JP5540689B2 - Radiation-sensitive composition, cured film and method for forming the same - Google Patents

Description

  The present invention relates to a radiation-sensitive composition, a cured film formed from the composition, and a method for forming the cured film.

  A liquid crystal display element or the like is subjected to an immersion treatment with a solvent, an acid, an alkali solution or the like during its manufacturing process. In such a liquid crystal display element, the surface of the element is locally exposed to a high temperature when the wiring electrode layer is formed by sputtering. Accordingly, in order to prevent the liquid crystal display element from being deteriorated or damaged by such immersion treatment with a solvent or the like or high temperature treatment, a protective film having resistance to these treatments is provided on the surface of the element. ing. In addition, liquid crystal display elements and the like are generally provided with an interlayer insulating film for insulating between wirings arranged in layers, and a spacer for keeping a distance (cell gap) between two substrates constant. .

  As a material for such a protective film, an interlayer insulating film, a spacer, etc. (hereinafter also referred to as a protective film), a material having a small number of steps for obtaining a required pattern shape and having sufficient flatness is used. Because of its preference, radiation sensitive compositions are widely used. The material such as the protective film has high adhesion when cured to the substrate or lower layer on which the protective film or the like is to be formed, and further to the layer formed on each layer, and has transparency. Performances such as being excellent, coating properties and patterning properties are required. An acrylic resin is mainly used as a material for forming a protective film or the like that satisfies these various characteristics. On the other hand, an attempt has been made to use a polysiloxane material, which is superior in heat resistance and transparency as compared with an acrylic resin, as a component of the radiation-sensitive composition (JP 2000-1648 A, JP 2006-178436 A). No. publication). However, since the refractive index of the polysiloxane material is lower than that of the acrylic resin, the difference in refractive index becomes large when applied to the surface of another layer such as an ITO (indium tin oxide) transparent conductive film pattern. There is an inconvenience that the ITO pattern becomes easy to see and the visibility of the liquid crystal display screen is lowered.

  Further, such a radiation sensitive composition is preferably a positive radiation sensitive curable composition from the viewpoint of superiority of contact hole formation in an interlayer insulating film, for example. It is used. However, as a positive radiation sensitive composition in a polysiloxane-based material, a composition using a quinone diazide compound is generally used as a radiation sensitive acid generator because of its high patterning property. The use of compounds is a factor in high costs.

  Also, semiconductor sealing materials, semiconductor underfill materials, semiconductor protective film materials, semiconductor interlayer insulating film materials, circuit substrate materials, planarization materials, circuit board protection materials, etching resist materials, plating resists There is no radiation-sensitive composition capable of obtaining a cured film excellent in heat resistance, adhesion, electrical insulation and the like in a short time as a material for sealing or liquid crystal sealing (see US Pat. No. 5,385,955). ).

JP 2000-1648 A JP 2006-178436 A US Pat. No. 5,385,955

  The present invention has been made based on such circumstances, and has patterning properties required for a material for forming a conventional protective film, etc., and the obtained cured product is added to transparency and adhesion. A polysiloxane-based radiation-sensitive composition having a high refractive index and a positive radiation-sensitive property, a cured product formed from the composition, and a method for forming the same Objective.

  Furthermore, semiconductor sealing materials, semiconductor underfill materials, semiconductor protective film materials, semiconductor interlayer insulating film materials, circuit substrate materials, planarization materials, circuit board protection materials, etching resist materials, plating resists Another object of the present invention is to provide a radiation-sensitive composition capable of obtaining a cured film excellent in heat resistance, adhesion, electrical insulation, and the like in a short time by being used as a material for sealing or a liquid crystal sealing material. And

The invention made to solve the above problems is
[A] siloxane polymer,
[B] metal oxide particles, and [C] a radiation sensitive acid generator or a radiation sensitive base generator,
[B] The metal oxide particles are a radiation-sensitive composition that is oxide particles of at least one metal selected from the group consisting of aluminum, zirconium, titanium, zinc, indium, tin, antimony, and cerium.

