JP5476758B2 - Radiation sensitive resin composition, interlayer insulating film of liquid crystal display element, protective film, spacer and method for forming the same - Google Patents

Description

The present invention relates to an interlayer insulating film, a protective film, a radiation-sensitive resin composition for forming a spacer, an interlayer insulating film formed from the composition, a protective film, a spacer, and a method for forming them. More specifically, in the present invention, an interlayer insulating film, a protective film, and a spacer used for a liquid crystal display element (LCD) and a charge coupled device can be formed of one kind of radiation-sensitive resin composition. The present invention relates to an interlayer insulating film, a protective film, a spacer, and a method for forming them.

  In an electronic component such as a thin film transistor (hereinafter referred to as “TFT”) type liquid crystal display element, magnetic head element, integrated circuit element, solid-state imaging element, etc., an interlayer insulation is generally used to insulate between wirings arranged in layers. A membrane is provided. Among the electronic components, for example, a TFT-type liquid crystal display element is manufactured through a step of forming a transparent electrode film on the interlayer insulating film and further forming a liquid crystal alignment film thereon. For this reason, the interlayer insulating film is exposed to high temperature conditions in the transparent electrode film forming process or exposed to a resist stripping solution used for electrode pattern formation. .

  Conventionally, a positive-type radiation-sensitive resin composition using a radiation-sensitive acid generator such as naphthoquinonediazide is used as an interlayer insulating film for liquid crystal display elements from the viewpoint of patterning performance (see Patent Document 1). . In recent years, attention has been paid to performances such as high sensitivity of the negative radiation sensitive resin composition and high transparency of the resulting cured film, and application of the negative radiation sensitive resin composition is proceeding (see Patent Document 2). .

On the other hand, among members used for liquid crystal display elements, many spacers, protective films, and the like are formed using a negative radiation-sensitive resin composition (for example, refer to Patent Document 3 for a protective film). In recent years, the spread and enlargement of liquid crystal panels has been rapidly progressing, and from the viewpoints of cost reduction and process time reduction, it is desired to shorten the irradiation time, increase the resolution, and shorten the development time in the photolithography process. ing.
However, when a spacer or a protective film is formed by a radiation exposure process with a low exposure amount, the irradiation time of which has been shortened using a conventionally known radiation-sensitive resin composition, high resolution cannot be achieved. There is a problem that the dimensional stability and strength of the obtained spacer pattern are insufficient, resulting in a panel failure.

Liquid crystal display elements are widely applied to liquid crystal televisions, mobile phones, and the like, and higher quality is demanded than conventional liquid crystal display elements. In recent years, liquid crystal display devices have a trend toward larger screens, higher brightness, higher definition, faster response, thinner thickness, and the like. In order to meet these requirements, interlayer insulating films and protective films are required to shorten the irradiation time of radiation (hereinafter, increase sensitivity), lower dielectric constant, higher flatness, adhesion, and higher transmittance. The spacer is required to have high resolution and high sensitivity (see Patent Document 4).

The radiation-sensitive resin composition used inside the element of the liquid crystal display element is a colored radiation-sensitive resin composition used for forming a color filter, an interlayer insulating film material for forming an interlayer insulating film, and a protective film material for forming a protective film In addition, a spacer material for forming a spacer material, and the like, a radiation sensitive resin composition satisfying each required performance has been used specifically for each application site.

For example, in a colored radiation-sensitive resin composition, an invention that attempts to solve the problems using a compound having a hindered phenol structure, for the problems of improving alkali developability and improving the dimensional stability of a pattern to be formed. It is disclosed (see Patent Document 5). Similarly, an invention that achieves high sensitivity and high resolution by applying a compound having a hindered phenol structure to a radiation-sensitive resin composition for forming a spacer is disclosed (see Patent Document 4).

As described above, a variety of radiation-sensitive resin compositions are used in the manufacture of liquid crystal display elements in order to overcome the objects and problems. Recently, from the viewpoint of cost reduction, attempts have been made to reduce the types of radiation-sensitive resin compositions. However, the colored radiation-sensitive resin composition for forming a color filter, the interlayer insulating film material, and the protective film material are required to have contradictory performance requirements, i.e., color clarity and transparency, respectively. Is possible. On the other hand, since the interlayer insulating film material for forming the interlayer insulating film, the protective film material for forming the protective film, and the spacer material for forming the spacer material do not need color sharpness, the common use of the material is in principle Is possible.

Therefore, high sensitivity, high flatness, high adhesion of interlayer insulating films and protective films, high transmittance and high resolution of spacers, high sensitivity and high sensitivity required performance can be achieved with one kind of radiation sensitive resin composition. Development of a resin composition is strongly desired.

JP 2001-354822 A JP 2000-162769 A JP-A-6-43643 JP 2009-36858 A JP 2002-22925 A

  The present invention has been made based on the circumstances as described above, and its purpose is to form an interlayer insulating film, a protective film and a spacer with one kind of radiation-sensitive resin composition. An object of the present invention is to provide a radiation-sensitive resin composition that can achieve high sensitivity, high flatness, high adhesion, and high transmittance in interlayer insulating films and protective films, and high resolution and high sensitivity in spacers.

The invention made to solve the above problems is
(A) (a1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, (a2) radical polymerizable compound having an epoxy group and (a3) (meth) acrylic acid alkyl ester, (meth) acrylic acid alicyclic ring Formula ester, unsaturated hetero 5- and 6-membered ring (meth) acrylic acid ester containing oxygen atom, (meth) acrylic acid aryl ester, maleimide compound, hydroxyalkyl ester of (meth) acrylic acid, styrene, α-methylstyrene, A resin that is soluble in an alkaline aqueous solution that is a copolymer of at least one other radically polymerizable compound selected from the group consisting of 1,3-butadiene, and is a co-polymer of component (a1) in the copolymer. The polymerization rate is 5 to 40% by mass, the copolymerization rate of the component (a2) is 10 to 70% by mass, and the copolymerization rate of the component (a3) is 10 to 70%. Copolymer having an amount of%, (B) a polymerizable compound having an ethylenically unsaturated bond, and (C) a radiation-sensitive polymerization initiator, and (D) a compound having a hindered phenol structure, having a hindered amine structure A radiation-sensitive resin composition comprising at least one selected from the group consisting of a compound, a compound having an alkyl phosphate structure, and a compound having a thioether structure.

In the radiation sensitive resin composition, one of the radiation sensitive polymerization initiators (C) can form an interlayer insulating film and a protective film with high sensitivity by using an O-acyloxime compound. , Making it possible to form spacers with high resolution.

An interlayer insulating film, a protective film, and a spacer of a liquid crystal display element are formed by a step of forming a coating film using the radiation-sensitive resin composition, a step of irradiating radiation, a step of developing, and a step of heat-treating the coating film. be able to. By such a method, the interlayer insulating film, the protective film, and the spacer can be easily formed on the substrate in the liquid crystal display element. In addition, an interlayer insulating film and a protective film can be formed with high sensitivity, and the obtained interlayer insulating film and protective film have high flatness, high adhesion, and high transmittance. Further, the spacer can be formed with high sensitivity and high resolution.

As described above, the radiation-sensitive resin composition for forming the interlayer insulating film, protective film and spacer of the liquid crystal display element of the present invention is composed of one kind of radiation-sensitive resin composition. The interlayer insulating film and the protective film can be formed with high sensitivity, and the obtained interlayer insulating film and protective film have high flatness, high adhesion, and high transmittance. Further, the spacer can be formed with high sensitivity and high resolution.

<Radiation sensitive resin composition>
Hereinafter, each component of the radiation sensitive resin composition of this invention is explained in full detail.

(A) Copolymer The copolymer in the present invention is preferably an alkali-soluble resin having solubility in an alkali developer used in the development processing step of the radiation-sensitive resin composition containing the component. ) Unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride (hereinafter also referred to as compound (a1)) and (a2) a radical polymerizable compound having an epoxy group (hereinafter also referred to as compound (a2)) and (a3) (Meth) acrylic acid alkyl ester, (meth) acrylic acid alicyclic ester, unsaturated hetero 5- and 6-membered ring (meth) acrylic acid ester containing oxygen atom, (meth) acrylic acid aryl ester, maleimide compound, (meta ) Selected from the group consisting of hydroxyalkyl esters of acrylic acid, styrene, α-methylstyrene, 1,3-butadiene At least one other radically polymerizable compound that (hereinafter, compound (a3) also referred) is a copolymer of (hereinafter also referred to as copolymer (A)).

