-isopropylphenyl)iodonium Citrate, methylnaphthyl iodonium hexafluoroantimonate, ethylnaphthyl iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris(p-tolyl)phosphonium hexafluoroantimonate Salt, tris(p-isopropylphenyl)phosphonium hexafluoroantimonate, tris(2,6-dimethylphenyl)phosphonium hexafluoroantimonate, tris(p-tert-butylphenyl)phosphonium Fluoride, tris(p-cyanophenyl)phosphonium hexafluoroantimonate, tris(p-chlorophenyl)phosphonium hexafluoroantimonate, dimethylnaphthylphosphonium hexafluoroantimonate, Ethylnaphthylfluorene hexafluoroantimonate, dimethyl(methoxy)phosphonium hexafluoroantimonate, dimethyl(ethoxy)phosphonium hexafluoroantimonate, dimethyl(propoxy)fluorene Hexafluoroantimonate, dimethyl(butoxy)phosphonium hexafluoroantimonate, dimethyl(octyloxy)phosphonium hexafluoroantimonate, dimethyl(octadecyloxy)phosphonium hexafluoroantimonate Acid salt, dimethyl(isopropoxy)phosphonium hexafluoroantimonate, dimethyl(tert-butoxy)phosphonium hexafluoroantimonate, dimethyl(cyclopentyloxy)phosphonium hexafluoroantimonate , dimethyl(cyclohexyloxy)phosphonium hexafluoroantimonate, dimethyl(fluoromethoxy)phosphonium hexafluoroantimonate, dimethyl(2-chloroethoxy)phosphonium hexafluoroantimonate Acid salt, dimethyl (3- Propyloxy)phosphonium hexafluoroantimonate, dimethyl(4-cyanobutoxy)phosphonium hexafluoroantimonate, dimethyl(8-nitrooctyloxy)phosphonium hexafluoroantimonate, Dimethyl (18-trifluoromethyloctadecyloxy)phosphonium hexafluoroantimonate, dimethyl(2-hydroxyisopropoxy)phosphonium hexafluoroantimonate, dimethyl (tris(trichloro) Methyl)methyl)phosphonium hexafluoroantimonate; diphenyliodonium tetrakis(pentafluorophenyl)borate, di(p-tolyl)iodonium tetrakis(pentafluorophenyl)borate, di(p- Tert-butylphenyl)iodonium tetrakis(pentafluorophenyl)borate, bis(p-octylphenyl)iodonium tetrakis(pentafluorophenyl)borate, di(p-octadecylphenyl) Iodine tetrakis(pentafluorophenyl)borate, bis(p-octyloxyphenyl)iodonium tetrakis(pentafluorophenyl)borate, di(p-octadecyloxyphenyl)iodonium tetra(4) Pentafluorophenyl)borate, phenyl(p-octadecyloxyphenyl)iodonium tetrakis(pentafluorophenyl)borate, (p-tolyl)(p-isopropylphenyl)iodonium Tetrakis(pentafluorophenyl)borate, methylnaphthyliodonium tetrakis(pentafluorophenyl)borate, ethylnaphthyliodonium tetrakis(pentafluorophenyl)borate, triphenylsulfonium tetrakis(pentafluoro) Phenyl) borate, three (p-tolyl) ruthenium tetrakis(pentafluorophenyl)borate, tris(p-isopropylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, tris(2,6-dimethylphenyl) Tetrakis(pentafluorophenyl)borate, tris(p-tert-butylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, tris(p-cyanophenyl)phosphonium tetrakis(pentafluorophenyl)borate Salt, tris(p-chlorophenyl)phosphonium tetrakis(pentafluorophenyl)borate, dimethylnaphthylphosphonium tetrakis(pentafluorophenyl)borate, diethylnaphthylphosphonium tetrakis(pentafluorophenyl) Borate, dimethyl (methoxy) ruthenium tetrakis(pentafluorophenyl) borate, dimethyl (ethoxy) ruthenium tetrakis(pentafluorophenyl) borate, dimethyl (propoxy) Tetrakis(pentafluorophenyl)borate, dimethyl(butoxy)phosphonium tetrakis(pentafluorophenyl)borate, dimethyl(octyloxy)phosphonium tetrakis(pentafluorophenyl)borate, two Methyl(octadecyloxy)phosphonium tetrakis(pentafluorophenyl)borate, dimethyl(isopropoxy)phosphonium tetrakis(pentafluorophenyl)borate, dimethyl(tert-butoxy)anthracene Tetrakis(pentafluorophenyl)borate, dimethyl(cyclopentyloxy)phosphonium tetrakis(pentafluorophenyl)borate, dimethyl(cyclohexyloxy)phosphonium tetrakis(pentafluorophenyl)borate, Dimethyl (fluoromethoxy) fluorene tetra ( Fluorophenyl)borate, dimethyl(2-chloroethoxy)phosphonium tetrakis(pentafluorophenyl)borate, dimethyl(3-bromopropoxy)phosphonium tetrakis(pentafluorophenyl) Borate, dimethyl(4-cyanobutoxy)phosphonium tetrakis(pentafluorophenyl)borate, dimethyl(8-nitrooctyloxy)phosphonium tetrakis(pentafluorophenyl)borate, two Methyl (18-trifluoromethyloctadecyloxy)phosphonium tetrakis(pentafluorophenyl)borate, dimethyl(2-hydroxyisopropoxy)phosphonium tetrakis(pentafluorophenyl)borate, two Methyl (tris(trichloromethyl)methyl)phosphonium tetrakis(pentafluorophenyl)borate.