  The said radiation sensitive composition has high patternability by containing said each component, and the obtained hardened | cured material can be equipped with high transparency and adhesiveness. In particular, according to the said radiation sensitive composition, the refractive index of the hardened | cured material obtained improves by containing the said kind of metal oxide particle as a [B] component. Moreover, the said radiation sensitive composition can exhibit a positive radiation sensitive characteristic with high patternability by using the said oxide particle as a metal oxide particle of [B] component.

[A] The siloxane polymer may be a hydrolysis condensate of a hydrolyzable silane compound represented by the following formula (1).
_{^{(R 1) n -Si- (OR}} 2) 4-n (1)
(In formula (1), each R ¹ is independently hydrogen or a non-hydrolyzable organic group having 1 to 20 carbon atoms. R ² is each independently hydrogen or alkyl having 1 to 6 carbon atoms. Group, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, n is an integer of 0 to 3).

  [A] Since the siloxane polymer is a hydrolysis condensate of the hydrolyzable silane compound represented by the above formula (1), the radiation-sensitive composition has high coatability, radiation sensitivity, and patternability. And the obtained hardened | cured material can be equipped with still higher transparency and adhesiveness.

  The radiation-sensitive composition may further contain a [D] dispersant. By containing the [D] dispersant, the radiation-sensitive composition can uniformly disperse the metal oxide particles of the component [B], further improve applicability, and adherence of the resulting cured film. Increases more and the refractive index becomes uniform.

  [D] The dispersant is a compound represented by the following formula (2), formula (3) or formula (4), polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, alkyl glucoside, polyoxyethylene fatty acid ester, It is preferably a sugar fatty acid ester, a sorbitan fatty acid ester, a polyoxyethylene sorbitan fatty acid ester or a fatty acid alkanolamide.

（式（２）中、Ｒ^３は、各々独立に、Ｃ_ｑＨ_２ｑ＋１−ＣＨ_２Ｏ−（ＣＨ_２ＣＨ_２Ｏ）_ｐ−ＣＨ_２ＣＨ_２Ｏ−である。ｐは８〜１０、ｑは１２〜１６、ｘは１〜３の整数である。）

(In the formula (2), ^{R 3} is, _{independently, C q H 2q + 1 -CH} 2 O- (CH 2 CH 2 O) p -CH 2 CH 2 O- in which .p is 8 to 10, q is 12-16, x is an integer of 1-3.)

（式（３）中、ｒ及びｓは、ゲルパーミエーションクロマトグラフィーにより求められたポリスチレン換算数平均分子量が、１０，０００〜４０，０００となるように選択される数である。）

(In Formula (3), r and s are numbers selected so that the polystyrene-equivalent number average molecular weight determined by gel permeation chromatography is 10,000 to 40,000.)

（式（４）中、ｔ及びｕは、ゲルパーミエーションクロマトグラフィーにより求められたポリスチレン換算数平均分子量が１，０００〜３０，０００となるように選択される数である。）

(In formula (4), t and u are numbers selected such that the polystyrene-equivalent number average molecular weight determined by gel permeation chromatography is 1,000 to 30,000.)

  According to the radiation-sensitive composition, when the dispersant of the component [D] is the above compound, it is possible to exhibit higher patterning properties having positive radiation-sensitive characteristics.

The radiation-sensitive composition of the present invention is suitably used for forming a patterned cured film.
(1) The process of forming the coating film of a radiation sensitive composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) a step of developing the coating film irradiated with radiation in step (2), and (4) a step of heating the coating film developed in step (3).

  In the method, each cured film having a fine and elaborate pattern can be easily formed by using the radiation-sensitive composition having excellent patternability and forming a pattern by exposure and development utilizing radiation sensitivity. Can be formed.

  Therefore, the patterned cured film formed from the radiation-sensitive composition of the present invention has high refraction in addition to high transparency and adhesiveness, so that the visibility of the liquid crystal display screen can be improved. And can be suitably used as a material for liquid crystal display elements and the like. In addition, the patterned cured film formed from the radiation-sensitive composition of the present invention has high transparency, adhesion, and high refractive index, so that it can be used for semiconductor protective films, interlayer insulating films, and LEDs. It can also be suitably used as a material for the lens.

  Further, the radiation-sensitive composition of the present invention comprises a semiconductor sealing material, a semiconductor underfill material, a circuit substrate material, a planarizing material, a circuit board protecting material, an etching resist material, a plating resist material, Alternatively, by using it as a liquid crystal sealing material or the like, a cured film excellent in heat resistance, adhesion, electrical insulation and the like can be obtained in a short time.