Examples of the compound (a1) include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl hexa Examples thereof include monocarboxylic acids such as hydrophthalic acid; dicarboxylic acids such as maleic acid, fumaric acid and citraconic acid; and acid anhydrides of the dicarboxylic acids.

  Among these compounds (a1), acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, and 2-methacryloyl from the viewpoint of copolymerization reactivity and solubility of the resulting polymer and copolymer in an alkaline developer. Oxyethyl succinic acid, maleic anhydride and the like are preferable.

  In the copolymer (A), the compound (a1) can be used alone or in admixture of two or more. In the copolymer (A), the content of the repeating unit derived from the compound (a1) is preferably 5 to 40% by mass, more preferably 7 to 30% by mass, and particularly preferably 8 to 25% by mass. When the content of the repeating unit derived from the compound (a1) is 5 to 40% by mass, the radiation-sensitive resin composition is optimized at a higher level of various characteristics such as radiation sensitivity, developability and storage stability. A thing is obtained.

  As the compound (a2), a radical polymerizable compound having an epoxy group can be used. Specific examples of the radical polymerizable compound having an epoxy group include, for example, glycidyl acrylate, 2-methylglycidyl acrylate, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, and 3,4 acrylate. -Epoxy cyclohexyl, acrylic acid epoxy alkyl esters such as acrylic acid-3,4-epoxycyclohexyl methyl; glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate , Methacrylic acid epoxy alkyl esters such as 3,4-epoxycyclohexyl methacrylate, methacrylic acid-3,4-epoxycyclohexylmethyl; glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α-n- Α-alkylacrylic acid epoxy alkyl esters such as glycidyl acetyl acrylate and α-ethyl acrylate 6,7-epoxyheptyl; glycidyl such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether Mention may be made of ethers.

  Specific examples of the oxetanyl group-containing polymerizable unsaturated compound include, for example, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2- Methyl oxetane, 3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (methacryloyloxyethyl) oxetane, 3- (acryloyloxymethyl) oxetane, 3- ( (Acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3 − ( Acryloyloxyethyl) oxetane, 2- (methacryloyloxymethyl) oxetane, 2-methyl-2- (methacryloyloxymethyl) oxetane, 3-methyl-2- (methacryloyloxymethyl) oxetane, 4-methyl-2- (methacryloyl) Oxymethyl) oxetane, 2- (2- (2-methyloxetanyl)) ethyl methacrylate, 2- (2- (3-methyloxetanyl)) ethyl methacrylate, 2- (methacryloyloxyethyl) -2-methyloxetane, 2- (Methacryloyloxyethyl) -4-methyloxetane, 2- (acryloyloxymethyl) oxetane, 2-methyl-2- (acryloyloxymethyl) oxetane, 3-methyl-2- (acryloyloxymethyl) oxetane, 4-methyl- 2- Acryloyloxymethyl) oxetane, 2- (2- (2-methyloxetanyl)) ethyl methacrylate, 2- (2- (3-methyloxetanyl)) ethyl methacrylate, 2- (acryloyloxyethyl) -2-methyloxetane, 2 And (meth) acrylic acid esters such as-(acryloyloxyethyl) -4-methyloxetane.

Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 3- (acryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl)- 3-ethyloxetane, 2- (methacryloyloxymethyl) oxetane, etc. have high adhesion to the substrate of the obtained interlayer insulating film, protective film and spacer, have high heat resistance, and further improve the reliability in liquid crystal display elements It is preferably used from the viewpoint.
The said unsaturated compound (a2) can be used individually or in mixture of 2 or more types.

  In the copolymer (A), the copolymerization ratio of the compound (a2) is preferably 10 to 70% by mass, more preferably 15 to 65% by mass with respect to the total unsaturated compounds. When the copolymerization ratio of the compound (a2) is 10 to 70% by mass, it is particularly easy to control the molecular weight of the copolymer, and a radiation-sensitive resin composition optimized at a higher level of developability, sensitivity, etc. can get.

  As the compound (a3), (meth) acrylic acid alkyl ester, (meth) acrylic acid alicyclic ester, unsaturated hetero penta- and six-membered ring (meth) acrylic acid ester containing oxygen atom, (meth) acrylic acid aryl Examples include esters, maleimide compounds, hydroxyalkyl esters of (meth) acrylic acid, styrene, α-methylstyrene, and 1,3-butadiene.

  Specific examples of the (meth) acrylic acid alkyl ester include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, Mention may be made of t-butyl acrylate.

Specific examples of (meth) acrylic acid alicyclic alkyl ester include cyclopentyl methacrylate, cyclohexyl methacrylate, (methacrylic acid-2-methylcyclohexyl, (tricyclo [5.2.1.0 ^2,6 ] decane methacrylate). -8-yl (hereinafter, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl may be referred to as “dicyclopentanyl”), methacrylic acid-2-dicyclopentanyloxy Ethyl, isobornyl methacrylate, cyclopentyl acrylate, cyclohexyl acrylate, acrylate-2-methylcyclohexyl, acrylate tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, acrylate-2-dicycloacrylate Examples include pentanyloxyethyl and isobornyl acrylate.

Specific examples of unsaturated hetero-5- and 6-membered cyclic methacrylates containing an oxygen atom include unsaturated compounds containing a tetrahydrofuran skeleton, such as tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl. Esters, such as 3- (meth) acryloyloxytetrahydrofuran-2-one;
Examples of unsaturated compounds containing a furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-ene-2. -One, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2-yl --Hexyl-1-en-3-one, acrylic acid-2-furan-2-yl-1-methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-heptene -3-one etc .;
Examples of unsaturated compounds containing a tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-en-3-one, 2-methacrylic acid tetrahydropyran-2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, etc .;
Examples of unsaturated compounds containing a pyran skeleton include 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyran, 4- (1,5-dioxa-6-oxo- 7-octenyl) -6-methyl-2-pyran and the like.

Examples of (meth) acrylic acid ester having a hydroxyl group include (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-3-hydroxypropyl, and (meth) acrylic acid. -2,3-dihydroxypropyl and the like. Specific examples of the (meth) acrylic acid aryl ester include phenyl (meth) acrylate, benzyl (meth) acrylate, and the like. Specific examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate and the like. Specific examples of the (meth) acrylic acid aryl ester include benzyl methacrylate and benzyl acrylate.

  Examples of maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidobenzoate, N -Succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.

  In the copolymer (A), the copolymerization ratio of the compound (a3) is preferably 10 to 70% by mass, more preferably 15 to 65% by mass with respect to the total unsaturated compounds. When the copolymerization ratio of the compound (a2) is from 10 to 70% by mass, the molecular weight of the copolymer is particularly easily controlled, and the radiation sensitive resin is optimized at a higher level of developability, sensitivity, adhesion and the like. A composition is obtained.

Next, the polymerization method for producing the copolymer (A) will be described.
The polymerization may be performed, for example, by polymerizing the compound (a1), the compound (a2), and the compound (a3) constituting the copolymer (A) in a solvent using a radical polymerization initiator. And thereby the copolymer (A) can be obtained.

The radical polymerization initiator is appropriately selected according to the type of the polymerizable unsaturated compound used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2 , 4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4′-azobis (4-cyanovaleric acid), dimethyl-2,2′-azobis Azo compounds such as (2-methylpropionate) and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile);
Of these radical polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) and the like are preferable.
The radical polymerization initiators can be used alone or in admixture of two or more.

  In the said polymerization, the usage-amount of a radical polymerization initiator is 0.1-50 mass% normally with respect to 100 mass% of polymerizable unsaturated compounds, Preferably it is 0.1-20 mass%.

  Moreover, the usage-amount of molecular weight control agent (1) is 0.1-50 mass% normally with respect to the total of 100 mass% of a compound (a1), a compound (a2), and a compound (a3), Preferably it is 0.2. -16% by mass, particularly preferably 0.4-8% by mass.

  In the polymerization reaction for producing the copolymer (A), a molecular weight modifier can be used to adjust the molecular weight. Specific examples of molecular weight modifiers include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and thioglycolic acid. Xanthogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide; terpinolene, α-methylstyrene dimer and the like. The polymerization temperature is usually 0 to 150 ° C., preferably 50 to 120 ° C., and the polymerization time is usually 10 minutes to 20 hours, preferably 30 minutes to 6 hours.

