TWI415890B - Sensitive radiation linear resin composition, spacer and its manufacturing method and liquid crystal display element - Google Patents

Abstract

A radiation-sensitive resin composition is provided to form a spacer for a liquid crystal display device having excellent adhesion, rubbing resistance and heat resistance even under a low light dose, and showing flexibility, high elastic restorability and excellent developability to an alkaline developer. A radiation-sensitive resin composition comprises: [A] a copolymer of (a1) at least one selected from unsaturated carboxylic acids and anhydrides thereof, (a2) an unsaturated compound represented by the following formula 1, and (a3) at least one unsaturated compound selected from the group consisting of alkyl acrylate, alkyl methacrylate, alicyclic acrylate, alicyclic methacrylate, aryl acrylate, aralkyl acrylate, aryl methacrylate, aralkyl methacrylate, dialkyl dicarboxylate, hydroxyalkyl methacrylate, methacrylate of an unsaturated 5- or 6-membered ring containing one oxygen atom, epoxyalkyl acrylate, epoxyalkyl methacrylate, epoxyalkyl alpha-alkylacrylate, glycidyl ether having an unsaturated bond, vinyl aromatic compounds, dicarbonyl imide derivatives, conjugated dienes, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride and vinyl acetate; [B] a polymerizable unsaturated compound; and [C] a radiation-sensitive polymerization initiator. In formula 1, each of R1 and R2 is H or monovalent organic group; R3 is H or methyl; and X is a divalent organic group.

Description

Sensitive radiation linear resin composition, spacer, manufacturing method thereof and liquid crystal display element

The present invention relates to a radiation sensitive linear resin composition, a spacer, a method of manufacturing the same, and a liquid crystal display element. More specifically, it relates to a radiation sensitive linear resin composition suitable as a material for forming a spacer used for a display element such as a liquid crystal display panel or a touch panel, and a spacer for a display element formed of the composition, and A liquid crystal display element formed by the spacer is provided.

In the liquid crystal display device, it is conventional to use spacer particles such as glass beads or plastic beads having a predetermined particle size in order to maintain a certain interval (cell gap) between the two substrates, but the spacer particles are irregular. Disperse on a transparent substrate such as a glass substrate. If spacer particles are present in the pixel formation region, glare of the spacer particles will occur, and the incident light will be scattered, and the contrast of the liquid crystal panel will be reduced. The problem.

Therefore, in order to solve such problems, a method of forming a spacer by lithographic photolithography has been started. In the method, the sensitive radiation linear resin composition is applied onto a substrate, and the ultraviolet ray is exposed and developed through a mask to form a dot or strip-shaped spacer, since it can be set only outside the pixel formation region. The spacer is formed, so that the aforementioned problems can be basically solved. Since such a spacer forms a spacer formed of a linear radiation-sensitive resin composition, it must satisfy the functions required for the spacer, and thus is different from a conventional composition for forming an interlayer insulating film, and has a space for forming spacers. Specialized composition or composition of the device.

However, in recent years, even with the related new sensitive radiation linear resin composition, the case of using the same steps as the conventionally used materials has gradually increased from the viewpoint of reducing the manufacturing cost. In this case, the spacer is used with the sensitive radiation linear resin composition in a condition that deviates from the optimum step condition, and in particular, when the prebaking temperature deviates from the optimum condition, sufficient resolution, or pattern, may not be obtained. The problem of stripping. Further, as the substrate is enlarged, even on the same substrate, due to the distribution of the baking temperature, the warpage of the substrate tends to be more pronounced in the case of proximity baking, and therefore it is necessary to have a wider process boundary. The spacer of the process margin is made of a sensitive radiation linear resin composition.

Therefore, in order to solve this problem, the applicant of the present application has disclosed that it has a wide process boundary which can be changed in accordance with the condition of the step, and can impart heat resistance and resistance as a spacer. A sensitive radiation linear resin composition of a graphic form of a cured product of chemical properties, transparency and hardness.

In addition, in recent years, from the viewpoint of improving productivity, there is a technique of dropping a liquid crystal material on a glass surface in front of a glass to which a liquid crystal panel is bonded in the manufacture of a liquid crystal display element, that is, a so-called ODF (One Drop One Fill) The Drop Fill method is imported. By this method, the time required to manufacture the liquid crystal display element can be greatly shortened. For example, when the liquid crystal for a panel of 30 inches is filled by a conventional method, it takes about 5 days, and if the ODF method is introduced, it can be completed in 2 hours, and the productivity can be greatly improved.

In the conventional bonding method, when the TFT array and the color filter are attached, the spacer is uniformly pressed due to the load due to the application of the load, and the spacer can be retained. The uniformity of the height of the spacer. However, in the ODF method, initially, the load is applied to the atmospheric pressure only by the load of the substrate weight, and the load of the initial bonding is small as compared with the conventional method. Therefore, even if the spacer is pressed with a small load, the uniformity of the height can be exhibited under the average pressure, which is very important. Therefore, it is necessary for the spacer to have flexibility and a high elastic recovery rate. If the height of the spacer is not uniform, the average of the cell gap cannot be maintained, and voids are generated in the cell, which causes uneven display. However, in the conventional spacer, those having flexibility tend to exhibit a high elastic deformation amount in the compression load test, but tend to have a low elastic recovery rate.

In order to coexist with flexibility and high elastic recovery rate, Japanese Laid-Open Patent Publication No. 2002-174812 proposes a resin-containing radiation sensitive linear resin composition obtained by using an alicyclic compound having a polycyclic stereo structure. However, in this case, since the resin has a multi-ringed three-dimensional structure, the developability of the film of the composition to the alkali developer is remarkably lowered.

Further, in recent years, from the viewpoint of reduction in manufacturing cost or energy saving, it is strongly desired that the exposure amount of the sensitive radiation linear resin composition can be minimized.

Invention

Therefore, an object of the present invention is to provide adhesion in a small amount of exposure, for example, even at an exposure amount of 1,500 J/m ² or less, which is excellent in polishing resistance and heat resistance, and further has flexibility and high elastic recovery. A radiation sensitive linear resin composition of a liquid crystal display element spacer having excellent developability to an alkali developer.

Another object of the present invention is to provide a spacer which is excellent in adhesion, heat resistance and heat resistance, and which has both flexibility and high elastic recovery, a method for producing the same, and a liquid crystal display element having a spacer.

Other objects and advantages of the present invention will be apparent from the description.

According to the present invention, the above objects and advantages of the present invention are at least one selected from the group consisting of [A](a1) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter, referred to as "compounds"A1)"), (a2) following formula (1) (In the formula (1), R ¹ and R ² each represent an unsaturated hydrogen atom or a monovalent organic group, R ^{3 represents a} hydrogen atom or a methyl group, and X represents a divalent organic group) (hereinafter, It is called "compound (a2)"), and (a3) is selected from alkyl acrylate, alkyl methacrylate, alicyclic alicyclic ester, alicyclic methacrylate, aryl acrylate, aryl acrylate, Aryl methacrylate, arylalkyl methacrylate, dialkyl dicarboxylate, hydroxyalkyl methacrylate, unsaturated 5- or 6-membered ring methacrylate containing 1 atom of oxygen, acrylic ring Oxyalkylalkyl ester, epoxy methacrylate alkyl ester, α-alkyl acrylate epoxy alkyl ester, glycidyl ether with unsaturated bond, vinyl aromatic compound, dicarbonyl ruthenium imide derivative a conjugated diene and at least one unsaturated compound of acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride and vinyl acetate (hereinafter, a copolymer called "compound (a3)") (hereinafter referred to as "copolymer [A]"), [B] polymerizable unsaturated Thereof, and [C] a linear radiation-sensitive polymerization initiator, the radiation-sensitive resin composition and the linear reached. The radiation sensitive linear resin composition is suitable as a spacer for forming a liquid crystal display element.

The above objects and advantages of the present invention are attained by a spacer for a liquid crystal display element formed from the above-mentioned sensitive radiation linear resin composition, and a liquid crystal display element comprising the same.

The above-described objects and advantages of the present invention are achieved by the method of forming a spacer for a liquid crystal display element characterized by including at least the steps described below.

(1) a step of forming a film of the above-mentioned radiation-sensitive linear resin composition on a substrate, (2) a step of exposing at least a portion of the film, (3) a step of developing the film after exposure, and (4) The step of heating the film after development.

The above objects and advantages of the present invention are attained by the above copolymer [A].

Best form for implementing the invention

The details of the invention are as follows.

Sensitive radiation linear resin composition The radiation sensitive linear resin composition of the present invention contains at least a copolymer [A], [B] a polymerizable unsaturated compound and [C] a radiation-sensitive linear polymerization initiator.