  As described above, the radiation-sensitive composition of the present invention contains the above [A] to [C] components, so that it has high patternability and a cured product obtained from the composition is highly transparent. In addition to adhesiveness and adhesion, it has high refraction. Furthermore, the radiation-sensitive composition of the present invention can further improve coating properties and positive radiation-sensitive characteristics by containing a dispersant of the component [D]. Accordingly, the patterned cured film formed from the radiation-sensitive composition of the present invention has high refraction in addition to high transparency and adhesion, so each cured film for liquid crystal display elements, for semiconductors It can be used suitably as each material etc. of each cured film, LED lens, etc.

  Further, the radiation-sensitive composition of the present invention comprises a semiconductor sealing material, a semiconductor underfill material, a circuit substrate material, a planarizing material, a circuit board protecting material, an etching resist material, a plating resist material, By using it as a liquid crystal sealing material or the like, a cured film excellent in heat resistance, adhesion, electrical insulation and the like can be obtained in a short time.

  The radiation-sensitive composition of the present invention contains [A] a siloxane polymer, [B] metal oxide particles, [C] a radiation-sensitive acid generator or a radiation-sensitive base generator, and if necessary, [D] Contains a dispersant and other optional ingredients.

[A] component: siloxane polymer The siloxane polymer of the [A] component is not particularly limited as long as it is a polymer of a compound having a siloxane bond. This [A] component hydrolyzes and condenses to form a cured product.

  The siloxane polymer of the component [A] is preferably a hydrolysis condensate of a hydrolyzable silane compound represented by the above formula (1).

  The hydrolyzable silane compound in the present application is usually hydrolyzed to form a silanol group by heating in the temperature range of room temperature (about 25 ° C.) to about 100 ° C. in the presence of a catalyst and excess water. Or a compound having a “hydrolyzable group” capable of forming a siloxane condensate. Further, the “non-hydrolyzable group” refers to a group that does not cause hydrolysis or condensation and exists stably under such hydrolysis conditions.

  In the hydrolysis reaction of the hydrolyzable silane compound represented by the above formula (1), some hydrolyzable groups may remain in an unhydrolyzed state. The “hydrolyzable condensate of hydrolyzable silane compound” referred to here means a hydrolyzed condensate obtained by reacting and condensing some silanol groups of the hydrolyzed silane compound.

As the non-hydrolyzable organic group having 1 to 20 carbon atoms represented by R ¹ , one or more unsubstituted, vinyl, (meth) acryloyl or epoxy groups having 1 to 20 carbon atoms are used. Examples include substituted alkyl groups, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms. These may be linear, branched, or cyclic, and when a plurality of R ¹ are present in the same molecule, a combination thereof may be used. R ¹ may include a structural unit having a hetero atom. Examples of such a structural unit include ether, ester, sulfide and the like.

The group represented by R ² is preferably hydrogen or an alkyl group having 1 to 6 carbon atoms, particularly preferably hydrogen, a methyl group, or an ethyl group, from the viewpoint of ease of hydrolysis.

  The subscript n is an integer of 0 to 3, more preferably an integer of 0 to 2, particularly preferably 0 or 1, and most preferably 1. When n is an integer of 0 to 2, the hydrolysis / condensation reaction proceeds more easily, and as a result, the rate of the curing reaction of the component [A] is further increased. Melt flow resistance in the heating process can be improved.

  The hydrolyzable silane compound represented by the above formula (1) is a silane compound substituted with four hydrolyzable groups, substituted with one non-hydrolyzable group and three hydrolyzable groups. Silane compound substituted with two non-hydrolyzable groups and two hydrolyzable groups, substituted with three non-hydrolyzable groups and one hydrolyzable group Mention may be made of silane compounds or mixtures thereof.