The copolymer (A) has a polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”), preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably 5 × 10 ^{3 to} 5 × 10 ⁴ . When the Mw of the copolymer (A) is 2 × 10 ³ or more, a sufficient development margin of the radiation-sensitive resin composition is obtained, and the remaining film ratio of the formed coating film (the patterned thin film remains properly) Ratio) can be prevented, and the pattern shape and heat resistance of the obtained insulating film can be kept good. On the other hand, when the Mw of the copolymer (A) is 1 × 10 ⁵ or less, high radiation sensitivity can be maintained and a good pattern shape can be obtained. The molecular weight distribution (hereinafter referred to as “Mw / Mn”) of the copolymer (A) is preferably 5.0 or less, more preferably 3.0 or less. By making Mw / Mn of the copolymer [A] 5.0 or less, the pattern shape of the obtained insulating film can be kept good. In addition, since the radiation-sensitive resin composition containing the copolymer (A) having a preferable range of Mw and Mw / Mn as described above has high developability, no development residue is generated in the development process. A predetermined pattern shape can be easily formed.

  Examples of the solvent used in the polymerization reaction for producing the copolymer (A) include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, and propylene glycol monoalkyls. Examples include ether acetate, propylene glycol monoalkyl ether propionate, aromatic hydrocarbons, ketones, and other esters.

(B) a polymerizable compound having an ethylenically unsaturated bond,
As the polymerizable compound (B) having an ethylenically unsaturated bond contained in the radiation-sensitive resin composition of the present invention, a compound having 4 or more polymerizable unsaturated bonds in one molecule (hereinafter referred to as “polymerizable”). It is preferably an unsaturated compound (B1) ") or a compound having 1 to 3 polymerizable unsaturated bonds in one molecule (hereinafter referred to as" polymerizable unsaturated compound (B2) ").
Examples of the polymerizable unsaturated compound (B1) include pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tri (2- (meth) acryloyloxyethyl). ) In addition to phosphate, etc., a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups, one or more hydroxyl groups in the molecule and 3 to 5 (meta ) Urethane (meth) acrylate compounds obtained by reacting with a compound having an acryloyloxy group.

  Examples of commercially available polymerizable unsaturated bonds (B1) include Aronix M-400, M-402, M-405, M-450, M-1310, M-1600, M-1960, M-7100, M-8030, M-8060, M-8100, M-8100, M-8530, M-8560, M-9050, Aronix TO-1450, TO-1382 (above, Toagosei ( KAYARAD DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DPCA-120, MAX-3510 (manufactured by Nippon Kayaku Co., Ltd.), Biscote 295, 300, 360, GPT, 3PA, 400 (Osaka Organic Chemical Co., Ltd.) and urethane acrylate compounds such as New Frontier R-1150 (No. Ichi Kogyo Seiyaku Co., Ltd.), KAYARAD DPHA-40H, UX-5000 (Nippon Kayaku Co., Ltd.), UN-9000H (Negami Kogyo Co., Ltd.), and the like.

  Examples of the polymerizable unsaturated bond (B2) include ω-carboxypolycaprolactone mono (meth) acrylate, ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol. Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenoxyethanol full orange (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, 2- (2′-vinyloxyethoxy) ethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, , And the like pentaerythritol tri (meth) acrylate.

  Examples of commercially available polymerizable unsaturated bonds (B2) include, for example, Aronix M-5300, M-5600, M-5700, M-210, M-220, M-240, M-270, M-6200, M-305, M-309, M-309, M-310, M-315 (above, manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, KAYARAD HX-220, HX-620, R -526, R-167, R-604, R-684, R-551, R-712, UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX- 6101, UX-7101, UX-8101, UX-0937, MU-2100, MU-4001 (manufactured by Nippon Kayaku Co., Ltd.), Art Resin UN-9000PEP, UN-9200 A, UN-7600, UN-333, UN-1003, UN-1255, UN-6060PTM, UN-6060P (manufactured by Negami Industrial Co., Ltd.), SH-500B Biscuit 260, 312 and 335HP (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.).

In this invention, (B) polymeric unsaturated compound can be used individually or in mixture of 2 or more types.
The use ratio of the polymerizable unsaturated compound (B) in the radiation sensitive resin composition of the present invention is preferably 20 to 200 parts by mass, more preferably 40 to 160 parts by mass with respect to 100 parts by mass of the copolymer. It is.
(B) As the polymerizable unsaturated compound, the polymerizable unsaturated bond (B1) can be used alone or in combination with (B2). In this case, the proportion of the polymerizable unsaturated bond (B2) in the total of the polymerizable unsaturated bonds (B1) and (B2) is preferably 0 to 50% by mass, more preferably 0 to 30% by mass. It is.
By containing the polymerizable unsaturated compound (B) in such a ratio, the radiation-sensitive resin composition of the present invention has excellent adhesion and an interlayer insulating film and protective film having sufficient hardness even at a low exposure amount. And spacers can be obtained.

(C) Radiation-sensitive polymerization initiator (C) The radiation-sensitive polymerization initiator contained in the radiation-sensitive resin composition of the present invention is sensitive to radiation and starts polymerization of (B) a polymerizable unsaturated compound. It is a component that produces a possible active species. Examples of such (C) radiation-sensitive polymerization initiators include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and benzophenone compounds.

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], and ethanone-1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like.

  Among these, preferable O-acyloxime compounds include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], and ethanone-1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) or ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime). These O-acyloxime compounds can be used alone or in admixture of two or more.

  Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound.

  Specific examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and the like can be mentioned.

  Specific examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane-1- ON, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone and the like.

  Of these acetophenone compounds, α-aminoketone compounds are preferred, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one or 2-dimethylamino-2- (4-methylbenzyl) -1- (4-Morpholin-4-yl-phenyl) -butan-1-one is particularly preferred.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -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 Examples include '-biimidazole.

  Among these biimidazole compounds, 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 or 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5 '-Tetraphenyl-1,2'-biimidazole is preferred, especially 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole Is preferred.

  In the radiation-sensitive resin composition of the present invention, when a biimidazole compound is used as the (C) radiation-sensitive polymerization initiator, an aliphatic or aromatic compound having a dialkylamino group (hereinafter, referred to as sensitization) "Amino sensitizer") can be added.

  Examples of such amino sensitizers include 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone. Of these amino sensitizers, 4,4'-bis (diethylamino) benzophenone is particularly preferable. The amino sensitizers can be used alone or in admixture of two or more.

  Furthermore, when a biimidazole compound and an amino sensitizer are used in combination in the radiation-sensitive resin composition of the present invention, a thiol compound can be added as a hydrogen radical donor. The biimidazole compound is sensitized and cleaved by an amino sensitizer to generate an imidazole radical, but as it is, high polymerization initiating ability is not expressed, and the resulting spacer has a larger pattern upper part and a smaller pattern lower part. Such an unfavorable shape may be obtained. However, by adding a thiol compound to a system in which a biimidazole compound and an amino sensitizer coexist, a hydrogen radical is donated from the thiol compound to the imidazole radical. As a result, the imidazole radical is converted to neutral imidazole, and a component having a sulfur radical having a high polymerization initiating ability is generated, thereby making the shapes of the interlayer insulating film, the protective film and the spacer more preferable. it can.

  Examples of the thiol compound include aromatic thiol compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole; 3-mercaptopropionic acid, 3-mercapto Examples thereof include aliphatic monothiol compounds such as methyl propionate; bifunctional or higher aliphatic thiol compounds such as pentaerythritol tetra (mercaptoacetate) and pentaerythritol tetra (3-mercaptopropionate). Of these thiol compounds, 2-mercaptobenzothiazole is particularly preferable.

  When a biimidazole compound and an amino sensitizer are used in combination, the addition amount of the amino sensitizer is preferably 0.1 to 50 parts by mass, more preferably 100 parts by mass of the biimidazole compound. 1 to 20 parts by mass. When the added amount of the amino sensitizer is 0.1 to 50 parts by mass, the shape of the obtained spacer becomes good.

  Moreover, when using together a biimidazole compound and an amino-type sensitizer, and a thiol compound, as an addition amount of a thiol compound, Preferably it is 0.1-50 mass parts with respect to 100 mass parts of biimidazole compounds, More preferably, it is 1-20 mass parts. When the addition amount of the thiol compound is 0.1 to 50 parts by mass, the shapes and adhesion of the interlayer insulating film, the protective film and the spacer are the best.