Preferred is bis(p-tolyl)iodonium hexafluorophosphate, (p-tolyl)(p-isopropylphenyl)iodonium hexafluorophosphate, di(p-tert-butylphenyl). Iodine hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris(p-tert-butylphenyl)phosphonium hexafluorophosphate, di(p-tolyl)iodonium hexafluoroaluminate, (p- Tolyl)(p-isopropylphenyl)iodonium hexafluoroaluminate, di(p-tert-butylphenyl)iodonium hexafluoroaluminate, triphenylsulfonium hexafluoroaluminate, three (pair) -tert-Butylphenyl)phosphonium hexafluoroaluminate, bis(p-tolyl)iodonium hexafluoroantimonate, (p-tolyl)(p-isopropylphenyl)iodonium hexafluoroantimonate Salt, di(p-tert-butylphenyl)iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris(p-tert-butylphenyl)phosphonium hexafluoroantimonate, di(pair) -toluyl)iodonium tetrakis(pentafluorophenyl)borate, (p-tolyl)(p-isopropylphenyl)iodonium tetrakis(pentafluorophenyl)borate, di(p-tert-butyl) Phenyl) iodonium tetrakis(pentafluorophenyl)borate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, tris(p-tert-butylphenyl)phosphonium tetrakis(pentafluorophenyl)borate Wait.

More preferred is bis(p-tolyl)iodonium hexafluoroantimonate, (p-tolyl)(p-isopropylphenyl)iodonium hexafluoroantimonate, di(p-tert-butyl) Phenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris(p-tert-butylphenyl)phosphonium hexafluoroantimonate, di(p-tolyl)iodonium tetrachloride (five Fluorophenyl)borate, (p-tolyl)(p-isopropylphenyl)iodonium tetrakis(pentafluorophenyl)borate, di(p-tert-butylphenyl)iodonium tetra(pentafluoro) Phenyl)borate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, tris(p-tert-butylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, and the like.

The component [C] is used in a proportion of 0.01 to 15 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the copolymer [A]. In the above-mentioned range, if the amount is 0.01 to 15 parts by weight, the curing speed of the exposed portion can be increased, the film of the pattern at the time of development can be reduced, and the residual film ratio can be increased, which is preferable.

Thioxanthone compound [D]

As the [D] thioxanthone compound, for example, thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,3-diethylthioxanthone, 2, 4 may be mentioned. 2-Diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-cyclohexylthioxanthone, 4-cyclohexylthioxanthone, and the like.

The use ratio of the component [D] is usually 15 parts by weight or less, preferably 0.01 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the copolymer [A]. When the content of the component [D] is 0.01 to 15 parts by weight, the photocationic polymerization initiator can be sensitized, the curing speed at the time of curing can be increased, the resolution at the time of curing can be suppressed, and the solvent resistance of the cured film can be improved. Preferably.

Other ingredients

The radiation sensitive resin composition of the present invention contains the above-mentioned copolymer [A], [B] and [C] components, or the [D] component is an essential component, and may further contain [E] at least one vinyl group if necessary. A polymerizable compound of a saturated double bond, [F] a polyvalent phenol compound, an epoxy resin of [G] copolymer [A], [H] surfactant, [I] adhesion aid or [J] cross-linking Agent.

The polymerizable compound having at least one ethylenically unsaturated double bond (hereinafter referred to as "E component") as the above [E] is preferably, for example, a monofunctional (meth) acrylate or a bifunctional (methyl group). An acrylate or a trifunctional or higher (meth) acrylate.

Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth)propionate, carbitol (meth) acrylate, and isophorone (meth) acrylate. 3-methoxybutyl methacrylate, 2-(meth) propylene methoxyethyl 2-hydroxypropyl phthalate, and the like. In addition, as a commercial item, for example, ARONIX M-101, ARONIX M-111, ARONIX M-114 (above, manufactured by Toagosei Co., Ltd.); KAYARAD TC-110S, KAYARAD TC-120S (above, Japan) Pharmaco Co., Ltd.); VISCOAT 158, VISCOAT 2311 (above, Osaka Organic Chemical Industry Co., Ltd.).

Further, examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexane diol di(meth) acrylate, and 1,9-nonanediol. Di(meth)acrylate, polypropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, diphenoxyethanoloxime diacrylate, diphenoxyethanoloxime dimethacrylate Wait. In addition, as a commercial item, for example, ARONIX M-210, ARONIX M-240, ARONIX M-6200 (above, manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 (above) , manufactured by Nippon Kayaku Co., Ltd., VISCOAT 260, VISCOAT 312, and VISCOAT 335HP (above, Osaka Organic Chemical Industry Co., Ltd.).