As a specific example of the hydrolyzable silane compound represented by the above formula (1),
Examples of the silane compound substituted with four hydrolyzable groups include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, etc. ;
As a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, ethyltrimethoxy Silane, ethyltriethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, γ-glycidoxypro Le trimethoxysilane, .gamma.-glycidoxypropyl triethoxy silane, beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like;
As a silane compound substituted with two non-hydrolyzable groups and two hydrolyzable groups, dimethyldimethoxysilane, diphenyldimethoxysilane, dibutyldimethoxysilane and the like;
Examples of the silane compound substituted with three non-hydrolyzable groups and one hydrolyzable group include tributylmethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, tributylethoxysilane, and the like.

  Of these hydrolyzable silane compounds represented by the above formula (1), silane compounds substituted with four hydrolyzable groups (n = 0), one non-hydrolyzable group and three A silane compound (n = 1) substituted with one hydrolyzable group is preferred, and a silane compound (n = 1) substituted with one non-hydrolyzable group and three hydrolyzable groups is particularly preferred. preferable. Specific examples of this preferred hydrolyzable silane compound include tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, ethyl Examples include triethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane. . Such hydrolyzable silane compounds may be used alone or in combination of two or more.

  The conditions for hydrolyzing and condensing the hydrolyzable silane compound represented by the above formula (1) are hydrolyzable by hydrolyzing at least a part of the hydrolyzable silane compound represented by the above formula (1). Although it does not specifically limit as long as it converts a group into a silanol group and causes a condensation reaction, it can implement as follows as an example.

The water used for hydrolysis / condensation of the hydrolyzable silane compound represented by the above formula (1) is preferably water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment or distillation. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved. The amount of water used is preferably from 0.1 to 3 mol, more preferably from 1 mol of the total amount of hydrolyzable groups (—OR ² ) of the hydrolyzable silane compound represented by the above formula (1). Is an amount of 0.3-2 mol, more preferably 0.5-1.5 mol. By using such an amount of water, the hydrolysis / condensation reaction rate can be optimized.

  The solvent that can be used for hydrolysis / condensation of the hydrolyzable silane compound represented by the above formula (1) is not particularly limited, and examples thereof include ethylene glycol monoalkyl ether acetate and diethylene glycol dialkyl ether. , Propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and propionic acid esters. Among these solvents, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate or methyl 3-methoxypropionate is particularly preferable.

The hydrolysis / condensation reaction of the hydrolyzable silane compound represented by the above formula (1) is preferably an acid catalyst (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid). , Phosphoric acid, acidic ion exchange resins, various Lewis acids), basic catalysts (eg, nitrogen-containing compounds such as ammonia, primary amines, secondary amines, tertiary amines, pyridine; basic ion exchange resins; water) In the presence of a catalyst such as hydroxide such as sodium oxide; carbonate such as potassium carbonate; carboxylate such as sodium acetate; various Lewis bases] or alkoxide (eg, zirconium alkoxide, titanium alkoxide, aluminum alkoxide). Done. For example, tetra-i-propoxyaluminum can be used as the aluminum alkoxide. The amount of the catalyst used is preferably 10 ⁻⁶ mol or more and 0.2 mol or less, more preferably 0, with respect to 1 mol of the hydrolyzable silane compound monomer from the viewpoint of promoting hydrolysis / condensation reaction. It is 0.0001 or more and 0.1 mol or less.

  The reaction temperature and reaction time in hydrolysis / condensation of the hydrolyzable silane compound represented by the above formula (1) are appropriately set. For example, the following conditions can be adopted. The reaction temperature is preferably 40 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours. By setting such reaction temperature and reaction time, the hydrolysis / condensation reaction can be performed most efficiently. In this hydrolysis / condensation, the reaction may be carried out in one step by adding a hydrolyzable silane compound, water and a catalyst to the reaction system at one time. Alternatively, the hydrolyzable silane compound, water and the catalyst may be The hydrolysis and condensation reaction may be performed in multiple stages by adding them into the reaction system in several times. After the hydrolysis / condensation reaction, water and the produced alcohol can be removed from the reaction system by adding a dehydrating agent and then subjecting it to evaporation.

  The molecular weight of the hydrolysis condensate of the hydrolyzable silane compound represented by the above formula (1) is measured as a number average molecular weight in terms of polystyrene using GPC (gel permeation chromatography) using tetrahydrofuran as a mobile phase. be able to. The number average molecular weight of the hydrolysis-condensation product is usually preferably a value within the range of 500 to 10,000, and more preferably within the range of 1000 to 5000. By setting the value of the number average molecular weight of the hydrolysis-condensation product to 500 or more, the film formability of the coating film of the positive radiation sensitive composition can be improved. On the other hand, the fall of the radiation sensitivity of a radiation sensitive composition can be prevented by making the value of the number average molecular weight of a hydrolysis-condensation product into 10,000 or less.