-copolymer [A]- The copolymer [A] can be produced by radical polymerization of a mixture of the compound (a1), the compound (a2) and the compound (a3), preferably in the presence of a polymerization initiator in a solvent.

The compound (a1) used in the production of the copolymer [A] is at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides.

The related compound (a1) may, for example, be a monocarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, 2-methylpropenyloxyethyl succinic acid or 2-methylpropenyloxyethyl hexahydrophthalic acid. a dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, mesaconic acid or itaconic acid; an anhydride of the dicarboxylic acid;

In the compound (a1), acrylic acid, methacrylic acid, maleic anhydride, or 2-methyl is used in terms of copolymerization reactivity, solubility in an aqueous alkali solution of the obtained copolymer, and ease of availability. Acryloxyethylhexahydrophthalic acid is preferred.

The compound (a1) may be used singly or in combination of two or more.

In the copolymer [A], the content of the repeating unit derived from the compound (a1) is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, most preferably 15 to 30% by weight. When the content of the repeating unit derived from the compound (a1) is less than 5% by weight, the solubility in the aqueous alkali solution is insufficient. On the other hand, when the content exceeds 50% by weight, the solubility in the aqueous alkali solution is excessively high. .

The compound (a2) used for the production of the copolymer [A] is a compound represented by the above formula (1).

In the above formula (1), the monovalent organic group of R ¹ and R ² may, for example, be an alkyl group having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an isobutyl group and the like. .

In the above formula (1), the divalent organic group of X may, for example, be a methylene group or an alkylene group having 2 to 6 carbon atoms. Specific examples of the alkylene group having 2 to 6 carbon atoms include a vinyl group, a 1,3-propenyl group, and a 1,4-butenyl group.

Specific examples of the compound (a2) include 4-propenyloxymethyl-2,2-dimethyl-1,3-dioxolane, 4-propenyloxymethyl- 2-methyl-2-ethyl-1,3-dioxolane, 4-propenyl methoxymethyl-2,2-diethyl-1,3-dioxolane, 4-propenyl fluorenyl Oxymethylmethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-propenyloxymethyl-2-cyclopentyl-1,3-dioxolane, 4- Propylene decyloxymethyl-2-cyclohexyl-1,3-dioxolane, 4-propenyl methoxyethyl-2-methyl-2-ethyl-1,3-dioxolane, 4 - propylene decyloxypropyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methylpropenyloxybutyl-2-methyl-2-ethyl-1, An acrylic acid derivative such as 3-dipentane; 4-methylpropenyl methoxymethyl-2,2-dimethyl-1,3-dioxolane, 4-methylpropenyl methoxymethyl-2-methyl-2-ethyl-1 , 3-dioxapentane, 4-methylpropenyloxymethyl-2,2-diethyl-1,3-dioxolane, 4-methylpropenyloxymethyl-2-methyl 2-isobutyl-1,3-dioxolane, 4-methylpropenyloxymethyl-2-cyclopentyl-1,3-dioxolane, 4-methylpropenyl Oxymethyl-2-cyclohexyl-1,3-dioxolane, 4-methylpropenyloxyethyl-2-methyl-2-ethyl-1,3-dioxolane, 4- Methyl propylene decyloxypropyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methylpropenyl oxybutyl-2-methyl-2-ethyl-1 a methacrylic acid derivative such as 3-dipentane or the like.

Among these, from the viewpoint of excellent polymerizability, the viewpoint that the obtained radiation-sensitive linear resin composition is excellent in developability to an alkali developer, and the viewpoint that the obtained spacer has both high flexibility and high elastic recovery ratio is considered. To use 4-propenyl methoxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-propenyl methoxymethyl-2-methyl-2-isobutyl -1,3-dioxapentane, 4-propenyl methoxymethyl-2-cyclohexyl-1,3-dioxolane, 4-methylpropenyl methoxymethyl-2-methyl-2 -ethyl-1,3-dioxolane, 4-methylpropenyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane or 4-methylpropene oxime Preferably, oxymethyl-2-cyclohexyl-1,3-dioxolane is preferred.

The compound (a2) may be used singly or in combination of two or more.

In the copolymer [A], the content of the repeating unit derived from the compound (a2) is preferably from 1 to 70% by weight, particularly preferably from 3 to 50% by weight. When the content of the repeating unit derived from the compound (a2) is less than 1% by weight, the linearity of the linear radiation-sensitive resin composition tends to be insufficient for the developability of the alkali developing solution. On the other hand, if it exceeds 70% by weight When the developability is too high, right The sensitivity of the radiation is insufficient to detract from the shape of the resulting pattern.

The compound (a3) used for the production of the copolymer [A] is selected from the group consisting of alkyl acrylates, alkyl methacrylates, acrylate alicyclic esters, methacrylate alicyclic esters, aryl acrylates, acrylic acid. Aralkyl ester, aryl methacrylate, arylalkyl methacrylate, dialkyl dicarboxylate, hydroxyalkyl methacrylate, unsaturated 1 or 6 ring methacrylic acid containing 1 atom of oxygen Esters, epoxy acrylates, epoxy methacrylates, α-alkyl acrylates, glycidyl ethers with unsaturated bonds, vinyl aromatic compounds, dicarbonyl ruthenium At least one type of imide derivative, conjugated diene and acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride and vinyl acetate Compound.

In the above, specific examples of the compound (a3) represented by the name include alkyl acrylate and i-propyl acrylate; and alkyl methacrylate; Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, butyl methacrylate, butyl methacrylate, etc.; in terms of acrylate cyclic ester, cyclohexyl acrylate can be exemplified. 2-methylcyclohexyl acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate, 2-(tricyclo[5.2.1.0 ^2,6 ]decane-8-yloxy) acrylate Ethyl ester The ester or the like; the methacrylate alicyclic ester may, for example, be cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[meth] methacrylate [5.2.1.0 ^2,6 ] decane- 8-yl ester, 2-(tricyclo[5.2.1.0 ^2,6 ]decane-8-yloxy)ethyl methacrylate, methacrylic acid The aryl acrylate may, for example, be phenyl acrylate or the like; the aryl acrylate may, for example, be benzyl acrylate; and the aryl methacrylate may, for example, be phenyl methacrylate; The aryl methacrylate may, for example, be benzyl methacrylate or the like; and the dialkyl dicarboxylate may, for example, be diethyl maleate or diethyl fumarate, ork. Diethyl acrylate or the like; hydroxyalkyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-(6-hydroxyethylhexyl oxymethacrylate) Ethyl ester or the like; an oxyalkyl ester of an unsaturated 5- or 6-membered ring containing 1 atom of oxygen, which may, for example, be tetrahydrofurfuryl methacrylate, tetrahydrofuran methacrylate or tetrahydropyran methacrylate- 2-methyl ester or the like; the epoxy acrylate alkyl acrylate, exemplified by glycidyl acrylate, 2-methylglycidyl acrylate, 3,4-epoxybutyl acrylate, acrylate 6,7- Epoxyheptyl heptyl ester, 3,4-epoxycyclohexyl acrylate or the like; epoxy methacrylate alkyl acrylate, for example Glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, methacrylic acid 3 , 4-epoxycyclohexyl ester, etc.; α -alkyl acrylate epoxy alkyl ester, exemplified by α-ethyl methacrylate, propyl propyl α-n-propyl acrylate, α- Glycidyl butyl butyl acrylate, 6,7-epoxyheptyl ester of α-ethyl acrylate, etc.; glycidyl ether having an unsaturated bond, an o-vinylbenzyl glycidyl ether, an ethylene Benzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc.; ethylene aromatic compound, exemplified by styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene, para The oxystyrene or the like; the dicarbonyl quinone imine derivative may, for example, be phenyl maleimide, cyclohexyl maleimide, benzyl maleimide, N- Amber succinimide-3-methyleneimine benzoate, N-succinimide-4-butyleneimine butyrate, N-succinate醯imino-6-m-butyleneimine hexanoate, N-succinimide-3-oxenimide propionate, N-(9-acridine)-n-butene Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among these, 2-methylcyclohexyl acrylate, 2-hydroxyethyl methacrylate, styrene, and methacrylic acid ring are used in view of copolymerization reactivity and solubility of the obtained copolymer in an aqueous alkali solution. Oxypropyl propyl ester, tetrahydrofurfuryl methacrylate, 1,3-butadiene or 2-(6-hydroxyethylhexyloxy)ethyl methacrylate is preferred.

The compound (a3) may be used singly or in combination of two or more.

In the copolymer [A], the content of the repeating unit derived from the compound (a3) is preferably from 10 to 70% by weight, more preferably from 20 to 50% by weight, most preferably from 30 to 50% by weight. When the content of the repeating unit derived from the compound (a3) is less than 10% by weight, the storage stability of the obtained radiation sensitive linear resin composition is lowered, and when it exceeds 70% by weight, the radiation is sensitive. The alkali developability of the resin composition is insufficient.