Examples of the trifunctional or higher (meth) acrylate include trimethylolpropane tri(methyl)propionate, pentaerythritol tri(meth)acrylate, and tris((meth) propylene oxychloride. Ethyl ethyl) phosphate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Commercial products of a trifunctional or higher (meth) acrylate include, for example, ARONIX M-309, ARONIX M-400, ARONIX M-405, ARONIX M-450, ARONIX M-7100, ARONIX M-8030. , ARONIX M-8060 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 (above, Nippon Kayaku Co., Ltd.) Manufacturing), VISCOAT 295, VISCOAT 300, VISCOAT 360, VISCOAT GPT, VISCOAT 3PA, VISCOAT 400 (above, Osaka Organic Chemical Industry Co., Ltd.).

Among them, a trifunctional or higher (meth) acrylate is preferably used, and among them, trimethylolpropane tri(meth) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol hexa(methyl) is particularly preferable. )Acrylate.

These monofunctional, bifunctional or trifunctional or higher (meth) acrylates may be used singly or in combination. The use ratio of the component [E] is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of the copolymer [A].

By containing the [E] component in such a ratio, heat resistance, surface hardness, and the like of the protrusions and/or spacers obtained from the radiation sensitive resin composition of the present invention can be improved. If the amount exceeds 50 parts by weight, film roughening occurs in the step of forming a coating film of the radiation sensitive resin composition on the substrate.

Further, examples of the polyvalent phenol compound of the above [F] include a polymer having at least a hydroxystyrene as a raw material monomer. Specific examples of the [F] polyvalent phenol compound include polyhydroxystyrene, hydroxystyrene/methyl methacrylate copolymer, hydroxystyrene/cyclohexyl methacrylate copolymer, and hydroxystyrene/benzene. A resin obtained by polymerizing hydroxystyrene such as an ethylene copolymer or a hydroxystyrene/alkoxystyrene copolymer. In addition, a novolac resin obtained by polycondensing at least one compound selected from the group consisting of phenols, cresols, and catechols with one or more compounds selected from the group consisting of aldehydes and ketones.

The amount of the above-mentioned [F] polyvalent phenol compound added is preferably from 0 to 40%, more preferably from 0.1 to 40%, based on the solid content of the radiation sensitive resin composition. Good is 1~25%. The content of the polyvalent phenol compound is from 0 to 40%, which is preferable because the visible light transmittance of the obtained film can be increased and the performance as a transparent cured resin pattern can be improved.

The epoxy resin other than the above [G] copolymer [A] (hereinafter referred to as "F component") is not limited as long as it does not affect compatibility, and is preferably a bisphenol A type epoxy resin or a novolac type ring. Oxygen resin, cresol novolak type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, heterocyclic epoxy resin, (co)polymerized methacrylic acid shrinkage A glyceride resin or the like. Among them, a bisphenol A type epoxy resin, a cresol novolac type epoxy resin, a glycidyl ester type epoxy resin, and the like are preferable.

The use ratio of the component [G] is preferably 30 parts by weight or less based on 100 parts by weight of the resin [A]. By containing the [G] component in such a ratio, heat resistance, surface hardness, and the like of the protrusions and/or spacers obtained from the radiation sensitive resin composition of the present invention can be improved. When the ratio exceeds 30 parts by weight, when the coating film of the radiation sensitive resin composition is formed on the substrate, the film thickness uniformity of the film may be insufficient.

Further, the copolymer [A] can also be referred to as "epoxy resin", but differs from the [G] component in terms of having hydrazine solubility.

The above [H] surfactant can be used in the radiation sensitive resin composition of the present invention to further improve coatability. As the [H] surfactant used herein, a fluorosurfactant, an anthrone surfactant, and a nonionic surfactant can be used.

Specific examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl)ether and 1,1,2,2-tetrafluorooctene. Hexyl hexyl ether, octaethylene glycol bis(1,1,2,2-tetrafluorobutyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl)ether, eight Propylene glycol di(1,1,2,2-tetrafluorobutyl)ether, hexapropylene glycol bis(1,1,2,2,3,3-hexafluoropentyl)ether, sodium perfluorododecyl sulfonate 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, and fluoroalkylbenzene Sodium sulfonates, fluoroalkyl oxyethylene ethers, fluoroalkyl ammonium iodides, fluoroalkyl polyoxyethylene ethers, perfluoroalkyl polyoxyethylenes, perfluoroalkyl alkoxides , fluorine alkyl esters and the like. In addition, as a commercial item, BM-1000, BM-1100 (made by the above BM Chemie company), Megafac F142D, Megafac F172, Megafac 173, Megafac F183, Megafac F178, Megafac F191, Megafac F471 (above, Dainippon Ink Chemical Industry Co., Ltd., Flourad FC-170C, FC-171, FC-430, FC-431 (above, Sumitomo 3M Co., Ltd.), Surflon S-112, Surflon S-113, Surflon S -131, Surflon S-141, Surflon S-145, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (above, Asahi Glass Co., Ltd., Eftop EF301, Eftop EF 303, Eftop EF 352 (above, New Akita Chemicals Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC -57, DC-190 (made by Toray Silicone Co., Ltd.), etc.