[B] component: metal oxide particles The metal oxide particles of the [B] component can be contained in the composition of the present invention, whereby the refractive index of the resulting cured product can be improved.

  [B] The metal oxide particles of the component are oxide particles of at least one metal selected from the group consisting of aluminum, zirconium, titanium, zinc, indium, tin, antimony and cerium. Among these, zirconium, titanium or Zinc oxide particles are preferred, and zirconium or titanium oxide particles are particularly preferred. These can be used alone or in combination of two or more. The metal oxide particles may be composite oxide particles of the above metals. Examples of the composite oxide particles include ATO (antimoy-tin oxide), ITO (indium-tin oxide), and IZO (indium-zinc oxide). As these metal oxide particles, commercially available ones such as Nanotech, CCI Kasei Co., Ltd. can be used.

  By using the above-mentioned types of particles as the metal oxide particles of the component [B], the radiation sensitive composition can exhibit positive radiation sensitive characteristics having high patterning properties. The reason for having positive radiation sensitive characteristics by using the above-mentioned types of metal oxide particles is not clear, but for example, the surface of the metal oxide particles acts as a photocatalyst upon irradiation with radiation such as ultraviolet rays. It is conceivable that the [A] component siloxane polymer covering the metal oxide particles is decomposed and the composition is melted.

  In addition, the reason why the positive patterning property is further enhanced when the above-mentioned preferable oxide particles (zirconium, titanium, and zinc) are used is not clear, but the high photocatalytic ability of these metal oxides has an influence. I think that. In addition, when zirconium or titanium is used as a particularly preferable metal, a higher refractive index can be obtained, and positive patterning property can be enhanced. The reason why the refractive index is further increased by using zirconium or titanium is not clear, but due to the low electronegativity, the polarization in the particles is high, and as a result, the refractive index can be improved. Therefore, the metal oxide particles of the component [B] are preferably metal oxide particles having an electronegativity of 1.7 or less, and particularly preferably metal oxide particles having an electronegativity of 1.6 or less. The electronegativity is a polling value.

  The shape of the metal oxide particles is not particularly limited, and may be spherical or indefinite, and may be hollow particles, porous particles, core / shell particles, or the like. The number average particle diameter of the metal oxide particles determined by the dynamic light scattering method is preferably 5 nm to 200 nm, more preferably 5 nm to 100 nm, and particularly preferably 10 nm to 80 nm. If the number average particle diameter of the metal oxide particles is less than 5 nm, the hardness of the cured film may be reduced, and if it exceeds 200 nm, the haze of the cured film may be increased.

  Although it does not specifically limit as a compounding quantity of the said metal oxide particle, 50 mass parts or less are preferable on a 0.1 mass site | part with respect to 100 mass parts of [A] component siloxane polymers, 1 mass part or more and 20 mass parts The following are particularly preferred: The refractive index improvement property of the hardened | cured material obtained as the compounding quantity of a metal oxide particle is 0.1 mass part or less is not high. On the contrary, when the compounding amount of the metal oxide particles exceeds 100 parts by mass, the applicability is lowered, and the haze of the obtained cured film may be increased.

The specific surface area of the metal oxide particles (by the BET specific surface area measurement method using nitrogen) is preferably 10 m ² / g or more and 1000 m ² / g or less, and more preferably 100 m ² / g or more and 500 m ² / g or less. When the specific surface area of the metal oxide particles is in the above range, the photocatalytic action is effectively exhibited, and higher desired radiation sensitive characteristics are exhibited.

Component [C]: Radiation sensitive acid generator or radiation sensitive base generator [C] The radiation sensitive acid generator or radiation sensitive base generator of component [A] It is defined as a compound capable of releasing an acidic active substance or a basic active substance that acts as a catalyst in the condensation / curing reaction of a siloxane polymer. The radiation irradiated to decompose the component [C] and generate a cation of an acidic active substance or an anion of a basic active substance includes visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, γ A line etc. can be mentioned. Among these radiations, it is preferable to use ultraviolet rays because they have a constant energy level, can achieve a high curing rate, and the irradiation device is relatively inexpensive and small.