The solvent used in the production of the copolymer [A] may, for example, be an alcohol, an ether, a glycol ether, an ethylene glycol alkyl ether acetate, a diethylene glycol, a dipropylene glycol, a propylene glycol monoalkyl ether or a propylene glycol alkane. Ethyl ether acetate, propylene glycol alkyl ether propionate, aromatic hydrocarbon, ketone, ester, and the like.

In terms of the specific examples, the alcohol may, for example, be methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol or 3-phenyl-1-propanol; and the ether may, for example, be tetrahydrofuran; The alcohol ether may, for example, be ethylene glycol monomethyl ether or ethylene glycol monoethyl ether; and the ethylene glycol alkyl ether acetate may, for example, be methyl cellosolve acetate or ethyl ester. Fibrous acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc.; in the case of diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol Alcohol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc.; in the case of dipropylene glycol, dipropylene glycol monomethyl ether, two Propylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether, etc.; propylene glycol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc.; propylene glycol alkyl ether propionate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, Glycol propyl ether acetate, propylene glycol butyl ether acetate; Examples of the propylene glycol alkyl ether acetate include propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, and the like; For example, toluene, xylene, and the like; and the ketone may, for example, be methyl ethyl ketone, cyclohexanone or 4-hydroxy-4-methyl-2-pentanone; and the ester may, for example, be methyl acetate. Ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropanoate, methyl hydroxyacetate , ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate , butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate , ethoxyacetic acid methyl ester, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate Propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, 3-methoxybutyl acetate , methyl 2-methoxypropionate 2-ethyl methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, 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, 3- Propyl ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3- Esters such as butyl propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate .

Among these, ethylene glycol alkyl ether acetate, diethylene glycol, dipropylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate are preferred, especially diethylene glycol dimethyl ether Further, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate or 3-methoxybutyl acetate is preferred.

These solvents may be used singly or in combination of two or more.

The polymerization initiator used in the production of the copolymer [A] is not particularly limited, and may, for example, be 2,2'-azobisisobutyronitrile or 2,2'-azobis-(2,4-dimethyl Valeronitrile, 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), dimethyl An azo compound such as 2,2'-azobis(2-methylpropionate), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as phenylhydrazine peroxide, lauryl peroxide, tertiary butyl peroxytrimethyl acetate, 1,1-bis(tertiary butylperoxy)cyclohexane; Hydrogen peroxide, etc. In the case of a polymerization initiator, when a peroxide is used, these and a reducing agent may be used in combination as a redox type initiator.

These polymerization initiators may be used alone or in combination of two or more.

The weight average molecular weight (hereinafter referred to as "Mw") of the converted polystyrene by gel permeation chromatography (GPC) of the copolymer [A] is preferably 2,000 to 100,000, more preferably 5,000 to 50,000. When the Mw is less than 2,000, the developability of the obtained film, the residual film ratio, and the like are lowered, and the pattern shape is feared to be impaired. On the other hand, when it exceeds 100,000, the resolution is lowered, and the shape of the pattern may be impaired.

The copolymer [A] produced as described above has at least one selected from the group consisting of a carboxyl group and a carboxylic acid anhydride group derived from the compound (a1), and a dioxopentane structure derived from the compound (a2). It has an appropriate solubility to an alkali developer, and has an advantage that it can be easily cured by heating without using a special hardener.

The copolymer [A] obtained by the above-mentioned method may be used as a linear resin composition for modulating a radiation sensitive agent as it is in a solution state, or may be used for modulating a radiation-sensitive linear resin composition from a solution.

Further, in the present invention, other polymers may be used in combination with the copolymer [A]. As the other polymer, an alkali-soluble copolymer obtained by copolymerizing the above compounds (a1) and (a3) is preferred. In the alkali-soluble copolymer, the content of the repeating unit derived from the compound (a1) is preferably from 1 to 40% by weight, more preferably from 8 to 30% by weight. The Mw of the alkali-soluble copolymer is preferably from 1,000 to 50,000, more preferably from 3,000 to 30,000. The related alkali-soluble copolymer can be produced by using a mixture of the compounds (a1) and (a3) and a method for producing the reference copolymer [A].

In the present invention, when the copolymer [A] and other polymers are used in combination, the use ratio of the other polymer is preferably 80% by weight or less, and 60% by weight based on the total of the copolymer [A] and the other polymer. The following is more preferable, and 50% by weight or less is optimal.

-[B]Polymerizable unsaturated compounds - The [B] polymerizable unsaturated compound contained in the radiation sensitive linear resin composition of the present invention is preferably a polymerizable compound having an ethylenically unsaturated bond.

[B] The polymerizable unsaturated compound is not particularly limited as long as it has an ethylenically unsaturated bond, and is polymerizable, and is excellent in polymerizability and can improve the strength of the obtained spacer. Or a trifunctional or higher (meth) acrylate is preferable.

The monofunctional (meth) acrylate may, for example, be 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl Ether methacrylate, different Acrylate Methyl methacrylate, 3-methoxybutyl acrylate, 3-methoxybutyl methacrylate, 2-propenyl methoxyethyl 2-hydroxypropyl phthalate, 2-methyl Propylene methacryl oxime oxyethyl-2-hydroxypropyl phthalate, ω-carboxy polycaprolactone monoacrylate, etc., and commercially available products, aronix M-101, the same M- 111, same as M-114, same as M-5300 (manufactured by Toagosei Co., Ltd.); KAYARAD TC-110S, same as TC-120S (manufactured by Nippon Kayaku Co., Ltd.); bisuko-to158, same as 2311 (made by Osaka Organic Chemical Industry Co., Ltd.) .

The bifunctional (meth) acrylate may, for example, be ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethyl b. Diol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol II Acrylate, 1,9-nonanediol dimethacrylate, bisphenoxyethanol oxime diacrylate, bisphenoxy Ethyl alcohol dimethacrylate, etc., and commercially available products, aronix M-210, M-240, M-6200 (manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, HX-220, and R- 604 (made by Nippon Kayaku Co., Ltd.), bisuko-to260, the same 312, the same as 335HP (made by Osaka Organic Chemical Industry Co., Ltd.).

The trifunctional or higher (meth) acrylate may be exemplified by trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, and pentaerythritol. Methacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate Examples of esters, dipentaerythritol hexamethacrylate, tris(2-propenyl decyloxyethyl) phosphate, tris(2-methylpropenyl methacryloxyethyl) phosphate, etc. A compound having an alkylene group linear structure, an alicyclic structure, and two or more isocyanate groups in the molecule, and a trifunctional, tetrafunctional or pentafunctional (meth) acrylate compound having one or more hydroxyl groups in the molecule. The resulting urethane acrylate compound is reacted. For such commercial products, aronix M-309, the same M-400, the same M-405, the same M-450, the same M-7100, the same M-8030, the same M-8060, the same TO-1450 (made by East Asia Synthetic Co., Ltd.), KAYARAD TMPTA, with DPHA, with DPCA-20, with DPCA-30, with DPCA-60, with DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), bisuko-to 295, with 300, with 360 In the same way as GPT, the same as 3PA, the same as 400 (made by Osaka Organic Chemical Industry Co., Ltd.), new frontier R-1150 (manufactured by Daiichi Kogyo Co., Ltd.), KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.).

Among the monofunctional, bifunctional or trifunctional or higher functional (meth) acrylates, a trifunctional or higher (meth) acrylate is more preferable, and trimethylolpropane triacrylate, neopentyl alcohol Triacrylate, neopentyltetraol tetraacrylate, dipentaerythritol pentaacrylate or dipentaerythritol hexaacrylate is particularly preferred.

The monofunctional, bifunctional or trifunctional or higher functional (meth) acrylate may be used singly or in combination of two or more.

In the radiation sensitive linear resin composition of the present invention, the use ratio of the [B] polymerizable unsaturated compound means the total amount of the polymer (referred to as the total amount of the copolymer [A] and other polymers. The same applies hereinafter. It is preferably 50 to 200 parts by weight, more preferably 60 to 150 parts by weight, based on 100 parts by weight. [B] If the use ratio of the polymerizable unsaturated compound is less than 50 parts by weight, there may be development residue during development. On the other hand, when it exceeds 200 parts by weight, the adhesion of the resulting spacer may be lowered.

-[C]sensitive radiation linear polymerization initiator - The [C] radiation sensitive linear polymerization initiator contained in the sensitive radiation linear resin composition of the present invention is exposed by radiation such as visible light, ultraviolet rays, far ultraviolet rays, charged particle rays, X-rays, etc., so that the above [B] The polymerizable unsaturated compound starts to polymerize to form a component of the active species. Such a [C] sensitive radiation linear polymerization initiator uses a ruthenium compound, a biimidazole compound, a benzoin compound, an acetophenone compound, a diphenyl ketone compound, an α-diketone compound, a radiation-sensitive linear cationic polymerization initiator, and the like. It is better.