Further, examples of the anthrone-based surfactants include Toray Silicone DC3PA, Toray Silicone DC7PA, Toray Silicone SH11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone FS-1265-300 (for example). Sales of the above-mentioned products such as Toray Dow, manufactured by Corning Silicne Co., Ltd., TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, and TSF-4452 (above, GE Toshiba Silicone Co., Ltd.) The product.

As the nonionic surfactant, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and the like; polyoxyethylene octylbenzene can be used. Polyoxyethylene aryl ethers such as alkyl ethers and polyoxyethylene nonylphenyl ethers; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, and Acrylic copolymer Polyflow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

These surfactants can be used singly or in combination of two or more.

The [H] surfactant is preferably used in an amount of 5 parts by weight or less, more preferably 2 parts by weight or less, based on 100 parts by weight of the copolymer [A]. When the amount of the surfactant [H] is more than 5 parts by weight, when the coating film is formed on the substrate, the coating film is likely to be rough.

Further, in order to further improve the adhesion to the substrate, the adhesion aid [I] may be mixed in the radiation sensitive resin composition of the present invention. As such a binder auxiliary [I], a functional decane coupling agent is preferably used, and examples thereof include a decane coupling agent having a reactive substituent such as a carboxyl group, a methacryl group, an isocyanate group or an epoxy group. Specific examples thereof include trimethoxymethyl decyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy methoxy decane, vinyl triethoxy methoxy methoxy decane, vinyl trimethoxy methoxy decane, and γ. - Isocyanatopropyltriethoxymethane, γ-glycidoxypropyltrimethoxymethane, β-(3,4-epoxycyclohexyl)ethyltrimethoxyformane, and the like. The amount of the adhesion aid [I] is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the copolymer [A]. When the amount of the adhesion aid exceeds 20 parts by weight, development of the image is likely to occur in the development step.

The above [J] crosslinking agent is a component which forms a crosslinked structure between specific sulfonium-soluble resin molecules as the component [A]. As such a crosslinking agent, a condensation product of urea and formaldehyde (hereinafter referred to as "urea-formaldehyde condensation product"), a condensation product of melamine and formaldehyde (hereinafter referred to as "condensation product of melamine-formaldehyde") can be used. These condensation products and hydroxymethyl urea alkyl ethers obtained from alcohols, and methylol melamine alkyl ethers and the like.

Specific examples of the urea-formaldehyde condensation product include monomethylol urea, dimethylol urea, and the like.

Specific examples of the melamine-formaldehyde condensation product include hexamethylol melamine, and a product obtained by partially condensing melamine and formaldehyde.

The hydroxymethyl urea alkyl ether is obtained by reacting a part or all of a methylol group in a urea-formaldehyde condensation product with an alcohol, and specific examples thereof include monomethylol urea methyl ether and dimethylol. Urea methyl ether and the like.

The above-mentioned methylol melamine alkyl ether is obtained by reacting a part or all of a methylol group of a melamine-formaldehyde condensation product with an alcohol such as methanol or n-butanol, and specific examples thereof include hexamethylol melamine hexamethacrylate. a compound having a structure in which a hydrogen atom of an amino group having a melamine is substituted with a methylol group and a methoxymethyl group, and a hydrogen atom having an amino group of melamine is an oxymethyl group. A compound having a structure substituted with a methoxymethyl group or the like.

Among them, methylol melamine alkyl ethers are preferably used, and commercially available products of such hydroxymethyl melamine alkyl ethers include "CYMEL 300", "CYMEL 370", and "CYMEL" manufactured by Mitsui Cytec Co., Ltd. 232", "MYCOD 505", etc.

The use ratio of the component [J] is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of the component [A].

When the ratio exceeds 50 parts by weight, the thickness of the portion where the coating film is not irradiated with radiation is remarkably reduced during the development treatment, and the transparency of the obtained coating film is lowered.

Radiation-sensitive resin composition

The radiation sensitive resin composition of the present invention can be produced by uniformly mixing the above copolymer [A], [B] and [C] components and other components added as described above. In general, the radiation resin composition of the present invention is dissolved in a suitable solvent and used in the form of a solution. For example, the copolymer [A], [B], and [C] components and any other components added arbitrarily are mixed at a predetermined ratio to prepare a radiation sensitive resin composition in a solution state.

As the solvent used in the preparation of the radiation sensitive resin composition of the present invention, various components capable of uniformly dissolving the copolymer [A], [B] and [C] components and other components added as above may be used, and The solvent for the reaction of each component.

As such a solvent, the same solvent as the solvent exemplified in the production of the copolymer [A] can be mentioned.