  In addition, according to the said radiation sensitive composition, it specified as a radiation sensitive acid generator or a radiation sensitive base generator of a [C] component by using the said thing as a metal oxide particle of a [B] component. The positive patterning property can be exhibited without using any of those. In particular, as a positive polysiloxane-type radiation-sensitive composition, a quinonediazide compound is often used as an acid generator. According to the radiation-sensitive composition, the component [B] is used as described above. By using a predetermined metal oxide particle, positive type high patterning property can be exhibited without using a specific [C] component radiation sensitive acid generator or radiation sensitive base generator. Can do.

  As the radiation sensitive acid generator of component [C], diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, ammonium salt, phosphonium salt, onium salt such as tetrahydrothiophenium salt, sulfonimide Compounds. The quinonediazide compound is also a radiation sensitive acid generator that generates carboxylic acid by radiation. However, the acid generated is a carboxylic acid having a low acidity, which is not sufficient as a catalyst for the condensation / curing reaction. Therefore, the radiation sensitive acid generator of the [C] component is preferably other than the quinonediazide compound.

  Examples of diphenyliodonium salts include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyl Iodonium butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoroarce Bis (4-tert-butylphenyl) iodonium trifluorometa Examples include sulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium camphorsulfonic acid, and the like. .

  Examples of triphenylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, triphenyl Examples include sulfonium butyl tris (2,6-difluorophenyl) borate.

  Examples of the sulfonium salt include alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts and the like.

As these sulfonium salts,
Examples of the alkylsulfonium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- ( Benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate, etc .;
Examples of benzylsulfonium salts include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, and benzyl-4-methoxyphenylmethyl. Sulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethyl Sulfonium hexafluorophosphate, etc .;
Examples of dibenzylsulfonium salts include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyl dibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexa Fluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4 -Hydroxyphenylsulfonium hexafluorophosphate and the like;
Examples of substituted benzylsulfonium salts include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and p-chlorobenzyl-4-hydroxyphenylmethylsulfonium. Hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro Examples include -4-hydroxyphenylmethylsulfonium hexafluoroantimonate.

  Examples of benzothiazonium salts include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p-methoxy Benzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, and the like.

  Examples of tetrahydrothiophenium salts include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium Nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1- (4-n-Butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (5-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2, 2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydro Ofenium-2- (6-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4,7-dibutoxy-1 -Naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate and the like.

  Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide (trade name “SI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) succinimide (trade name “SI-”). 106 "(manufactured by Midori Chemical Co., Ltd.)), N- (4-methylphenylsulfonyloxy) succinimide (trade name" SI-101 "(manufactured by Midori Chemical Co., Ltd.)), N- (2-trifluoromethylphenyl) Sulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide N- (2-fluoropheny Sulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide (trade name “PI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) diphenylmaleimide, 4-methylphenylsulfonyloxy ) Diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (phenylsulfonyl) Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide (trade name “NDI-100” (manufactured by Midori Chemical Co., Ltd.)), N- (4-methylphenylsulfonyloxy) ) Bishik [2.2.1] Hept-5-ene-2,3-dicarboxylimide (trade name “NDI-101” (manufactured by Midori Chemical Co., Ltd.)), N- (trifluoromethanesulfonyloxy) bicyclo [2. 2.1] Hept-5-ene-2,3-dicarboxylimide (trade name “NDI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (nonafluorobutanesulfonyloxy) bicyclo [2.2. 1] Hept-5-ene-2,3-dicarboxylimide (trade name “NDI-109” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) bicyclo [2.2.1] hept- 5-ene-2,3-dicarboxylimide (trade name “NDI-106” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept- 5- Ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4- Methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept -5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- ( 2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4- (Luorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- ( Camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5 6-oxy-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane- , 6-oxy-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- ( Trifluoromethylsulfonyloxy) naphthyl dicarboximide (trade name “NAI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) naphthyl dicarboxyimide (trade name “NAI-106” (Midori Chemical) N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-101” (manufactured by Midori Chemical Co., Ltd.)), N- (phenylsulfonyloxy) naphthyl dicarboxylimide (Trade name “NAI-100” (manufactured by Midori Chemical Co., Ltd.)), N- (2-trifluoromethylphenol) Nylsulfonyloxy) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide, N- (pentafluoroethylsulfonyloxy) naphthyl dicarboxylimide, N- (heptafluoropropylsulfonyloxy) naphthyl dicarboxyl Imido, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-109” (manufactured by Midori Chemical Co., Ltd.)), N- (ethylsulfonyloxy) naphthyl dicarboxylimide, N- (propylsulfonyl) Oxy) naphthyl dicarboxylimide, N- (butylsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-1004” (manufactured by Midori Chemical Co., Ltd.)), N- (pentylsulfonyloxy) na Tildicarboxylimide, N- (hexylsulfonyloxy) naphthyldicarboxylimide, N- (heptylsulfonyloxy) naphthyldicarboxylimide, N- (octylsulfonyloxy) naphthyldicarboxylimide, N- (nonylsulfonyloxy) naphthyldi Examples thereof include carboxylimide.