  The radiation-sensitive polymerization initiator (C) contained in the radiation-sensitive resin composition of the present invention preferably contains at least one selected from the group consisting of O-acyloxime compounds and acetophenone compounds. -It is more preferable to contain at least one selected from the group consisting of acyloxime compounds and acetophenone compounds and biimidazole compounds.

  (C) As a ratio of the O-acyloxime compound and the acetophenone compound in the radiation-sensitive polymerization initiator, the total amount is preferably 40% by mass or more based on the total amount of (C) the radiation-sensitive polymerization initiator, More preferably, it is 45 mass% or more, Most preferably, it is 50 mass% or more. By using the radiation-sensitive polymerization initiator (C) at such a ratio, the radiation-sensitive resin composition of the present invention has an interlayer insulating film and protective film having high hardness and adhesion even in the case of a low exposure amount. And spacers can be formed.

(D) A compound having a hindered phenol structure, a compound having a hindered amine structure, a compound having an alkyl phosphate structure, a compound having a thioether structure The component (D) used in the present invention comprises a compound having a hindered phenol structure and a hindered amine structure. A compound having an alkyl phosphate structure, a compound having a thioether structure (hereinafter also referred to as (D) compound).
The compound (D) is effective in improving flatness and adhesion in the interlayer insulating film and protective film, and is effective in increasing the resolution in forming the spacer.
Specific examples of the hindered phenol antioxidant include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene bis [3- (3,5-di- -Tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide) ), 4,6-bis (dodecylthiomethyl)-o-cresol, ethylenebis (oxyethylene) bis [3- 5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris ( 3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris [(4- tert-butyl-3-hydroxy-2,6-xylin) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl- 4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamine) phenol and the like can be mentioned. Examples of commercially available products include Adeka Stub AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80 and ADK STAB AO manufactured by ADEKA Corporation. -330, Sumitizer Chemical Co., Ltd., Sumilizer GM, Sumilizer GS, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer WX-R, Sumilizer GA-80, IR26 NOX10, IRGANOX1035, IRGANOX1035 , IRGANOX1520L, RGANOX245, IRGANOX259, IRGANOX3114, IRGANOX565, IRGAMOD295, (Ltd.) API Corporation made Yoshinox BHT, Yoshinox BB, Yoshinox 2246G, Yoshinox 425, Yoshinox 250, Yoshinox 930, Yoshinox SS, Yoshinox TT, Yoshinox 917, include the Yoshinox 314.
These hindered phenols can be used alone or in combination with other hindered phenols, hindered amines, alkyl phosphates, thioethers, and the like.
Examples of commercially available hindered amines include ADK STAB LA-52, ADK STAB LA57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63P, ADK STAB LA-68LD, ADK STAB LA-77 and ADK STAB LA, manufactured by ADEKA Corporation. -82, Adekastab LA-87, Sumitizer 9A manufactured by Sumitomo Chemical Co., Ltd., CHIMASSORB119FL, CHIMASSORB2020FDL, CHIMASORB944FDL, TINUVIN622LD, TINUVIN144, TINUVIN765, and TINUVIN770DF manufactured by Ciba Japan Co., Ltd.

Examples of commercially available alkyl phosphates include ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, and ADK STAB manufactured by ADEKA Corporation. 260, ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 135A, ADK STAB 3010, ADK STAB TPP, and IRGAFOS 168 manufactured by Ciba Japan.
Examples of commercially available thioethers include: ADEKA Adeka Stub AO-412S, Adeka Stub AO-503, Sumitomo Chemical Co., Ltd., sumilizer TPL-R, sumizizer TPM, sumizizer TPS, sumizizer TP-D, sumibazer MB, Ciba Japan IRGANOXPS800FD, IRGANOXPS802FD, DLTP, DSTP, DMTP, and DTTP manufactured by API Corporation.
In the radiation-sensitive resin composition of the present invention, the proportion of the compound (D) used is preferably 0.1 to 10 parts by mass, more preferably 0 with respect to 100 parts by mass of the (A) copolymer. 2 to 5 parts by mass.

    Although the radiation sensitive resin composition of this invention contains said (A) copolymer, (B) polymerizable unsaturated compound, (C) radiation sensitive polymerization initiator, and (D) compound as an essential component. As other optional components, (E) a compound having two or more oxiranyl groups in one molecule, (F) an adhesion assistant, (G) a surfactant, (H) a storage stabilizer, (I) ) It can contain a heat resistance improver and the like.

(E) A compound having two or more oxiranyl groups in one molecule (hereinafter, also referred to as “component (E)”) is added to further improve the hardness of the resulting spacer or protective film. Can do. Examples of such component (E) include compounds having two or more 3,4-epoxycyclohexyl groups in one molecule and other components (E).
Examples of the compound having two or more 3,4-epoxycyclohexyl groups in one molecule include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4- Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3 , 4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4) of ethylene glycol -Epoxycyclohexylmethyl) ether Ethylenebis (3,4-epoxycyclohexane carboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3 ', 4'-like epoxycyclohexane carboxylate and the like.

Examples of the other component (E) include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD di Diglycidyl ethers of bisphenol compounds such as glycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether;
Poly of polyhydric alcohol such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether Glycidyl ether;
Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; phenol novolac type epoxy resins; cresol novolac type epoxy resins A polyphenol type epoxy resin; a diglycidyl ester of an aliphatic long-chain dibasic acid; a glycidyl ester of a higher fatty acid; an epoxidized soybean oil, an epoxidized linseed oil, and the like.

As these commercially available products, for example, as bisphenol A type epoxy resin, Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (above, manufactured by Japan Epoxy Resins Co., Ltd.), etc. Bisphenol F type epoxy resin, Epicoat 807 (manufactured by Japan Epoxy Resin Co., Ltd.), etc .; phenol novolak type epoxy resins, Epicoat 152, 154, 157 S65 (above, Japan Epoxy Resin Co., Ltd.), EPPN201, 202 (above, manufactured by Nippon Kayaku Co., Ltd.), etc .; As a cresol novolac type epoxy resin, EOCN102, 103S, 104S, 1020, 1025, 1027 (above, manufactured by Nippon Kayaku Co., Ltd.), Epicort 180S75 ( Japan Epoch Resin Co., Ltd.), etc .; Polyphenol type epoxy resin, Epicoat 1032H60, XY-4000 (above, Japan Epoxy Resin Co., Ltd.), etc .; Cyclic aliphatic epoxy resins, CY-175, 177, 179 Araldite CY-182, 192, 184 (above, manufactured by Ciba Specialty Chemicals), ERL-4234, 4299, 4221, 4206 (above, manufactured by UC Corporation), Shodyne 509 (Showa Denko ( Co., Ltd.), Epicron 200, 400 (above, Dainippon Ink Co., Ltd.), Epicoat 871, 872 (Japan Epoxy Resin Co., Ltd.), ED-5661, 5562 (above, Celanese) Coating));
Examples of the aliphatic polyglycidyl ether include Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.) and Epiol TMP (manufactured by Nippon Oil & Fats Co., Ltd.).
Of such epoxy compounds (E), phenol novolac type epoxy resins and polyphenol type epoxy resins are preferred.

  The use ratio of the component (E) is preferably 50 parts by mass or less, more preferably 2 to 50 parts by mass, and further 5 to 30 parts by mass with respect to 100 parts by mass of the copolymer (A). Preferably there is. By using the component (E) at such a ratio, it is possible to further improve the hardness of the interlayer insulating film, spacer, or protective film obtained without impairing the developability.

The (F) adhesion aid can be used to further improve the adhesion between the obtained interlayer insulating film, spacer or protective film and the substrate.
As such (F) adhesion aid, a functional silane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, or an oxiranyl group is preferable. Benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane and the like.
These (F) adhesion assistants can be used alone or in admixture of two or more.
(F) The use amount of the adhesion assistant is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, with respect to 100 parts by mass of the (A) copolymer. (F) When the usage-amount of an adhesion aid exceeds 20 mass parts, there exists a tendency for it to become easy to produce the image development residue.