Among these solvents, glycol ether, ethylene glycol alkyl ether acetate, ester, and digan are preferably used from the viewpoints of solubility of each component, reactivity with each component, and easiness of formation of a coating film. Alcohols. Among them, it is particularly preferable to use diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxypropionate, ethoxy propyl Ethyl acetate.

In the preparation of the radiation sensitive linear resin composition of the present invention in a solution state, components other than the solvent in the solution (that is, the total amount of the copolymer [A], [B], and [C] components and any other components added arbitrarily) The ratio may be arbitrarily set depending on the purpose of use and the desired film thickness value, and is usually 5 to 50% by weight, preferably 10 to 40% by weight, and more preferably 15 to 35% by weight.

The composition solution thus prepared is filtered using a micropore filter having a pore size of about 0.2 μm or the like.

Formation of protrusions and/or spacers

Next, a method of forming the protrusions and spacers of the present invention using the radiation sensitive resin composition of the present invention will be described. The method of forming the protrusions and/or spacers of the present invention comprises at least the following steps.

(1) A step of forming a coating film of the radiation sensitive resin composition of the present invention on a substrate.

(2) a step of irradiating radiation on at least a part of the coating film.

(3) Development step.

(4) Heating step.

(1) Step of forming a coating film of the radiation sensitive resin composition of the present invention on a substrate

In the above step (1), the composition solution of the present invention is applied onto the surface of the substrate, and the solvent is prebaked to form a film of the radiation sensitive resin composition.

Examples of the type of the substrate used in the present invention include a glass substrate, a tantalum wafer, and a substrate on which various metals are formed on the surface.

As a method of forming the coating film of the photosensitive resin composition of the present invention, for example, (1) coating method and (2) dry film method can be employed.

As a coating method of the composition solution, for example, a suitable method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit coating method, a bar coating method, or an inkjet coating method can be employed. A spin coating method or a slit (die) coating method is preferred.

Further, when the coating film of the photosensitive resin composition of the present invention is formed by the (2) dry film method, the dried film is laminated on the base film, preferably a flexible base film, by the photosensitive resin of the present invention. The photosensitive layer formed of the composition is formed (hereinafter referred to as "photosensitive dry film").

The photosensitive dried film is obtained by applying the photosensitive resin composition of the present invention, preferably a liquid composition, to a base film, followed by drying, and laminating a photosensitive layer. As the base film of the photosensitive dried film, for example, a synthetic resin film such as polyethylene terephthalate (PET), polyethylene, polypropylene, polycarbonate, or polyvinyl chloride can be used. The thickness of the base film is suitably 15 to 125 μm. The thickness of the obtained photosensitive layer is preferably about 1 to 30 μm.

Further, when the photosensitive dried film is not used, a protective film may be further laminated on the photosensitive layer for storage. When the protective film is not used, it is not peeled off and can be easily peeled off during use, so that it is necessary to have appropriate peelability. The protective film which satisfies such a condition is, for example, a film formed by coating or sintering an anthrone-based release agent on the surface of a synthetic resin such as a PET film, a polypropylene film, a polyethylene film or a polyvinyl chloride film. The thickness of the protective film is usually about 25 μm. The conditions of the prebaking vary depending on the type of each component, the ratio of use, and the like. For example, it can be carried out at 60 to 110 ° C for about 30 seconds to 15 minutes.

(2) a step of irradiating at least a part of the coating film with radiation

In the above step (2), after the radiation is irradiated by a mask having a predetermined pattern, the developing portion is irradiated with a developing solution to remove the radiation irradiated portion, and the formed coating film is patterned. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like.

Examples of the ultraviolet rays include a g line (wavelength: 436 nm), an i line (wavelength: 365 nm), and the like. Examples of the far ultraviolet rays include KrF excimer lasers and the like. Examples of the X-rays include synchrotron radiation and the like. Examples of the charged particle beam include an electron beam and the like.

Among them, ultraviolet rays are preferred, and radiation containing g-lines and/or i-lines is particularly preferred.

The pattern mask and the exposure operation used at the time of exposure may be: (1) using one type of photomask having a pattern of two portions of the protruding portion and the spacer portion, and a method of one exposure (the smaller the portion of the mask, the more It is impossible to ignore the influence of the transmitted light, which corresponds to the melt flow during baking, and form a height difference); (2) Two exposures are performed using a photomask having only a protruding portion and two photomasks having only a spacer. method. Further, as the pattern mask used in the method of (1), a mask having a different transmittance of the protruding portion and the spacer portion may be used. However, in the present invention, depending on the case, only one of the protrusions and the spacers may be formed on the substrate, in which case, (3) a photomask having only the protruding portion and only the spacer portion may be employed. Any one of the masks, a method of one exposure. Further, in this case, protrusions or spacers which must remain in the vertical alignment type liquid crystal display element are formed by a conventionally known method.