  Among these radiation-sensitive acid generators, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, tetrahydrothiophene are used from the viewpoint of improving the radiation sensitivity of the radiation-sensitive composition and the adhesion of the resulting cured product. Nilium salts and sulfonimide compounds are preferably used. Among these, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium Hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexa Fluorophosphate, 1- (4-n-butoxynaphtha N-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate, N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide Preferably used.

  Examples of the radiation sensitive base generator include transition metal complexes such as cobalt, orthonitrobenzyl carbamates, α, α-dimethyl-3,5-dimethoxybenzyl carbamates, acyloxyiminos and the like.

  Examples of transition metal complexes include bromopentammonium cobalt perchlorate, bromopentamethylamine cobalt perchlorate, bromopentapropylamine cobalt perchlorate, hexaammonium cobalt perchlorate, hexamethylamine cobalt perchlorate. Examples include chlorate and hexapropylamine cobalt perchlorate.

  Examples of orthonitrobenzyl carbamates include [[(2-nitrobenzyl) oxy] carbonyl] methylamine, [[(2-nitrobenzyl) oxy] carbonyl] propylamine, [[(2-nitrobenzyl) oxy]. Carbonyl] hexylamine, [[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2-nitrobenzyl) oxy] carbonyl] aniline, [[(2-nitrobenzyl) oxy] carbonyl] piperidine, bis [ [(2-Nitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] phenylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] toluenediamine, bis [[ (2-Nitrobenzyl) oxy] ca Bonyl] diaminodiphenylmethane, bis [[(2-nitrobenzyl) oxy] carbonyl] piperazine, [[(2,6-dinitrobenzyl) oxy] carbonyl] methylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl ] Propylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] hexylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2,6-dinitrobenzyl) oxy] Carbonyl] aniline, [[(2,6-dinitrobenzyl) oxy] carbonyl] piperidine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2,6-dinitrobenzyl) Oxy] carbonyl] phenylenediamine, bis [[( , 6-dinitrobenzyl) oxy] carbonyl] toluenediamine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] diaminodiphenylmethane, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] piperazine and the like. It is done.

  Examples of α, α-dimethyl-3,5-dimethoxybenzyl carbamates include [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] methylamine, [[(α, α-dimethyl. −3,5-dimethoxybenzyl) oxy] carbonyl] propylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] hexylamine, [[(α, α-dimethyl-3,5 -Dimethoxybenzyl) oxy] carbonyl] cyclohexylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] aniline, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy ] Carbonyl] piperidine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] hexa Tylenediamine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] phenylenediamine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] toluenediamine Bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] diaminodiphenylmethane, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] piperazine, and the like. It is done.

  Examples of acyloxyiminos include propionyl acetophenone oxime, propionyl benzophenone oxime, propionyl acetone oxime, butyryl acetophenone oxime, butyryl benzophenone oxime, butyryl acetone oxime, adipoyl acetophenone oxime, adipoyl benzophenone oxime, adipoyl Acetone oxime, acryloyl acetophenone oxime, acryloyl benzophenone oxime, acryloyl acetone oxime and the like can be mentioned.