The above hydrazine compound may, for example, be a carbazole compound, and other deuterated compounds. Compound.

In view of the above carbazole compound, an O-fluorenyl hydrazine type polymerization initiator having a 9.H.-carbazole structure is preferred. Specific examples thereof include 1-[9-ethyl-6-benzoin-9.H.-oxazol-3-yl]-nonane-1,2-decane-2-indole-O. -benzoate, 1-[9-ethyl-6-benzoin-9.H.-oxazol-3-yl]-nonane-1,2-decane-2-indole-O-acetic acid Salt, 1-[9-ethyl-6-phenylindol-9.H.-oxazol-3-yl]-pentane-1,2-pentane-2-indole-O-acetate, 1- [9-ethyl-6-phenylhydrazin-9.H.-oxazol-3-yl]-octane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2 -methylphenylhydrazino)-9.H.-carbazol-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(1,3 ,5-trimethylphenylhydrazino)-9.H.-oxazol-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-butyl-6-( 2-ethylbenzoinyl)-9.H.-oxazol-3-yl]-ethane-1-one oxime-O-benzoate, ethanone, 1-[9-ethyl -6-(2-methylphenylhydrazino)-9.H.-carbazol-3-yl]-,1-(O-ethenyloxyindole), ethanone, 1-[9- Ethyl 6-[2-Methyl-4-(2,2-dimethyl-1,3-dioxolyl)methoxybenzoinyl]-9.H.-carbazol-3-yl ]-, 1-(O-Ethyloxyhydrazine), Ethanone, 1-[9-ethyl-6-(2-methylphenylhydrazino)-9.H.-carbazole-3 -yl]-, 1-(O-ethenyloxyhydrazine), etc., among these, ethanone, 1-[9-ethyl-6-(2-methylbenzoinyl)- 9.H.-carbazol-3-yl]-, 1-(O-ethenyloxypurine) or ethanone, 1-[9-ethyl-6-[2-methyl-4- (2,2-Dimethyl-1,3-dioxolyl)methoxybenzoinyl]-9.H.-carbazol-3-yl]-, 1-(O-acetamidine Base oxygen oxime) is particularly good.

These carbazole compounds may be used singly or in combination of two or more.

As the other ruthenium compound, 1,2-octanedione-1-[4- (phenylthio)phenyl]-2-(O-phenylhydrazinyloxy), 1,2-butanedione-1-[4-(phenylthio)phenyl]-2-(O -Benzyl oxindole), 1,2-butanedione-1-[4-(phenylthio)phenyl]-2-(O-ethenyloxy), 1,2-octane Keto-1-[4-(methylthio)phenyl]-2-(O-phenylhydrazinyloxy), 1,2-octanedione-1-[4-(phenylthio)phenyl ]-2-(O-(4-methylbenzohydrazinyloxy)) and the like. Among these, 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzofluorenyloxyindole) is particularly preferred.

In the above biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2' can be exemplified. -biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2 , 2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl) -4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5, 5'-Tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-bromo)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2 , 2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6 -Tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, etc. Among these, 2,2'-bis(2-chlorophenyl)- 4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetra Phenyl-1,2'-biimidazole or 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-linked Imidazole is preferred, preferably 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'- Imidazole.

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

By using these biimidazole compounds, the sensitivity, resolution and adhesion of the resulting radiation sensitive linear resin composition can be further improved.

In the sensitive radiation linear resin composition of the present invention, [C] sensitive radiation linearity In the case of using a biimidazole compound, an aromatic compound having a dialkylamine group (hereinafter referred to as "dialkylamine-based sensitizer") may be used in combination for the purpose of sensitization. As the related dialkylamine-based sensitizer, 4,4'-bis(dimethylamino)diphenyl ketone and 4,4'-bis(diethylamino)diphenyl ketone can be exemplified. , p-dimethylaminobenzoic acid ethyl, p-diethylaminobenzoic acid ethyl, p-dimethylaminobenzoic acid isoamyl ester, p-diethylaminobenzoic acid isoamyl ester, etc. Among them, 4,4'-bis(diethylamino)diphenyl ketone is preferred. These dialkylamine-based sensitizers may be used singly or in combination of two or more.

Further, when a biimidazole compound and a dialkylamine based sensitizer are used in combination, a thiol compound may be added to the hydrogen supply compound. The biimidazole compound is sensitized and cleaved by a dialkylamine-based sensitizer to produce an imidazole radical, but at this time, a high initial polymerization energy is not immediately found, and the resulting spacer is not inverted. The case of a good shape. In a system in which a biimidazole compound and a dialkylamine-based sensitizer coexist, this problem can be solved by adding a thiol compound. That is, in the imidazole radical, the imidazole radical is made neutral imidazole by supplying a hydrogen radical from the thiol compound, and as a result, a spacer shape is produced due to a component of a sulfur radical having a high initial polymerization energy. It becomes a better straight cone shape.

The above thiol compound may, for example, be 2-hydrothiobenzothiazole, 2-hydrothiobenzoxazole, 2-hydrothiobenzimidazole or 2-hydrothio-5-methoxybenzo Aromatic thiol such as thiazole, 2-hydrothio-5-methoxybenzimidazole, 3-hydrothiopropionic acid, methyl 3-hydrothiopropionate, 3-hydrothiopropionic acid An aliphatic monothiol such as an ester or an octyl 3-hydrothiopropionate; 3,6-dioxa-1,8-octane dithiol, isopentaerythritol tetrakis (hydrothioacetate), isopentaerythritol tetrakis(3-hydrothiopropionate), etc. 2 An aliphatic thiol or the like having a functional or higher. These thiol compounds can be used singly or in combination of two or more types.

The benzoin compound may, for example, be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether or 2-phenylmercaptobenzoic acid methyl group.

The acetonitrile compound may, for example, be an α -hydroxyketone compound, an α-amino ketone compound or a compound other than the above.

Specific examples of the above α -hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1-(4-isopropylphenyl)-2-hydroxy-2. -methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, etc.; the above α -amino ketone Specific examples of the compound include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2- Dimethylamino-1-(4-morpholinylphenyl)-butan-1-one and the like.

These acetophenone compounds may be used singly or in combination of two or more.

In the present invention, in terms of the [C] radiation-sensitive linear polymerization initiator, the sensitivity of the obtained radiation sensitive linear resin composition, the shape of the obtained spacer, the compressive strength, and the like can be further improved by using an acetophenone compound.

The diphenyl ketone compound may, for example, be 4,4'-bis(dimethylamino)diphenyl ketone or 4,4'-bis(diethylamino)diphenyl ketone.

The above α -diketone compound may, for example, be a diethylidene group, a diphenylfluorenyl group or a methylphenyl fluorenylcarboxylate.

The above-mentioned radiation-sensitive linear cationic polymerization initiator may, for example, be an onium salt, an aromatic metallocene compound or the like.

Specific examples of the above sulfonium salt include phenyl arsenazotetrafluoroborate, phenyl arsenazo hexafluorophosphonate, phenyl arsenazo hexafluoroarsenate, and phenyl arsenazo Fluoromethanesulfonate, phenyl arsenazo trifluoroacetate, phenyl arsenazo-p-toluenesulfonate, 4-methoxyphenyl arsenazotetrafluoroborate, 4-methoxy Phenyl arsenazo hexafluorophosphonate, 4-methoxyphenyl arsenazo hexafluoroarsenate, 4-methoxyphenyl arsenazo trifluoromethane sulfonate, 4-methoxybenzene Arsenazo trifluoroacetate, 4-methoxyphenyl arsenazo-p-toluenesulfonate, 4-tert-butylphenyl arsenazotetrafluoroborate, 4-tertiary butyl Phenyl arsenazo hexafluorophosphonate, 4-tris-butylphenyl arsenazo hexafluoroarsenate, 4-tert-butylphenyl arsenazo trifluoromethane sulfonate, 4-tertiary Butyl phenyl arsenazo trifluoroacetate, azo sulfonium salt such as 4-tris-butylphenyl arsenazo-p-toluenesulfonate; triphenylsulfonium tetrafluoroborate, triphenyl Hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenyl Trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylphosphonium tetrafluoroborate, 4-methoxyphenyldiphenylphosphonium hexafluorophosphonate , 4-methoxyphenyldiphenylphosphonium hexafluoroarsenate, 4-methoxyphenyldiphenylphosphonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylphosphonium trifluoride Acid ester, 4-methoxyphenyldiphenylphosphonium-p-toluenesulfonate, 4-phenylthiophene diphenyltetrafluoroborate, 4-phenylthiophene diphenyl hexafluorophosphonate, 4 -phenylthiophene diphenyl hexafluoroarsenate, 4-phenylthiophene diphenyl trifluoromethanesulfonate, 4- A sulfonium salt such as phenylthiophene diphenyl trifluoroacetate or 4-phenylthiophene diphenyl-p-toluenesulfonate.