(3) Development step

As the developer used in the development treatment, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium methyl citrate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, or the like can be used. Di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, acridine, 1,8-diaza An aqueous solution of hydrazine such as heterobicyclo[5,4,0]-7-undecene and 1,5-diazabicyclo[4,3,0]-5-decane. Further, in the above aqueous alkaline solution, a water-soluble organic solvent such as methanol or ethanol and a surfactant may be appropriately added to form an aqueous solution, and various organic solvents which form an aqueous solution or dissolve the composition of the present invention may be used as a developing solution. Further, as the developing method, a suitable method such as a liquid-filling method, a dipping method, a shaking dipping method, or a shower method may be employed. The development time at this time varies depending on the composition of the composition, and is usually about 30 to 180 seconds.

(4) Heating step

After the (3) development step as described above, it is preferred to perform a shower treatment based on the running water washing on the patterned film, and further preferably irradiate the radiation (post exposure) by a high pressure mercury lamp or the like, and the residual 1 in the film is After the 2-indene diazide compound is subjected to decomposition treatment, the film is subjected to heat treatment (post-baking treatment) by a heating device such as a hot plate or an oven, and the film is subjected to a curing treatment. The exposure amount in the above post-exposure step is preferably about 2,000 to 5,000 J/m ² . Further, the firing temperature of the curing treatment is, for example, 120 to 250 ° C, and the heating time varies depending on the type of the heater. For example, when heat treatment is performed on a hot plate, it is 5 to 30 minutes, and heat treatment is performed in an oven. It is 30-90 minutes. In this case, a step-by-step baking method or the like which performs a heating step of 2 times or more may be used.

In this manner, a patterned film corresponding to the target protrusions and/or spacers can be formed on the surface of the substrate.

The height of the protrusion thus formed is usually 0.1 to 3.0 μm, preferably 0.5 to 2.0 μm, particularly preferably 1.0 to 1.5 μm; and the height of the spacer is usually 1 to 10 μm, preferably 2 ~8 μ m, particularly preferably 3 to 5 μ m.

According to such a method of forming protrusions and/or spacers used in the vertical alignment type liquid crystal display element of the present invention, it is possible to finely process, and it is easy to control the shape and size (height and bottom size), and the pattern shape can be stably and productively formed. Further, fine protrusions and spacers excellent in heat resistance, solvent resistance, transparency, and the like, and vertical alignment type liquid crystal display elements excellent in alignment properties, voltage holding ratio, and the like can be provided.

The radiation sensitive resin composition for forming the protrusions and/or spacers used in the vertical alignment type liquid crystal display element of the present invention can be excellent in resolution and residual film ratio, and has a pattern shape, heat resistance, solvent resistance, and transparency. A protrusion and/or a spacer excellent in properties and the like, and a vertical alignment type liquid crystal display element excellent in an alignment property, a voltage holding ratio, and the like can be provided. Further, the method of forming the protrusions and/or spacers used in the vertical alignment type liquid crystal display element of the present invention can be finely processed, and the shape and size (height and bottom size) can be easily controlled, and the pattern shape can be stably and productively formed. A fine protrusion and a spacer excellent in heat resistance, solvent resistance, transparency, and the like, and a vertical alignment type liquid crystal display element excellent in an alignment property, a voltage holding ratio, and the like.

[Examples]

Hereinafter, the present invention will be more specifically described by showing Synthesis Examples and Examples, but the present invention is not limited to these Examples.

Synthesis example of copolymer [A] Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 4 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethyl methyl ether were added. Next, 20 parts by weight of styrene, 20 parts by weight of methacrylic acid, 40 parts by weight of 3-(methacryloxymethyl)-3-ethyloxetane and 20 parts by weight of phenyl malazone were added. The imine, after nitrogen replacement, began to stir slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-1).

The copolymer (A-1) had a polystyrene-equivalent weight average molecular weight (Mw) of 15,500 and a molecular weight distribution (Mw/Mn) of 2.4.

Synthesis Example 2

Except that in Synthesis Example 1, 40 parts by weight of glycidyl methacrylate was used instead of 40 parts by weight of 3-(methacryloxymethyl)-3-ethyloxetane, according to Synthesis Example 1, The copolymer (A-2) was obtained. The copolymer (A-2) had a polystyrene-equivalent weight average molecular weight of 13,000 and a molecular weight distribution (Mw/Mn) of 2.5.

Example 1 [Preparation of Radiation-sensitive Resin Composition]

A solution containing the polymer [A-1] as the component [A] synthesized in the above Synthesis Example 1 in an amount corresponding to 100 parts by weight of the polymer [A-1] (solid content), and 30 parts by weight as a component [ B] of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and chlorinated 1 a condensate of (2-naphthoquinonediazide-5-sulfonic acid (2.0 mol) (B-1), 2 parts by weight of (p-tolyl) as component [C] (p-isopropylbenzene) Iodine tetrakis(pentafluorophenyl)borate [Rhodorsil Photoinitiator 2074 (manufactured by Rhodia)], 2 parts by weight of 2,4-dimethylthioxanone as component [D], 210 parts by weight of 2-hydroxyl Methyl isobutyrate was mixed at 23 ° C, and then passed through a can filter having a pore size of 1.0 μm polytetrafluoroethylene, and filtered under pressure to obtain a radiation sensitive resin composition (S-1).