Said (G) surfactant can be used in order to improve the film formation property of a radiation sensitive resin composition more.
Examples of such (G) surfactants include fluorine-based surfactants, silicone-based surfactants, and other surfactants.
The fluorine-based surfactant is preferably a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of the terminal, main chain and side chain, and examples thereof include 1,1,2,2 -Tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycol di (1, 1,2,2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1,2, 2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluoro-n- Til) ether, sodium perfluoro-n-dodecanesulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10 -Decafluoro-n-dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarboxylate, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkylammonium iodide, fluoroalkylbetaine, other Fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, carboxylic acid fluoroalkyl ester and the like can be mentioned.
Examples of commercially available fluorosurfactants include BM-1000, BM-1100 (above, manufactured by BM CHEMIE), MegaFuck F142D, F172, F173, F183, F178, F191, F191, F471, F476 (above, Dainippon Ink & Chemicals, Inc.), Florard FC-170C, -171, -430, -431 (above, manufactured by Sumitomo 3M), Surflon S-112,- 113, -131, -141, -145, -382, Surflon SC-101, -102, -103, -104, -105, -106 (above, manufactured by Asahi Glass Co., Ltd.) ), F-top EF301, 303, 352 (above, Shin-Akita Kasei Co., Ltd.), FT-100, -110, -140A, -15 0, the same -250, the same -251, the same -300, the same -310, the same -400S, the tangent FTX-218, the same -251 (above, manufactured by Neos Co., Ltd.) and the like.

Examples of the silicone surfactant include Toray Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, SF- 8428, DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 ( As mentioned above, what is marketed by brand names, such as GE Toshiba Silicone Co., Ltd. and organosiloxane polymer KP341 (made by Shin-Etsu Chemical Co., Ltd.), can be mentioned.
Examples of the other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene-n-octylphenyl ether, polyoxyethylene-n -Polyoxyethylene aryl ethers such as nonylphenyl ether; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, (meth) acrylic acid copolymer polyflow No. 57, no. 95 (above, manufactured by Kyoeisha Chemical Co., Ltd.).
These (G) surfactants can be used alone or in admixture of two or more. (G) The usage-amount of surfactant becomes like this. Preferably it is 1.0 mass part or less with respect to 100 mass parts of (A) copolymers, More preferably, it is 0.5 mass part or less. In this case, when the amount of the (G) surfactant used exceeds 1.0 part by mass, film unevenness may easily occur.

Examples of the storage stabilizer (H) include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitronitroso compounds, and more specifically, 4-methoxyphenol, N-nitroso-N. -Phenylhydroxylamine aluminum etc. can be mentioned.
These (H) storage stabilizers can be used alone or in admixture of two or more.
(H) The usage-amount of a storage stabilizer becomes like this. Preferably it is 3.0 mass parts or less with respect to 100 mass parts of (A) copolymers, More preferably, it is 0.5 mass parts or less. (H) When the compounding quantity of a storage stabilizer exceeds 3.0 mass parts, a sensitivity may fall and a pattern shape may deteriorate.

Examples of the (I) heat resistance improver include N- (alkoxymethyl) glycoluril compounds and N- (alkoxymethyl) melamine compounds.
Examples of the N- (alkoxymethyl) glycoluril compound include N, N, N ′, N′-tetra (methoxymethyl) glycoluril, N, N, N ′, N′-tetra (ethoxymethyl) glycoluril, N, N, N ′, N′-tetra (n-propoxymethyl) glycoluril, N, N, N ′, N′-tetra (i-propoxymethyl) glycoluril, N, N, N ′, N′— Examples thereof include tetra (n-butoxymethyl) glycoluril, N, N, N ′, N′-tetra (t-butoxymethyl) glycoluril and the like. Of these N- (alkoxymethyl) glycoluril compounds, N, N, N ′, N′-tetra (methoxymethyl) glycoluril is preferred.
Examples of the 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-propoxymethyl) melamine, N, N, N ', N', N", N "- Hexa (i-propoxymethyl) melamine, N, N, N ′, N ′, N ″, N ″ -hexa (n-butoxymethyl) melamine, N, N, N ′, N ′, N ″, N ″ — Examples include hexa (t-butoxymethyl) melamine. Of these N- (alkoxymethyl) melamine compounds, N, N, N ′, N ′, N ″, N ″ -hexa (methoxymethyl) melamine is preferred, and examples of commercially available products thereof include Nicalac N-2702, MW-30M (manufactured by Sanwa Chemical Co., Ltd.).

(I) The usage-amount of a heat resistance improver becomes like this. Preferably it is 50 mass parts or less with respect to 100 mass parts of (A) copolymers, More preferably, it is 30 mass parts or less. (I) When the compounding quantity of a heat resistance improver exceeds 50 mass parts, a sensitivity may fall and a pattern shape may deteriorate.

<Preparation of radiation-sensitive resin composition>
The radiation-sensitive resin composition of the present invention comprises (A) a copolymer, (B) a polymerizable unsaturated compound, (C) a radiation-sensitive polymerization initiator, and (D) a compound as described above. It is prepared by mixing the other components added to the. This radiation-sensitive resin composition is preferably used in a solution state after being dissolved in an appropriate solvent. For example, (A) a copolymer, (B) a polymerizable unsaturated compound, and (C) a radiation sensitive polymerization initiator, (D) a compound and optionally added (E) two or more in one molecule By mixing a compound having an oxiranyl group, (F) an adhesion assistant, (G) a surfactant, (H) a storage stabilizer, and (I) a heat resistance improver in a solvent at a predetermined ratio, a solution state The radiation sensitive resin composition can be prepared.

  As the solvent used for the preparation of the radiation sensitive resin composition of the present invention, (A) a copolymer, (B) a polymerizable unsaturated compound, and (C) a radiation sensitive polymerization initiator and (D) a compound, A component that dissolves each component of other components optionally added and does not react with each component is used. As such a solvent, the thing similar to what was illustrated as a solvent which can be used in order to manufacture the above-mentioned (A) copolymer can be mentioned.

  Among these solvents, for example, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene from the viewpoint of solubility of each component, reactivity with each component, ease of film formation, and the like. Glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, cyclohexanol acetate, benzyl alcohol, and 3-methoxybutanol can be particularly preferably used. These solvents can be used alone or in combination of two or more.

  Furthermore, in order to improve the in-plane uniformity of the film thickness together with the above solvent, a high boiling point solvent can be used in combination. Examples of the high-boiling solvent that can be used in combination include N-methylpyrrolidone, N, N-dimethylacetamide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, and diethyl oxalate. , Diethyl maleate, γ-butyrolactone, propylene carbonate and the like. Of these, N-methylpyrrolidone, γ-butyrolactone or N, N-dimethylacetamide is preferred.

  When a high boiling point solvent is used in combination as the solvent of the radiation sensitive resin composition of the present invention, the amount used is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably based on the total amount of solvent. It can be 30 mass% or less. When the amount of the high-boiling solvent used is 50% by mass or less, the film thickness uniformity, sensitivity, and remaining film ratio are good.

  When preparing the radiation-sensitive resin composition of the present invention in a solution state, the solid content concentration (components other than the solvent in the composition solution, that is, the components (A), (B) and (C), and The ratio of the total amount of other components optionally added) can be set to an arbitrary concentration (for example, 5 to 50% by mass) depending on the purpose of use, a desired film thickness value, and the like. A more preferable solid content concentration varies depending on a method of forming a film on the substrate, which will be described later. The composition solution thus prepared can be used after being filtered using a Millipore filter having a pore size of about 0.5 μm.

<Method for forming interlayer insulating film, protective film or spacer>
Next, a method for forming an inter-insulating film, a protective film or a spacer using the radiation sensitive resin composition of the present invention will be described.

The method for forming an insulating film, protective film or spacer during the present invention is characterized by including at least the following steps (1) to (4) in the order described below.
(1) The process of forming the film of the radiation sensitive resin composition of this invention on a board | substrate.
(2) A step of irradiating at least a part of the coating with radiation.
(3) A step of developing the film after irradiation.
(4) A step of heating the film after development.

  Hereinafter, each of these steps will be described sequentially.

(1) The process of forming the film of the radiation sensitive resin composition of this invention on a board | substrate A transparent conductive film is formed in the single side | surface of a transparent substrate, and the film of a radiation sensitive resin composition is formed on this transparent conductive film To do. As a transparent substrate used here, a glass substrate, a resin substrate, etc. can be mentioned, for example. More specifically, examples include glass substrates such as soda lime glass and alkali-free glass; resin substrates made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide.