The above-mentioned metallocene compound may, for example, be (1-6-η-cumene) (η-cyclopentadienyl) iron (1+) hexafluorophosphoric acid (1-) or the like.

The commercially available product of the sensitizing radiation polymerization initiator may, for example, be Adecaultra set PP-33 (manufactured by ADEKA) of azo arsenic salt, OPTOMER SP-150 of bismuth salt, and -170 (manufactured by ADEKA Corporation) ) is Irgacure 261 (manufactured by Chiba Specialty Chemicals Co., Ltd.) which is an organolocene metal derivative compound.

In the present invention, the [C] radiation-sensitive linear polymerization initiator may be used singly or in combination of two or more kinds.

In the present invention, as the [C] radiation-sensitive linear polymerization initiator, it is preferred to use the above-mentioned hydrazine compound, and it is particularly preferred to use a carbazole compound in combination with other hydrazine compounds. [C] In terms of a linear radiation polymerization initiator, the sensitivity of the radiation-sensitive linear resin composition to radiation can be further improved by using a carbazole compound in combination with other ruthenium compounds, for example, even at a exposure amount of 1,500 J/m ² or less. In this case, a spacer for a display panel excellent in adhesion to a substrate can be formed.

In the radiation sensitive linear resin composition of the present invention, the use ratio of the [C] radiation-sensitive linear polymerization initiator is preferably from 1 to 30 parts by weight, more preferably from 1 to 30 parts by weight, based on 100 parts by mass of the [B] polymerizable unsaturated compound. 2 to 20 parts by weight. When the amount of the sensitive polymerization linear polymerization initiator used is less than 1 part by weight, the residual film ratio during development may be insufficient. When it is 30 parts by weight, the solubility of the unexposed portion to the alkaline developing solution at the time of development is insufficient.

In the [C] radiation sensitive linear polymerization initiator used in the radiation sensitive linear resin composition of the present invention, the occupation ratio of the cerium compound is preferably 20% by weight based on the total amount of the [C] radiation-sensitive linear polymerization initiator. More preferably, it is 40 weight% or more. Here, when the occupation ratio of the ruthenium compound is less than 20% by weight, it is difficult to find the effect expected by the present invention. In the ruthenium compound, the occupation ratio of the carbazole compound is preferably 30% by weight or more, and more preferably 50% by weight or more based on the total amount of the ruthenium compound.

In the radiation sensitive linear resin composition of the present invention, in the case of the [C] radiation-sensitive linear polymerization initiator, a biimidazole compound is used, and in the case where the dialkylamine-based sensitizer is used in combination, a dialkylamine is used. The use ratio of the sensitizer is preferably from 0.1 to 50 parts by weight, more preferably from 1 to 20 parts by weight, per 100 parts by weight of the total amount of the polymer. When the amount of the dialkylamine-based sensitizer used is less than 0.1 part by weight, the resulting spacer may cause film thinning to impair the shape of the pattern, and on the other hand, if it exceeds 50 parts by weight, it may be damaged. The shape of the pattern of the spacer. Further, in the case of the [C] radiation-sensitive linear polymerization initiator, a biimidazole compound is used, and when the dialkylamine-based sensitizer and the thiol compound are used, the use ratio of the thiol compound is relative to the total amount of the polymer. 100 parts by weight, preferably 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight. When the use ratio of the thiol compound is less than 0.1 part by weight, the resulting spacer may cause film thinning or poor shape of the pattern. On the other hand, if it exceeds 50 parts by weight, the pattern shape of the spacer may be impaired. .

-Other additives - The radiation sensitive linear resin composition of the present invention contains the above-mentioned copolymer [A], [B] a polymerizable unsaturated compound and an essential component of the [C] radiation-irradiation linear combination initiator, but does not impair the desired effect of the present invention. In the range, other additives may be included as needed.

Other related additives may, for example, be surfactants, adhesion aids, storage stabilizers, heat resistance improvers, and the like.

In order to improve the coatability of the resulting radiation sensitive linear resin composition, the above surfactant may be used. As a related surfactant, a fluorine-based surfactant, a polyoxyn surfactant, and other surfactants can be exemplified.

In the above-mentioned fluorine-based surfactant, a compound having a fluoroalkyl group or a fluoroalkylene group in at least one of the main chain and the side chain is preferably used. Specific examples thereof include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl)ether, 1,1,2,2-tetrafluorooctylhexyl ether. , octaethylene glycol di(1,1,2,2-tetrafluorobutyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl)ether, octapropylene glycol di 1,1,2,2-tetrafluorobutyl)ether, hexapropanediol bis(1,1,2,2,3,3-hexafluoropentyl)ether, sodium perfluorododecyl citrate, 1,1 , 2,2,3,3,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, sodium fluoroalkyl benzoate, halothane Sodium phosphinate, sodium fluoroalkylcarboxylate, fluoroalkyl polyoxyethylene ether, diglycerol four (fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl Polyoxyethylene ether, perfluoroalkyl polyoxyethylene, perfluoroalkyl alkoxide, fluoroalkyl ester, etc., such as commercially available products, BM-1000, BM-1100 (BM CHEMIE) System), megafuck F142D, Same as F172, same as F173, same as F183, same as F178, same as F191, same as F471, with F476 (made by Dainippon Ink Chemical Industry Co., Ltd.), Fluorad FC 170C, FC-171, FC-430, FC-431 (manufactured by Sumitomo 3M Co., Ltd.) ), Safron S-112, same as S-113, with S-131, with S-141, with S-145, with S-382, with SC-101, with SC-102, with SC-103, with SC- 104, with SC-105, with SC-106 (made by Asahi Glass Co., Ltd.), f-top EF301, with 303, with 352 (made by New Akita Chemical Co., Ltd.), Futazient FT-100, with FT-110, with FT-140A, Same as FT-150, same as FT-250, with FT-251, with FTX-251, with FTX-218, with FT-300, with FT-310, with FT-400S (manufactured by Neos).

The polyfluorene surfactant may be exemplified by Toray polyoxane DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, and SH-193. SZ-6032, same as SF-8428, with DC-57, with DC-190 (Toray. Dow Corning. manufactured by Polyoxo Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460 A commercial item such as TSF-4452 (made by Momentive Performance Materials Japan Co., Ltd.).

The above other surfactants may, for example, be polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl sulfonyl ether, polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl; a polyoxyethylene aryl ether such as an ether or a polyoxyethylene n-nonylphenyl ether; a nonionic system such as a polyoxyethylene dilaurate such as polyoxyethylene dilaurate or polyoxyethylene distearate; Surfactant, or Commercially available KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 57, 95 (manufactured by Kyoei Chemical Co., Ltd.), and the like.

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

The blending amount of the surfactant is preferably 5 parts by weight or less, more preferably 2 parts by weight or less based on 100 parts by weight of the total amount of the polymer. When the amount of the surfactant is more than 5 parts by weight, film breakage easily occurs during coating.

In order to further improve the adhesion between the resulting spacer and the substrate, the above-mentioned adhesion aid can be used.

The functional decane coupling agent is preferably a functional decane coupling agent, and examples thereof include a decane coupling agent having a reactive functional group such as a carboxyl group, a methacryl oxime group, an isocyanate group or an epoxy group. More specifically, trimethoxydecyl benzoic acid, γ -methyl propylene methoxy propyl trimethoxy decane, ethylene triethoxy decane, ethylene trimethoxy decane, γ-isocyanate propyl may, for example, be mentioned. Triethoxy decane, γ-glycidylpropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like.

These adhesion aids may be used singly or in combination of two or more.

The blending amount of the adhesion aid is preferably 20 parts by weight or less, more preferably 10 parts by weight or less based on 100 parts by weight of the total amount of the polymer. When the amount of the adhesion aid is more than 20 parts by weight, development residue may easily occur.

The above-mentioned storage stabilizer can be used for the purpose of improving the storage stability of the obtained radiation sensitive linear resin composition. The related storage stabilizer may, for example, be sulfur, an anthracene compound, a hydroquinone compound, a polyoxygen compound, an amine or a nitronitroso compound. Specific examples thereof include 4-methoxybenzene Phenol, N-nitroso-N-phenylhydroxylamine aluminum, and the like. The amount is preferably 3.0 parts by weight or less, more preferably 0.001 to 0.5 parts by weight, based on 100 parts by weight of the total amount of the polymer. When the amount of the storage stabilizer used exceeds 3.0 parts by weight, the radiation sensitivity of the radiation sensitive linear resin composition is insufficient, and the pattern shape of the resulting spacer will deteriorate.