Using the radiation sensitive resin composition prepared as above, protrusions and spacers were formed as follows, and various properties were evaluated.

[Formation of protrusions and spacers]

After coating the above composition on a ruthenium substrate with a spinner, it was prebaked on a hot plate at 90 ° C for 2 minutes to form a coating film having a film thickness of 4.0 μm. Thereafter, the PLA-501F exposure machine (super) manufactured by Canon Co., Ltd. was passed through a photomask having a pattern of the remaining 5 μm width corresponding to the protruding portion and a pattern of dots corresponding to the remaining 30 μm of the spacer portion. High-pressure mercury lamp), change the exposure time, and perform exposure. Thereafter, the film was developed for 100 seconds by the type of developer at 25° C., the developer concentration, and the development method described in the table, and then washed with pure water for 1 minute, dried, and patterned on a wafer. The amount of exposure required for forming a pattern of the remaining 5 μm width corresponding to the protruding portion and a pattern corresponding to the remaining 30 μm dot of the spacer portion was measured. This value is shown as sensitivity in the table. When the value is 3500 J/m ² or less, the sensitivity is considered to be good.

[Evaluation of the sectional shape of the protrusion]

When the cross-sectional shape A, B or C of the protrusion is defined as follows, the cross-sectional shape of the formed protrusion is observed by a scanning electron microscope, and it is "good" in the case of A or B, and "not good" in the case of C. A, B, and C of the cross-sectional shape of the protrusion are illustrated in Fig. 1 as shown.

A: The case where the bottom size is larger than 5 μm or less than or equal to 7 μm, B: the case where the bottom size is larger than 7 μm, and C: the case where the bottom size is a table shape.

[Evaluation of the sectional shape of the spacer]

When the cross-sectional shape A, B or C of the spacer is defined as follows, the cross-sectional shape of the formed spacer is observed by a scanning electron microscope, and it is "good" in the case of A or C, and "not good" in the case of B. A, B, and C of the cross-sectional shape of the spacer are illustrated in Fig. 1 as shown.

A: The case where the bottom size is larger than 30 μm or less than 36 μm, B: the case where the bottom size is larger than 36 μm, and C: the case where the bottom size is a table shape.

[Solvent resistance evaluation]

After the composition was coated on a ruthenium substrate with a spinner, it was prebaked on a hot plate at 90 ° C for 2 minutes to form a coating film having a film thickness of 3.0 μm. Thereafter, the obtained coating film was exposed to a cumulative irradiation amount of 3,000 J/m 2 by a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon Co., Ltd. The crucible substrate was heated in a cleaning oven at 220 ° C for 1 hour to obtain a cured film. The film thickness (T1) of the obtained cured film was measured. Then, the ruthenium substrate on which the cured film was formed was immersed in dimethyl sulfoxide having a temperature of 70 ° C for 20 minutes, and then the film thickness (t1) of the cured film was measured, and the film thickness change rate due to immersion was calculated {|t1 -T1|/T1}×100 (%). The results are shown in Table 2. When the value is 5% or less, the solvent resistance is considered to be good.

Further, in the evaluation of the solvent resistance, since it is not necessary to pattern the formed film, the irradiation step and the development step of the radiation can be omitted, and only the evaluation of the coating film forming step, the post-baking step, and the heating step can be performed.

[Heat resistance evaluation]

A cured film was formed in the same manner as the evaluation of the solvent resistance described above, and the film thickness (T2) of the obtained cured film was measured. Then, the cured film substrate was additionally baked at 240 ° C for 1 hour in a cleaning oven, and then the film thickness (t2) of the cured film was measured, and the film thickness change rate due to additional baking was calculated {|t2-T2| /T2}×100 (%). The results are shown in Table 2. When the value is 5% or less, heat resistance is considered to be good.

[Transparency evaluation]

In the evaluation of the solvent resistance, a cured film was formed on the glass substrate in the same manner except that the glass substrate "Corning 7059" (manufactured by Corning Co., Ltd.) was used instead of the ruthenium substrate. The light transmittance of the glass substrate having the cured film was measured at a wavelength of 400 to 800 nm using a spectrophotometer "150-20 Double Beam (manufactured by Hitachi, Ltd.). At this time, the lowest light transmittance is shown in the table. 2 shows that when the value is 90% or more, transparency is considered to be good.

[Evaluation of alignment and voltage retention]