As the transparent conductive film provided on one surface of the transparent substrate, a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) And so on.

  In the case of forming a film by a coating method, the film can be formed by applying a solution of the radiation sensitive resin composition on the transparent conductive film, and then preferably heating (prebaking) the coated surface. The solid content concentration of the composition solution used for the coating method is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 15 to 35% by mass. The coating method of the composition solution is not particularly limited, and examples thereof include spraying, roll coating, spin coating (spin coating), slit coating (slit die coating), bar coating, and ink jet coating. An appropriate method can be adopted. Among these coating methods, the spin coating method or the slit coating method is particularly preferable.

  The prebaking conditions vary depending on the type of each component, the blending ratio, and the like, but are preferably about 70 to 120 ° C. for about 1 to 15 minutes. The film thickness after pre-baking of the film is preferably 0.5 to 10 μm, more preferably about 1.0 to 7.0 μm.

(2) Step of irradiating at least a part of the coating film Next, radiation is applied to at least a part of the formed coating film. At this time, when irradiating only a part of the film, for example, the irradiation can be performed through a photomask having a predetermined pattern.

  Examples of radiation used for irradiation include visible light, ultraviolet light, and far ultraviolet light. Of these, radiation having a wavelength in the range of 250 to 550 nm is preferable, and radiation including ultraviolet light having a wavelength of 365 nm is particularly preferable.

Radiation irradiation amount (exposure amount) is preferably 100 to 5,000 J / m ² as a value obtained by measuring the intensity of irradiated radiation at a wavelength of 365 nm with an illuminometer (OAI model 356, manufactured by Optical Associates Inc.). preferably from 200~3,000J / ^{m 2.}

The radiation-sensitive resin composition of the present invention has extremely high radiation sensitivity as compared with conventionally known compositions, and the radiation dose is 700 J / m ² or less, and even 600 J / m ² or less. It has an advantage that an insulating film, a protective film or a spacer can be obtained while having a desired film thickness, good shape, excellent adhesion and high hardness.

(3) Step of developing the film after radiation irradiation Next, by developing the film after radiation irradiation, unnecessary portions are removed to form a predetermined pattern.

  As a developer used for development, for example, an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, or an aqueous solution of an alkaline compound such as a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide is used. can do. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant can be added to the aqueous solution of the alkaline compound.

  As a developing method, any of a liquid piling method, a dipping method, a shower method and the like may be used, and the developing time is preferably about 10 to 180 seconds at room temperature. Following the development process, for example, after washing with running water for 30 to 90 seconds, a desired pattern can be obtained by air drying with compressed air or compressed nitrogen.

(4) Step of heating the film after development Next, the obtained patterned film is heated at a predetermined temperature, for example, 100 to 250 ° C., for a predetermined time, for example, on the hot plate by an appropriate heating device such as a hot plate or oven. Then, a desired spacer or protective film can be obtained by heating (post-baking) for 5 to 30 minutes and in an oven for 30 to 180 minutes.

  As described above, a spacer or protective film excellent in various properties such as compressive strength, resistance to the rubbing process of the liquid crystal alignment film, and adhesion to the substrate can be obtained with a desired pattern size.

<Liquid crystal display element>
The liquid crystal display element of the present invention can be produced, for example, by the following method (a) or (b).

  (A) First, a pair (two) of transparent substrates having a transparent conductive film (electrode) on one side is prepared, and the radiation-sensitive resin composition of the present invention is used on the transparent conductive film of one of the substrates. According to the above-described method, the spacer and / or the protective film are formed. Subsequently, an alignment film having liquid crystal alignment ability is formed on the transparent conductive film and the spacer or protective film of these substrates. These substrates are arranged to face each other with a certain gap (cell gap) so that the liquid crystal alignment direction of each alignment film is orthogonal or antiparallel, with the surface on which the alignment film is formed on the inside. A liquid crystal is filled in the cell gap defined by the surface of the substrate (alignment film) and the spacer, and the filling hole is sealed to constitute a liquid crystal cell. Then, the liquid crystal display element of the present invention is bonded to both outer surfaces of the liquid crystal cell so that the polarizing direction is aligned or orthogonal to the liquid crystal alignment direction of the alignment film formed on one surface of the substrate. Can be obtained.

  (B) First, a pair of transparent substrates on which a transparent conductive film, an inter-layer insulating film, a protective film, a spacer, or both, and an alignment film are formed are prepared in the same manner as in the method (a). After that, along the edge of one substrate, an ultraviolet curable sealant is applied using a dispenser, and then the liquid crystal is dropped in the form of fine droplets using a liquid crystal dispenser, and the two substrates are bonded together under vacuum. . Then, both substrates are sealed by irradiating the above-mentioned sealant part with ultraviolet rays using a high-pressure mercury lamp. Finally, the liquid crystal display element of the present invention can be obtained by attaching polarizing plates to both outer surfaces of the liquid crystal cell.

  Examples of the liquid crystal used in each of the above methods include nematic liquid crystal and smectic liquid crystal. Further, as a polarizing plate used outside the liquid crystal cell, a polarizing film in which a polarizing film called an “H film” that absorbs iodine while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films, or an H film The polarizing plate which consists of itself can be mentioned.

  The present invention will be described more specifically with reference to production examples, synthesis examples, and examples. However, the present invention is not limited to the following description.

In the following synthesis examples, the weight average molecular weight Mw of the copolymer was measured by gel permeation chromatography (GPC) under the following apparatus and conditions.
Apparatus: GPC-101 (made by Showa Denko KK)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined Mobile phase: Tetrahydrofuran

EXAMPLES The present invention will be described more specifically with reference to the following synthesis examples and examples. However, the present invention is not limited to these synthesis examples and examples.

<Synthesis Example of (A) Copolymer>
Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol methyl ethyl ether. Subsequently, 20 parts by weight of styrene, 12 parts by weight of methacrylic acid, 28 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate and 40 parts by weight of glycidyl methacrylate were charged, and the atmosphere was replaced with nitrogen. While stirring the solution, the temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a solution containing the copolymer (A-1). The resulting polymer solution had a solid content concentration (ratio of the polymer weight to the total weight of the polymer solution) of 31.3%, and the weight average molecular weight Mw of the copolymer (A-1) was 12, 000.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol methyl ethyl ether. Subsequently, 10 parts by weight of styrene, 12 parts by weight of methacrylic acid, 23 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate and 20 parts by weight of glycidyl methacrylate, 20-methylglycidyl methacrylate 20 After 10 parts by weight and 10 parts by weight of tetrahydrofurfuryl methacrylate were substituted with nitrogen, 5 parts by weight of 1,3-butadiene was further added, and the temperature of the solution was raised to 70 ° C. while gently stirring. The solution containing a copolymer (A-2) was obtained by carrying out polymerization for 5 hours. The solid content concentration of the obtained polymer solution was 31.5%, and the weight average molecular weight Mw of the copolymer (A-2) was 10,100.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (isobutyronitrile) and 220 parts by weight of 3-methoxybutyl acetate. Subsequently, 10 parts by weight of styrene, 13 parts by weight of acrylic acid, 17 parts by weight of n-butyl methacrylate, 15 parts by weight of benzyl methacrylate and 40 parts by weight of 3- (methacryloyloxymethyl) -3-ethyloxetane were charged, and after nitrogen substitution. Further, 5 parts by weight of 1,3-butadiene was added, the temperature of the solution was raised to 80 ° C. while gently stirring, and polymerization was carried out while maintaining this temperature for 5 hours to obtain a copolymer (A-3) A solution containing was obtained. The solid content concentration of the obtained polymer solution was 30.9%, and the weight average molecular weight Mw of the copolymer (A-3) was 9,800.

Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol methyl ethyl ether. Subsequently, 10 parts by weight of styrene, 10 parts by weight of methacrylic acid, 20 parts by weight of tetrahydrofurfuryl methacrylate, 30 parts by weight of glycidyl methacrylate and 25 parts by weight of 3- (methacryloyloxymethyl) -3-ethyloxetane were added, and after nitrogen substitution Further, 5 parts by weight of 1,3-butadiene was added, the temperature of the solution was raised to 70 ° C. while gently stirring, and polymerization was carried out while maintaining this temperature for 5 hours to obtain a copolymer (A-4). A solution containing was obtained. The solid content concentration of the obtained polymer solution was 31.3%, and the weight average molecular weight Mw of the copolymer (A-4) was 1,1000.