In order to further improve the heat resistance of the resulting spacer, the above heat resistance improving agent can be used. The related heat resistance improving agent may, for example, be an N-(alkoxymethyl)acetylene urea compound, an N-(alkoxymethyl)melamine compound, or a compound having a bifunctional or higher epoxy group in one molecule.

Specific examples of the above N-(alkoxymethyl)acetylene urea compound may, for example, be N,N,N',N'-tetrakis(methoxymethyl)acetyleneurea, N,N,N',N '-tetrakis(ethoxymethyl)acetylene urea, N,N,N',N'-tetrakis(n-propoxymethyl)acetylene urea, N,N,N',N'-tetra(isopropoxy Methyl)acetylene urea, N,N,N',N'-tetrakis(n-butoxymethyl)acetylene urea, N,N,N',N'-tetrakis(tris-butoxymethyl)acetylene Urea, etc. Among these, N, N, N', N'-tetrakis(methoxymethyl) acetylene urea is particularly preferred.

Specific examples of the above N-(alkoxymethyl)melamine compound include N, N, N', N', N'', N''-hexa(methoxymethyl)melamine, N, N,N',N',N'',N''-hexa(ethoxymethyl)melamine, N,N,N',N',N'',N''-hexa-n-propoxy Base) melamine, N, N, N', N', N'', N''-hexa(isopropoxymethyl) melamine, N, N, N', N', N'', N'' - hexa(n-butoxymethyl)melamine, N,N,N',N',N'', N''-hexa(tris-butoxymethyl)melamine, and the like. Among these, N, N, N', N', N'', N''-hexa(methoxymethyl) melamine good. For the above-mentioned commercial products, NIKALAC N-2702, MW-30M (manufactured by Sanwa Chemical Co., Ltd.), and the like can be exemplified.

The compound having a bifunctional or higher epoxy group in one molecule may, for example, be ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether or propylene glycol dihydrate. Glyceryl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether , trimethylolpropane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, phenol novolac type epoxy resin, and the like. Such commercial products may, for example, be Epolight 40E, Epolight 100E, Epolight 200E, Epolight 70P, Epolight 200P, Epolight 400P, Epolight 400E, Epolight 1500NP, Epolight 1600, Epolight 80MF, Epolight 100MF, Epolight 4000, Epolight 3002 ( Co., Ltd., manufactured by Kyoeisha Chemical Co., Ltd., epitoke 152 (manufactured by Nippon Epoxy Resin Co., Ltd.). These may be used alone or in combination of two or more.

The use ratio of the heat resistance improver is preferably 30 parts by weight or less, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the total amount of the polymer.

- solvent - The radiation sensitive linear resin composition of the present invention is preferably prepared by dissolving the above copolymer [A], [B] polymerizable unsaturated compound and [C] radiation sensitive linear polymerization initiator, and any other additives used arbitrarily. Suitable solvent Medium is prepared as a composition solution.

In the solvent used for preparing the solution of the radiation sensitive linear resin composition of the present invention, those which can dissolve the components constituting the linear composition of the radiation sensitive resin and which do not react with the respective components can be used.

As such a solvent, those exemplified as the solvent used for the production of the above copolymer [A] can be exemplified.

In such a solvent, for example, an alcohol, a glycol ether, an ethylene glycol alkyl ether acetate, an ester, and the like are used in view of solubility of each component, reactivity with each component, and formation of a film. Diethylene glycol is preferred. Among these, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate are used. , diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methoxy propionate The base, ethyl ethoxypropionate, and 3-methoxybutyl acetate are particularly preferred.

Further, in order to simultaneously improve the uniformity in the film thickness plane, the solvent may be used in combination with a high boiling point solvent. The high-boiling solvent which can be used in combination may, for example, be N-methylformamide, N,N-dimethylformamide, N-methyl N-methylanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octyl Alcohol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve B Acid esters, etc. Among these, N-methylpyrrolidone, γ-butyrolactone, and N,N-dimethylacetamide are preferred.

The solid content of the sensitive radiation linear resin composition in terms of the amount of solvent used The concentration (the ratio of the total weight of the components of the solvent of the linear radiation-removing resin composition to the total weight of the linear radiation-sensitive resin composition) is preferably 10 to 80% by weight, and is 15 to 70% by weight. For better. The preferred solid content concentration varies depending on the method used to form the film of the radiation sensitive linear resin composition of the present invention on the substrate, and the details thereof will be described later.

The solution of the linear radiation-sensitive resin composition prepared in this manner can be used by filtering from a micropore filter having a pore diameter of, for example, about 0.2 to 0.5 μm, as needed.

The radiation sensitive linear resin composition of the present invention is particularly suitable for forming a spacer for a liquid crystal display element such as a liquid crystal panel or a touch panel.

<Method of Forming Spacer for Liquid Crystal Display Element> When the spacer for a liquid crystal display element is formed using the radiation sensitive linear resin composition of the present invention, for example, it can be achieved by a method comprising the following steps in at least the following order.

(1) a step of forming a film of the radiation sensitive linear resin composition of the present invention on a substrate, (2) a step of exposing at least a portion of the film, (3) a step of developing the film after exposure, and (4) The step of heating the film after development.

The respective steps of the method for forming the spacer for a liquid crystal display element of the present invention will be described below.

(1) Step of forming a film of the radiation sensitive linear resin composition of the present invention on a substrate When a spacer for a liquid crystal display element is formed using the radiation sensitive linear resin composition of the present invention, first, a film of the radiation sensitive linear resin composition of the present invention is formed on a substrate.

The film thickness of the film formed here is preferably 0.5 to 6.0 μm, more preferably 1.5 to 4.5 μm.

As the substrate to be used herein, a transparent substrate in which a transparent conductive film is formed on one side is preferable.

The material constituting the transparent substrate may, for example, be glass, resin or the like. Examples of the glass include soda lime glass, alkali-free glass, and the like; and examples of the resin include polyethylene terephthalate, polybutylene terephthalate (PBT), polyether oxime, and polycarbonate. , polyimine and the like.

The transparent conductive film may, for example, be a NESA film made of tin oxide (SnO ₂ ) (registered trademark of PPG, USA), and an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ). Wait.

The method of forming the film of the radiation sensitive linear resin composition of the present invention on the substrate can be achieved by, for example, (i) coating method or (ii) dry film method.

(i) When the coating method is used, a solution of the radiation sensitive linear resin composition of the present invention can be applied onto a substrate, and then the coated surface is formed by heating (prebaking) to form a film.

When the coating method is used, the solid content concentration of the composition solution is preferably from 10 to 50% by weight, more preferably from 15 to 40% by weight.

The coating method of the composition solution is not particularly limited, and an appropriate method such as a spray method, a coating method, and a spin coating method (spin) may be employed. The coating method, the slit coating method, the bar coating method, the inkjet coating method, and the like are particularly preferably a spin coating method or a slit die coating method.

The prebaking conditions vary depending on the type of the components contained in the sensitive radiation linear resin composition, the blending ratio, etc., and are preferably prebaked at 70 to 110 ° C for 1 to 15 minutes.

On the other hand, when the film is formed by the (ii) dry film method, the dry film is laminated on a substrate film, preferably a flexible substrate film, and laminated with the radiation sensitive linear resin composition of the present invention. The photosensitive layer is formed (hereinafter referred to as "photosensitive dry film").

The photosensitive dry film can be produced by coating the photosensitive radiation linear resin composition of the present invention as a solution composition on the substrate film, removing the solvent, and laminating the photosensitive layer. As the base film of the photosensitive dry film, a film of a synthetic resin such as polyethylene terephthalate (PET), polyethylene, polypropylene, polycarbonate, or polyvinyl chloride can be used. The thickness of the matrix film is suitably in the range of 15 to 125 μm. The thickness of the obtained photosensitive layer is preferably about 1 to 30 μm.

The solid content concentration of the radiation sensitive linear resin composition coated on the substrate film is preferably from 30 to 80% by weight, more preferably from 40 to 70% by weight.

As for the coating method of the composition solution on the substrate film, for example, a method using an applicator, a gravure method, a comma method, or the like, in which an applicator is used, or gravure printing (gravure) can be used. The law is better.

The removal of the solvent can be achieved, for example, by heat treatment at 80 to 110 ° C for about 1 to 10 minutes.

When the photosensitive dry film is not used, the outer film can be laminated on the photosensitive layer to prepare for storage. In order to prevent the outer film from being peeled off when it is not used, it is easy to peel off during use, and it is necessary to have appropriate mold release property. For the outer cover film which satisfies such conditions, for example, it can be coated on the surface of a synthetic resin film such as a PET film, a polypropylene film, a polyethylene film, a polyvinyl chloride film or a polyurethane film, and coated with polyoxyl It is a release agent or a baking film. The thickness of the outer cover film is usually about 5 to 30 μm. The outer cover film can be a two-layer or three-layer laminated outer cover film as needed.