Using the composition solution, protrusions and spacers were formed on the electrode surface of the glass substrate having the ITO (tin-coated indium oxide) film as an electrode in the same manner as the above method. After that, AL1H659 (trade name, manufactured by JSR Corporation), which is a liquid crystal alignment agent, was applied to a glass substrate on which a projection and a spacer were formed, and then dried at 180 ° C for 1 hour to form a film. A film thickness of 0.05 μm. Further, AL1H659 as a liquid crystal alignment agent was applied onto the electrode surface of another glass substrate having an ITO film by a printer for coating a liquid crystal alignment film, and dried at 180 ° C for 1 hour to form a coating film having a film thickness of 0.05 μm. Next, on the outer surface of each liquid crystal alignment film of the obtained two substrates, an epoxy resin adhesive of glass fibers having a diameter of 5 μm is screen-printed, and the two substrates are pressed to make the liquid crystal alignment film surfaces relatively overlap. To cure the adhesive. After that, the liquid crystal MLC-6608 (trade name) manufactured by Merck Co., Ltd. was filled between the two substrates from the liquid crystal injection port, and the liquid crystal injection port was sealed by an epoxy adhesive, and then the polarizer was bonded to the outer surfaces of the two substrates to be polarized. The direction is orthogonal to produce a vertical alignment type liquid crystal display element. 2 is a longitudinal cross-sectional view showing the obtained vertical alignment type liquid crystal display device, wherein reference numeral 1 denotes a spacer, reference numeral 2 denotes a projection, reference numeral 3 denotes a liquid crystal, reference numeral 4 denotes a liquid crystal alignment film, and reference numeral 5 denotes a color filter. A light sheet and reference numeral 6 denote a glass substrate.

Next, the alignment and voltage holding ratio of the obtained vertical alignment type liquid crystal display element were evaluated as follows.

In the evaluation of the alignment property, when an electric voltage was turned on and off, it was observed by a polarizing microscope whether or not an abnormal region was generated in the liquid crystal cell, and it was confirmed that the abnormal region was not "good". Further, when the voltage holding ratio was evaluated, after a voltage of 5 V was applied to the liquid crystal display element, the circuit was turned off, the holding voltage after 16.7 msec was measured, and the ratio of the holding voltage to the applied voltage (5 V) was calculated. When the value is 98% or more, it is considered to be good.

Example 2

The radiation sensitive resin composition solution (S-2) was prepared in the same manner as in Example 1 except that (A-2) was used instead of (A-1). Thereafter, protrusions and spacers were formed in the same manner as in Example 1, and various properties were evaluated. The results are shown in Table 1.

Example 3

A solution of the radiation sensitive resin composition was prepared in the same manner as in Example 1 except that in Example 1, 2 parts by weight of 2-isopropylthioxanthone was used instead of 2 parts by weight of 2,4-dimethylthioxanthone. (S-3). Thereafter, protrusions and spacers were formed in the same manner as in Example 1, and various properties were evaluated. The results are shown in Table 1.

Example 4

A solution (S-4) of the radiation sensitive resin composition was prepared in the same manner as in Example 1 except that in Example 1, 2 parts by weight of 2,4-dimethylthioxanthone was not used. Thereafter, protrusions and spacers were formed in the same manner as in Example 1, and various properties were evaluated. The results are shown in Table 1.

Comparative example 1

Except in Example 1, 2 parts by weight of (p-tolyl)(p-isopropylphenyl)iodonium tetrakis(pentafluorophenyl)borate [Rhodorsil Photoinitiator 2074 (manufactured by Rhodia)], 2 was not used. A solution (s-1) of the radiation sensitive resin composition was prepared in the same manner as in Example 1 except for 2 parts by weight of 2,4-dimethylthioxanthone. Thereafter, protrusions and spacers were formed in the same manner as in Example 1, and various properties were evaluated. The results are shown in Table 1.

1. . . Spacer

2. . . Protrusion

3. . . liquid crystal

4. . . Liquid crystal alignment film

5. . . Color filter

6. . . glass substrate

In the first drawing, A-C is a schematic view showing the cross-sectional shape of the protrusion and the spacer, respectively.

Fig. 2 is a schematic view showing a cross-sectional shape of a vertical alignment type liquid crystal display element having projections and spacers.

Claims (5)

A radiation sensitive resin composition for forming protrusions and/or spacers used in a vertical alignment type liquid crystal display element, characterized in that: [A] is an (a1) unsaturated carboxylic acid and/or unsaturated a carboxylic anhydride, (a2) an unsaturated compound having an oxetanyl group, and (a3) a copolymer obtained by copolymerizing an olefin-based unsaturated compound other than the above (a1) and (a2); [B] 1, 2 - quinone diazide compound; [C] photocationic polymerization initiator; and [D] thioxanthone compound, wherein the ratio of the [B] component is 5 to 100 with respect to 100 parts by weight of the copolymer [A] The proportion by weight of the component [C] is 0.01 to 15 parts by weight based on 100 parts by weight of the copolymer [A]; and the ratio of use of the component [D] is 0.01 to 15 with respect to 100 parts by weight of the copolymer [A]. Parts by weight. A protrusion for use in a vertical alignment type liquid crystal display element, which is formed by the radiation sensitive resin composition of the first application of the patent scope. A spacer for use in a vertical alignment type liquid crystal display element, which is formed of the radiation sensitive resin composition of claim 1 or 2. A vertical alignment type liquid crystal display element having a protrusion of the second application of the patent application and/or a spacer of the third item of the patent application. A method of forming protrusions and/or spacers, comprising the steps of: (1) forming a coating film of a radiation sensitive composition of claim 1 on a substrate; (2) a step of irradiating at least a portion of the coating film with radiation; (3) a developing step; and (4) a heating step.