<Preparation of radiation sensitive resin composition solution>
Example 1
(A) Copolymers of the types and amounts shown in Table 1, (B) polymerizable unsaturated compounds, (C) radiation sensitive polymerization initiators (optionally combined with amino sensitizers and thiol compounds), ( D) component and (E) component are mixed, and (F) 5 parts by weight of γ-glycidoxypropyltrimethoxysilane as an adhesion assistant, (G) FTX-218 (trade name, Co., Ltd.) as a surfactant. (Neos) 0.5 parts by weight and (H) 0.5 parts by weight of 4-methoxyphenol as a storage stabilizer were mixed, and propylene glycol monomethyl ether acetate was added so that the solid concentration would be 30% by weight. Then, the solution of the radiation sensitive resin composition was each prepared by filtering with a Millipore filter with a hole diameter of 0.5 micrometer.
The copolymer (A) was added as a copolymer solution containing the copolymers listed in Table 1 (obtained in any of Synthesis Examples 1 to 4 above), and the copolymer contained therein The amount was set to the amount described in Table 1.

<Evaluation of Radiation Sensitive Resin Composition Solution>
The radiation sensitive resin composition prepared as described above was evaluated as follows. The evaluation results are shown in Table 2.

(1) Evaluation of resolution After applying the solution of the radiation-sensitive resin composition prepared above on an alkali-free glass substrate with a spinner, the film thickness is 4 by pre-baking on a hot plate at 100 ° C. for 2 minutes. A film of 0.0 μm was formed.
Next, the obtained coating film is exposed to an exposure amount of 200 to 1,000 J / m ² using a high-pressure mercury lamp through a photomask having a plurality of circular residual patterns having different sizes in the diameter range of 8 to 15 μm. Irradiation was performed with variable amounts in the range.
Thereafter, development was performed by a puddle method using a 0.40 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. with the development time as a variable, and then washed with pure water for 1 minute. Furthermore, a patterned film was formed by post-baking in an oven at 230 ° C. for 30 minutes. At this time, if a pattern is formed in a photomask of 8 μm or less, it can be said that the resolution is good. In a photomask of 8 μm or less, when a pattern is not formed or resolved, it can be determined that the resolution is poor. The evaluation results are shown in Table 2.

(2) Evaluation of sensitivity Substrate in the same manner as in “(1) Evaluation of resolution” except that in (1) above, a photomask having a plurality of 15 μm-diameter circular residual patterns was used and the exposure amount was varied. A round residue pattern was formed on top. The height of the circular residual pattern before and after development was measured using a laser microscope (VK-8500 manufactured by Keyence). The remaining film rate (%) was obtained by applying these values to the following equation.
Residual film ratio (%) = (height after development / height before development) × 100
The exposure amount at which the remaining film ratio was 90% or more was defined as sensitivity. It can be said that the sensitivity is good when the exposure amount is 700 J / m ² or less. The evaluation results are shown in Table 2.

(3) Evaluation of developability When the development time is shortened to 40 seconds at the exposure amount of 700 J / m ² in (1), the pattern is good (◯) and the residue is poor. (X) was evaluated. The evaluation results are shown in Table 2.

(4) Evaluation of adhesion at the time of development In the above (1), the development process was changed to development at 25 ° C. for 180 seconds with a 0.5 wt% aqueous solution of tetramethylammonium hydroxide at an exposure amount of 700 J / m ² to form a pattern. At this time, it was observed with a laser microscope (VK-8500, manufactured by Keyence Corporation) how many patterns were peeled out of 100 patterns formed with an 8 um round mask. The evaluation results are shown in Table 2.

(5) Evaluation of light resistance In the above (1), the film obtained by exposing at 700 J / m ² without using a photomask was subjected to 800, at an illuminance of 130 mW with a UV irradiation apparatus (UVX-02516S1JS01, manufactured by USHIO). The film was irradiated with 000 J / m ² and evaluated as good (◯) if the film loss was 2% or less, and defective (×) if it was 3% or more. The evaluation results are shown in Table 2.

(6) Evaluation of heat resistance The film obtained by exposing to 700 J / m ² without passing through a photomask in (1) above, and the film thickness before and after heating in an oven at 230 ° C. for 20 minutes are measured. The thickness was measured with a thickness measuring machine (Alphastep IQ, manufactured by KLA Tencor), and the residual film ratio (film thickness after treatment / film thickness before treatment × 100) was calculated. The evaluation results are shown in Table 2.

(7) Evaluation of chemical resistance In the above (1), the alignment film stripping solution Chemiclean TS-204 (Sanyo Kasei Kogyo Co., Ltd.) heated to 60 ° C. was applied to the coating film obtained by exposure at 700 J / m ² without using a photomask. (Made by Co., Ltd.) for 15 minutes, washed with water, and further dried in an oven at 120 ° C. for 15 minutes. The film thickness before and after this treatment was measured with a stylus type film thickness measuring device (Alphastep IQ, manufactured by KLA Tencor), and the residual film ratio (film thickness after treatment / film thickness before treatment × 100) was calculated. The evaluation results are shown in Table 2.

(8) Transmittance Evaluation The transmittance at 400 nm wavelength of the coating obtained by (1) without exposure through a photomask at 700 J / m ² was measured with a spectrophotometer (150-20 type double beam (Hitachi, Ltd.). )))). At this time, it can be said that the transparency is poor when it is less than 90%. The evaluation results are shown in Table 2.

(8) Evaluation of flatness Using a pigment-based color resist (“JCR RED 689”, “JCR GREEN 706” and “CR 8200B” manufactured by JSR Corporation) on a SiO ₂ dip glass substrate, as follows: In addition, striped color filters of three colors of red, green and blue were formed. That is, using a spinner, one color of the color resist was applied to a SiO ₂ dip glass substrate and pre-baked on a hot plate at 90 ° C. for 150 seconds to form a coating film. Then, using an exposure machine Canon PLA501F (manufactured by Canon Inc.), ghi rays (wavelength ratios of 436 nm, 405 nm, 365 nm = 2.7: 2.5: 4.8) are passed through a predetermined pattern mask. Irradiation was performed at an exposure amount of 2,000 J / m ^{2 in} terms of i-line, followed by development using a 0.05 mass% aqueous potassium hydroxide solution and rinsing with ultrapure water for 60 seconds. Subsequently, a heat treatment was further performed in an oven at 230 ° C. for 30 minutes to form a single-color striped color filter. By repeating this operation for three colors, a striped color filter (stripe width 200 μm) of three colors of red, green and blue was formed.
Measurement length 2,000μm, measurement range 2,000μm square, measurement direction is red, green, blue stripe line minor axis direction and red / red, green / green, blue / blue same color stripe line major axis direction In two directions, the number of measurement points in each direction is n = 5 (the total number of n is 10), and the unevenness of the surface of the color filter substrate is changed to a contact-type film thickness measuring device (“Alpha-” manufactured by KLA-Tencor Corporation). It was 1.0 μm when measured in “Step”). Each thermosetting resin composition was applied to the substrate on which the color filter was formed with a spinner, then pre-baked on a hot plate at 90 ° C. for 5 minutes to form a coating film, and further in a clean oven Then, a protective film having a thickness of about 2.0 μm from the upper surface of the color filter was formed by post-baking at 230 ° C. for 60 minutes.
About the board | substrate which has a protective film on the color filter formed in this way, the unevenness | corrugation of the surface of a protective film was measured with the contact-type film thickness measuring apparatus ("Alpha step" by KLA-Tencor Co., Ltd.). This measurement has a measuring length of 2,000 μm, a measuring range of 2,000 μm square, measuring directions of red, green, blue stripe lines and minor axis directions, and red / red, green / green, blue / blue stripe lines of the same color. The major axis direction is two directions, and the number of measurement points is n = 5 (total n number is 10) in each direction, and the average value of 10 times of the height difference (nm) between the highest part and the lowest part is obtained for each measurement. Table 2 shows the evaluation of the planarization ability (flatness) of the protective film. When this value is 200 nm or less, it can be said that the planarization ability of the protective film is good.