When the film of the radiation sensitive linear resin composition of the present invention is formed on the substrate by using the photosensitive dry film as described above, a method such as a bonding method can be used.

(2) a step of exposing at least a portion of the film Next, at least a part of the film formed as described above is irradiated with radiation and exposed. For the radiation used for exposure, visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-ray, etc. may be appropriately selected, but radiation having a wavelength in the range of 190 to 450 nm is preferred. When only a part of the film is exposed, for example, a method of irradiating radiation through a mask of a setting pattern or the like can be performed.

Here, the exposure amount is preferably 400 to 2,000 J/m ^{2 and more} preferably 500 to 1,500 J/m ² .

Further, the conventional spacer-forming photosensitive radiation linear resin composition must have an exposure amount of at least 2,000 J/m ² at least, but the radiation sensitive linear resin composition of the present invention is at least 1,500 J/m ² or less. In the exposure amount of 1,200 J/m ² or less, an appropriate spacer having a desired pattern can be formed, which contributes to an advantage of shortening the step time and reducing the manufacturing cost.

(3) Step of developing the exposed film Next, a step of developing the film after exposure is provided.

The developing method may be, for example, any one of a liquid-filling method, a dipping method, a rinsing method, and the like, and the developing time is preferably from 30 to 180 seconds.

For the developer used for development, an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia or the like; an amine of the amine such as ethylamine or n-propylamine; a second-order amine such as diethylamine or di-n-propylamine; a tertiary amine such as trimethylamine, methyldiethylamine, ethyldimethylamine or triethylamine; dimethyl a tertiary alkanolamine such as ethanolamine, methyldiethanolamine or triethanolamine; pyrrolizole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo[5.4.0 An alicyclic tertiary amine such as -7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene; pyridine, collidine, quinoline, etc. An aromatic tertiary amine; an aqueous solution of a basic compound such as tetramethylammonium hydroxide or a tetrabasic ammonium salt such as tetraethylammonium hydroxide.

In the aqueous solution of the above-mentioned basic compound, at least one selected from the group consisting of a water-soluble organic solvent such as methanol or ethanol and a surfactant can be appropriately added.

After development, it can be washed by running water, such as 30~90 seconds. After removing the unwanted portion, it is blown with compressed air or compressed nitrogen to dry it to form a set pattern.

(4) Step of heating the developed film Next, by patterning as described above, a spacer for a liquid crystal display element can be formed on a substrate by heating (post-baking) using a hot plate or an appropriate heating means such as an oven. The heating temperature for the post-baking is preferably 150 to 250 ° C, and the preferred heating time varies depending on the apparatus used for heating. For example, when a heating device for a hot plate is used, the preferred heating time is 5 to 30 minutes, and when the oven is used, the preferred heating time is 30 to 90 minutes.

<spacer> As described above, the spacer formed of the radiation sensitive linear resin composition of the present invention can be understood from the examples described later, and has excellent adhesion to the substrate, excellent polishing resistance and heat resistance, and at the same time, has flexibility and high elastic recovery. The rate can be suitably used for a display element such as a liquid crystal display panel or a touch panel.

<Liquid crystal display element> The liquid crystal display element of the present invention includes a spacer formed by the above-described method.

The liquid crystal display element of the present invention has an advantage that it is difficult to cause display unevenness even when pressure is applied from the outside.

Example

The present invention will be specifically described below by way of examples and comparative examples, but the invention is not limited to the examples.

In the following, the weight average molecular weight of the polymer is the converted polystyrene molecular weight measured by gel permeation chromatography (GPC Shodex GPC-101 (manufactured by Showa Denko)).

Synthesis Example 1 (Synthesis of Copolymer [A] (1))

In a flask equipped with a cooling tube and a stirrer, 4 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 250 parts by weight of 3-methoxybutyl acetate were placed. Next, 5 parts by weight of styrene, 10 parts by weight of methacrylic acid, 40 parts by weight of 4-propenyl methoxymethyl-2-methyl-2-ethyl-1,3-dioxolane, methyl group 25 parts by weight of 2-methylglycidyl acrylate and 20 parts by weight of benzyl methacrylate were added, and after nitrogen substitution, stirring was started slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-1]. The solid solution concentration of the obtained polymer solution was 27.9% by weight, and the weight average molecular weight of the polymer was 26,000.

Synthesis Example 2 (Synthesis of Copolymer [A] (2))

In a flask equipped with a cooling tube and a stirrer, 4 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 250 parts by weight of propylene glycol monomethyl ether acetate were placed. Next, 5 parts by weight of styrene, 8 parts by weight of methacrylic acid, and 4-propylene decyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane 45 were placed. In parts, 20 parts by weight of glycidyl methacrylate and 22 parts by weight of benzyl methacrylate were added, and after nitrogen substitution, stirring was started slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-2]. The solid solution concentration of the obtained polymer solution was 28.5% by weight, and the weight average molecular weight of the polymer was 25,000.

Synthesis Example 3 (Synthesis of Copolymer [A] (3))

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobisisobutyronitrile and 250 parts by weight of 3-methoxybutyl acetate were placed, and then 5 parts by weight of styrene was placed. 10 parts by weight of methacrylic acid, 40 parts by weight of 4-propenyl methoxymethyl-2-methyl-2-ethyl-1,3-dioxolane, tricyclomethyline [5.2.1.0 ^2,6 10 parts by weight of decane-8-yl ester (tricyclodecyl methacrylate), 15 parts by weight of 2-hydroxyethyl methacrylate and 20 parts by weight of benzyl methacrylate, after nitrogen substitution, began to slowly Stir. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-3]. The solid solution concentration of the obtained polymer solution was 28.0% by weight, and the weight average molecular weight of the polymer was 22,000.

Synthesis Example 4 (Synthesis of Other Copolymers)

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobisisobutyronitrile and 250 parts by weight of propylene glycol monomethyl ether acetate were placed. Next, 5 parts by weight of styrene, 15 parts by weight of methacrylic acid, 35 parts by weight of tricyclo [5.2.1.0 ^2,6 ]decane-8-yl methacrylate (tricyclodecyl methacrylate) And 45 parts by weight of benzyl methacrylate, and after nitrogen substitution, stirring was started 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 solid solution concentration of the obtained polymer solution was 29.0% by weight, and the weight average molecular weight of the polymer was 28,000.

Example 1

<Preparation of Sensitive Radiation Linear Resin Composition> The copolymer [A] is a polymer solution containing the copolymer [A-1] obtained in the above Synthesis Example 1 in an amount equivalent to 100 parts by weight (solid content) of the copolymer [A-1], [B] The polymerizable unsaturated compound is 100 parts by weight of KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd.), and [C] a radiation-sensitive linear polymerization initiator of ethanone, 1-[9-ethyl-6 -(2-Methylphenylhydrazino)-9.H-carbazol-3-yl]-, 1-(O-ethenyloxyindole) (manufactured by Chiba Specialty Chemicals, trade name "Irgacure OX02" 5 parts by weight, and 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (Chiba 10 parts by weight of a special chemical company, "Irgacure 379", so that the solid content concentration is 30% by weight, and after being dissolved in propylene glycol monomethyl ether acetate, it is filtered by a micropore having a pore diameter of 0.2 μm. The filter was filtered, and the linear radiation-sensitive resin composition solution (S-1) was prepared, and various evaluations were carried out in accordance with the following methods. The results are shown in Table 2.

<Formation and evaluation of spacers> (I) Evaluation of sensitivity After coating the radiation sensitive linear resin composition solution (S-1) on the alkali-free glass substrate by spin coating, a film having a film thickness of 3.5 μm was formed by prebaking at 80 ° C for 3 minutes on a hot plate. (coating film).

On the coating film obtained above, the exposure gap was 150 μm through a mask having a circular pattern of 15 μm remaining, and exposure was performed with a variable amount of exposure. Subsequently, it was washed with pure water for 1 minute by using a 0.05% by weight aqueous solution of potassium hydroxide, and developing at 25 ° C for 1 minute by a rinsing method. Further, it was heated in an oven at 230 ° C for 30 minutes (after baking) to form a spacer.

At this time, the residual film ratio after development ((film thickness after baking/film thickness after exposure (before development) × 100) is a sensitivity of 90% or more minimum exposure amount.

(II) Evaluation of developability In the above (I), the exposure amount is exposed as the value of the sensitivity investigated in the above (I), and when development is performed using the development time as a variable, no residue (residual development) is formed in the unexposed portion, and a pattern can be formed. The shortest development time of the type is used as developability. The shorter the time, the better the developability.