(9) Evaluation of voltage holding ratio A soda glass substrate on which a prepared liquid composition is formed with an SiO ₂ film for preventing elution of sodium ions on the surface, and an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape After spin coating, pre-baking was performed for 10 minutes in a clean oven at 90 ° C. to form a coating film having a thickness of 2.0 μm.
Next, the coating film was exposed at an exposure amount of 500 J / m ² without using a photomask. Thereafter, the substrate is immersed in a developer comprising a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air-dried, and further post-baked at 230 ° C. for 30 minutes. And the coating film was cured to form a permanent cured film.
Next, the substrate on which this pixel is formed and the substrate on which ITO electrodes are simply deposited in a predetermined shape are bonded together with a sealant mixed with 0.8 mm glass beads, and then Merck liquid crystal MLC6608 (trade name) is injected. Thus, a liquid crystal cell was produced.
Next, the liquid crystal cell was placed in a constant temperature layer of 60 ° C., and the voltage holding ratio of the liquid crystal cell was measured with a liquid crystal voltage holding ratio measuring system “VHR-1A type” (trade name) manufactured by Toyo Corporation. The applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 60 Hz. Here, the voltage holding ratio is a value of (liquid crystal cell potential difference after 16.7 milliseconds / voltage applied at 0 milliseconds). If the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot hold the applied voltage at a predetermined level for a time of 16.7 milliseconds, and the liquid crystal cannot be sufficiently aligned. There is a high risk of “burn-in”.

表１中、各成分の略称はそれぞれ次の意味である。
（Ｂ）重合性不飽和化合物
Ｂ−１：ジペンタエリスリトールヘキサアクリレート
Ｂ−２：ＫＡＹＡＲＡＤ ＤＰＨＡ−４０Ｈ（日本化薬（株）製）
Ｂ−３：１，９−ノナンジオールジアクリレート
Ｂ−４：アロニックスＭ−５３００；（東亞合成（株）製）
（Ｃ）感放射線性重合開始剤
Ｃ−１：１，２−オクタンジオン，１−［４−（フェニルチオ）−，２−（Ｏ−ベンゾイルオキシム）］(商品名「イルガキュアＯＸＥ０１」、チバ・スペシャルティー・ケミカルズ社製）
Ｃ−２：エタノン−１−〔９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル〕−１−（Ｏ−アセチルオキシム）(商品名「イルガキュアＯＸＥ０２」、チバ・スペシャルティー・ケミカルズ社製）
Ｃ−３：２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン（商品名「イルガキュア９０７」、チバ・スペシャルティー・ケミカルズ社製）
Ｃ−４：２−ジメチルアミノ−２−（４−メチルベンジル）−１−（４−モルフォリン−4−イル−フェニル）−ブタン−１−オン（商品名「イルガキュア３７９」、チバ・スペシャルティー・ケミカルズ社製）
（Ｄ）成分
Ｄ−１：トリス−（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−イソシアヌレイト ：フェノール型酸化防止剤（商品名「アデカスタブＡＯ−２０」アデカ社製）
Ｄ−２：１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）ベンゼン ：フェノール型酸化防止剤（商品名「アデカスタブＡＯ−３３０」アデカ社製）
Ｄ−３：２，２´−メチレンビス（４，６−ジ−ｔｅｒｔ−ブチル−１−フェニルオキシ）（２−エチルヘキシルオキシ）ホスホラス ：ホスファイト型酸化防止剤（商品名「アデカスタブＨＰ−１０」アデカ社製）
Ｄ−４：ジステアリルペンタエリスリトールジフォスファイト ：ホスファイト型酸化防止剤（商品名「アデカスタブＰＥＰ−８」アデカ社製）
Ｄ−５：ペンタエリスリトールテトラキス（３−ラウリルチオプロピオネート） ：チオエーテル型酸化防止剤（商品名「アデカスタブＡＯ−４１２Ｓ」アデカ社製）
Ｄ−６：テトラキス（２，２，６，６−ペンタメチル−４−ピペリジル）１，２，３，４−ブタンテトラカルボキシレート ：アミン型酸化防止剤（商品名「アデカスタブＬＡ−５７」アデカ社製
（Ｅ）成分
Ｅ−１：ノボラック型エポキシ樹脂（商品名「エピコート１５２」、ジャパンエポキシレジン（株）製）
Ｅ−２：ノボラック型エポキシ樹脂（商品名「エピコート１５７Ｓ６５」、ジャパンエポキシレジン（株）製）
なお、欄中の「−」は該当する成分を使用しなかったことを表す。

In Table 1, the abbreviation of each component has the following meaning.
(B) Polymerizable unsaturated compound B-1: Dipentaerythritol hexaacrylate B-2: KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.)
B-3: 1,9-nonanediol diacrylate B-4: Aronix M-5300; (manufactured by Toagosei Co., Ltd.)
(C) Radiation-sensitive polymerization initiator C-1: 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (trade name “Irgacure OXE01”, Ciba Special Made by Tea Chemicals)
C-2: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (trade name “Irgacure OXE02”, Ciba Special Made by Tea Chemicals)
C-3: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name “Irgacure 907”, manufactured by Ciba Specialty Chemicals)
C-4: 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (trade name “Irgacure 379”, Ciba Specialty・ Made by Chemicals
(D) Component D-1: Tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate: Phenol type antioxidant (trade name “ADK STAB AO-20” manufactured by Adeka)
D-2: 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene: phenol type antioxidant (trade name “ADK STAB AO-330 “Adeka”
D-3: 2,2′-methylenebis (4,6-di-tert-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus: Phosphite type antioxidant (trade name “ADK STAB HP-10” ADEKA (Made by company)
D-4: Distearyl pentaerythritol diphosphite: Phosphite type antioxidant (trade name “ADK STAB PEP-8” manufactured by Adeka)
D-5: Pentaerythritol tetrakis (3-lauryl thiopropionate): Thioether type antioxidant (trade name “ADK STAB AO-412S” manufactured by Adeka)
D-6: Tetrakis (2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate: Amine-type antioxidant (trade name “ADK STAB LA-57” manufactured by ADEKA Corporation (E) Component E-1: Novolac type epoxy resin (trade name “Epicoat 152”, manufactured by Japan Epoxy Resins Co., Ltd.)
E-2: Novolac type epoxy resin (trade name “Epicoat 157S65”, manufactured by Japan Epoxy Resins Co., Ltd.)
In addition, “-” in the column represents that the corresponding component was not used.

Claims (4)

(A) (a1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, (a2) glycidyl acrylate, 2-methylglycidyl acrylate, 3,4-epoxybutyl acrylate, 6,7-epoxy acrylate Heptyl, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl methyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, α-ethyl acrylic Acid 6,7-epoxyheptyl At least one radically polymerizable compound selected from the group consisting of o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and oxetanyl group-containing polymerizable unsaturated compound, and (a3) (meth) Acrylic acid alkyl ester, (meth) acrylic acid alicyclic ester, unsaturated hetero-5- and 6-membered ring (meth) acrylic acid ester containing oxygen atom, (meth) acrylic acid aryl ester, maleimide compound, (meth) acrylic acid A resin soluble in an alkaline aqueous solution that is a copolymer of at least one other radical polymerizable compound selected from the group consisting of hydroxyalkyl esters, styrene, α-methylstyrene, and 1,3-butadiene, The copolymerization ratio of the component (a1) in the copolymer is 5 to 40 The amount% (a2) a copolymer ratio is 10 to 70% by weight of the component and (a3) a copolymer copolymerization ratio of components is 10 to 70 wt%,
(B) a polymerizable compound having an ethylenically unsaturated bond,
(C) a radiation-sensitive polymerization initiator, and (D) pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6- Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropion) amide), 4,6-bis (octylthiomethyl)-o-cresol, 4,6-bis (dodecylthiomethyl)-o-cresol , Ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate], 2,2′-methylenebis (4,6-di-tert-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus, distearyl pentaerythritol diphosphite A radiation-sensitive resin composition for forming an interlayer insulating film, comprising: One of the said (C) radiation sensitive polymerization initiators is an O-acyl oxime compound, The radiation sensitive resin composition for interlayer insulation film formation of Claim 1 characterized by the above-mentioned. A method for forming an interlayer insulating film, comprising the following steps in the order described below.
(1) The process of forming the coating film of the radiation sensitive resin composition for interlayer insulation film formation as described in any one of Claim 1 or Claim 2 on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) Development step, and (4) Heating step. An interlayer insulating film formed by the method according to claim 3.