(III) Formation of spacers In the above (I), the exposure amount is set to the value of the sensitivity measured by the above (I), and the development time is the time of the developability investigated in the above (II), and the substrate is the same as the above (I). A spacer is formed on the upper side.

The following evaluation was performed by the exposure amount and the development time.

(IV) Evaluation of grinding resistance In the method of the above (III), AL3046 (trade name, manufactured by JSR Corporation) as a liquid crystal alignment agent was applied to a substrate on which a spacer was formed, and a liquid crystal alignment film coating machine was applied thereto, and heated at 180 ° C for 1 hour. Forming a film thickness 0.05 μm alignment agent coating film.

The coating film was subjected to a grinding treatment using a polishing machine having a roll wound with a nylon-made cloth at a roller rotation speed of 500 rpm and a stepwise moving speed of 1 cm/sec. Check if the spacer pattern is detached or peeled off at this time.

(V) Evaluation of adhesion In the above (III), a pattern-free cured film was formed on the substrate in the same manner as in the above (III) except that the pattern mask was not used. Regarding the cured film, in the adhesion test of JIS K-5400 (1900) 8.5, the adhesion test was carried out by the crosscut taping method of 8.5.2. At this time, the number of remaining checkerboard eyes is checked in 100 (10 × 10) checkerboard eyes. Among the 100 checkerboard eyes, when it is completely left, it indicates that the adhesion is good.

(VI) Evaluation of heat stability The height of the spacer formed by the above method (III) was measured, and the height of the spacer after additional heating at 230 ° C for 30 minutes in an oven was measured. At this time, the maintenance rate of the height is obtained by the following formula retention rate (%) = (height after additional heating/height before additional heating) × 100. When the maintenance rate of this height is 99% or more, it shows that heat resistance stability is favorable.

(VII) Evaluation of elastic recovery rate For the spacer formed by the above method (III), a micro-compression tester (product name "DUH-201" manufactured by Shimadzu Corporation) is used, and the plane indentation having a diameter of 50 μm, the load speed and the speed of the load are the same. At 2.6 mN/sec, the load is applied after a load of 50 mN for 5 seconds, and the load is reduced. Load-deformation curve and load-deformation curve at load-time. At this time, as shown in Fig. 1, the difference between the amount of deformation at a load of 50 mN and the amount of deformation at a load of 5 mN is L1, and the difference between the amount of deformation at a load of 50 mN and the amount of deformation at a load of 5 mN. For L2, the elastic recovery rate (%) = L2 × 100 / L1

Calculate the elastic recovery rate.

Examples 2 to 10 and Comparative Examples 1, 2

In the first embodiment, except that the types and amounts of the respective components contained in the radiation-sensitive linear resin composition are as shown in Table 1, the same as in the first embodiment, each of which modulates the radiation-sensitive linear resin composition solution (S-2). - (S-10) and (s-1) and (s-2), various evaluations were carried out in the same manner as in Example 1 using each of the sensitive radiation linear resin composition solutions. The evaluation results are shown in Table 2.

Further, in Example 9 and Comparative Example 2, in addition to the copolymer [A], [B] polymerizable unsaturated compound and [C] radiation sensitive linear polymerization initiator, other phenol novolac type epoxy resins (Japan) The amount described in Table 1 was added to the product name "epitoke 152" manufactured by Epoxy Resin Co., Ltd.).

Further, in Example 10, the copolymer [A] and other polymers were used in combination.

Example 11

<Preparation of Sensitive Radiation Linear Resin Composition> In the first embodiment, the type and amount of each component contained in the linear radiation-sensitive resin composition are as shown in Table 1, except that the solid content concentration of the composition solution is 50% by weight, and the modulation radiation is modulated as in the first embodiment. line Resin composition solution (S-11).

In Example 11, the copolymer [A] and other polymers were used in combination.

<Formation and evaluation of spacers> In the first embodiment, various methods were carried out in the same manner as in Example 1 except that the film was formed on the substrate by the dry film method instead of the spin coating method. The results are shown in Table 2.

The production of the dry film and the transfer of the linear layer of the sensitive radiation on the substrate were carried out in the following manner.

On a polyethylene terephthalate film having a thickness of 38 μm, the liquid composition (S-11) of the radiation-sensitive linear resin composition was applied by using an applicator, and the coating film was heated at 100 ° C. A sensitive radiation linear dry film having a linear layer of 4 μm thick radiation was fabricated for 5 minutes. Then, on the surface of the alkali-free glass substrate, the surface of the sensitive radiation linear transfer layer is abutted, the sensitive radiation linear dry film is laminated, and the linear layer of the sensitive radiation is transferred onto the substrate by hot pressing. .

Observing the above-mentioned linear layer of sensitive radiation, the linear layer of sensitive radiation can be "○" when uniformly transferred on the substrate, and some dry film remains on the underlying film, and the dry film on the substrate cannot be closely adhered, etc., dried on the glass substrate. When the film cannot be uniformly transferred, it is "x". The results are shown in Table 2.

Comparative example 3

In the eleventh embodiment, the type and amount of each component contained in the linear radiation-sensitive resin composition are as shown in Table 1, and the other is the same as in the eleventh embodiment. Similarly, a linear radiation-sensitive resin composition solution (s-3) was prepared, and a linear radiation-sensitive film of the radiation radiation was produced in the same manner as in Example 11 and various evaluations were carried out. The evaluation results are shown in Table 2.

In Table 1, the abbreviation of the component means the following compound.

(B-1): dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD DPHA") (B-2): Commercial product containing a polyfunctional urethane acrylate compound (trade name KAYARAD DPHA-40H) (B-3): Pentaerythritol tetraacrylate (manufactured by Toagosei Co., Ltd., trade name "aronix M-450") (B-4): ω-carboxypolycaprolactone monoacrylate (manufactured by Toagosei Co., Ltd., trade name "aronix M-5300") (B-5): 1,9-decane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name "light acrylate 1,9-NDA") (C-1): ethanone, 1-[9-ethyl-6-(2-methylphenylindenyl)-9.H.-carbazol-3-yl]-, 1-(O -Ethyl oxyhydrazine) (product name "Irgacure OX02", manufactured by Chiba Special Chemicals Co., Ltd.) (C-2): ethanone, 1-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolyl) ) methoxybenzoinyl]-9.H.-carbazol-3-yl]-, 1-(O-ethenyloxyhydrazine) (manufactured by ADEKA, trade name "N-1919") (C-3): 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (Chiba Special chemical company, trade name "Irgacure379") (C-4): 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (C-5): 4,4'-bis(diethylamino)diphenyl ketone (C-6): 2-Hydroxythiobenzothiazole (C-7): 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (manufactured by Chiba Specialty Chemicals Co., Ltd., trade name "Irgacure 369") (C-8): 2-methyl-1-(4-methylthiophene)-2-morpholinopropan-1-one (manufactured by Chiba Specialty Chemicals Co., Ltd., trade name "Irgacure 907") (D-1): Phenolic novolak type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name "epitoke152")

In Table 1, the "-" symbol indicates that the component is not added in this column.

Fig. 1 is a view showing an example of a load-deformation amount curve at the time of load and at the time of load removal in the evaluation of the elastic recovery rate.

Claims (4)

A sensitive radiation linear resin composition comprising: [A] (a1) is at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and (a2) is represented by the following formula (1) (In the formula (1), R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group, R ^{3 represents a} hydrogen atom or a methyl group, and X represents a divalent organic group), and (a3) selected from the group consisting of alkyl acrylates, alkyl methacrylates, acrylate cyclic esters, alicyclic methacrylates, aryl acrylates, aryl acrylates, aryl methacrylates, methyl groups Aralkyl acrylate, dialkyl dicarboxylate, hydroxyalkyl methacrylate, unsaturated 5- or 6-membered ring methacrylate containing 1 atom of oxygen, epoxy acrylate alkyl acrylate, methacrylic acid An epoxyalkyl ester, an α-alkyl acrylate epoxy alkyl ester, a glycidyl ether having an unsaturated bond, a vinyl aromatic compound, a dicarbonyl quinone imine derivative, a conjugated diene, and acrylonitrile, a copolymer of at least one unsaturated compound of a group of methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride and vinyl acetate, [B] a polymerizable unsaturated compound, And [C] a radiation-sensitive linear polymerization initiator which is used for the formation of a liquid crystal display element spacer. A spacer for a liquid crystal display element, which is characterized in that it is formed of a sensitive radiation linear resin composition as in the first aspect of the patent application. A method for forming a spacer for a liquid crystal display element, comprising the steps of: (1) forming a film of a radiation-sensitive linear resin composition according to claim 1 of the patent application scope on at least the following steps; (2) a step of exposing at least a portion of the film, (3) a step of developing the film after exposure, and (4) a step of heating the film after development. A liquid crystal display element comprising a spacer as in the second aspect of the patent application.