  Other examples of the radiation sensitive base generator include 2-nitrobenzylcyclohexyl carbamate, O-carbamoylhydroxyamide, O-carbamoylhydroxyamide and the like.

  As the radiation-sensitive acid generator or radiation-sensitive base generator of component [C], either an acid or a base is used, and one kind may be used alone, or two or more kinds may be mixed and used. May be. The amount of component [C] used is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, relative to 100 parts by weight of component [A]. Obtaining an excellent radiation-sensitive composition having a good balance of radiation sensitivity and adhesion of the cured product formed by setting the amount of the component [C] to be 0.1 to 20 parts by mass. In addition, it is possible to prevent the formation of precipitates in the coating film forming step and facilitate the formation of the coating film.

[D] Component: Dispersant The radiation-sensitive composition of the present invention preferably contains a [D] dispersant in addition to the [A] to [C] components. The radiation-sensitive composition can further disperse [B] metal oxide particles by further containing [D] a dispersant, thereby improving the coating property, and improving the adhesion of the resulting cured film, The refractive index can be increased uniformly without bias.

  Examples of the dispersant for the component [D] include nonionic dispersants, cationic dispersants, anionic dispersants, etc. From the viewpoint of improving positive radiation sensitivity and patterning properties, nonionic dispersants A dispersant is preferred. The reason why the radiation-sensitive composition improves the positive radiation-sensitive characteristics and patterning properties by using a nonionic dispersant as a dispersant for the component [D] is not clear, but the following may be considered, for example. . Nonionic dispersants include a covalently bonded moiety that is polarized. [B] The metal oxide particles of the component are composed of a positive-type composition when irradiated with radiation because the polarized covalent bond portion of the nonionic dispersant is easily cut by the photocatalytic action of the radiation and metal oxide. It is considered that the exposed portion of the film melts and exhibits high patterning properties.

  As this nonionic dispersant, polyoxyethylene alkyl phosphate ester, amide amine salt of high molecular weight polycarboxylic acid, ethylenediamine PO-EO condensate, polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, alkyl glucoside, polyoxyethylene Fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or fatty acid alkanolamides are preferred.

  As a polyoxyethylene alkyl phosphate ester, what is represented by the said Formula (2) is preferable. As a commercial item of the dispersant represented by the above formula (2), PLAAD ED151 manufactured by Enomoto Kasei Co., Ltd. and the like can be mentioned. According to the polyoxyethylene alkyl phosphate ester, the uniform dispersibility of the metal oxide particles can be further improved.

  As an amide amine salt of high molecular weight polycarboxylic acid, what is represented by the said Formula (3) is preferable. As a commercial item of the dispersant represented by the above formula (3), PLAAD ED211 manufactured by Enomoto Kasei Co., Ltd. may be mentioned. The uniform dispersibility of the metal oxide particles can be further improved by the amide amine salt of the high molecular weight polycarboxylic acid.

  The ethylenediamine PO-EO condensate is preferably represented by the above formula (4). As a commercial item of the dispersant represented by the above formula (4), Adeka Pluronic TR-701, TR-702, TR-704, etc. manufactured by Asahi Denka Kogyo Co., Ltd. may be mentioned. Even with the ethylenediamine PO-EO condensate, the uniform dispersibility of the metal oxide particles can be further improved.

  As polyoxyethylene alkyl ether, what is represented by following formula (5) is preferable.

（式（５）中、Ｒ^４は炭素数１〜２０のアルキル基である。ｖは１０〜３００の整数である。）Ｒ^４としては、炭素数１〜１２にアルキル基が特に好ましい。上記式（５）で表される分散剤の市販品としては、アデカ（株）製アデカトールＴＮ／ＳＯ／ＵＡシリーズ等が挙げられる。

(In the formula (5), ^{R 4} is .v an alkyl group having 1 to 20 carbon atoms is an integer of 10 to 300.) As ^{R 4} is particularly preferably an alkyl group having 1 to 12 carbon atoms. As a commercial item of a dispersing agent denoted by the above-mentioned formula (5), Adeka Co., Ltd. Adekatol TN / SO / UA series etc. are mentioned.

  As polyoxyethylene alkylphenol ether, what is represented by following formula (6) is preferable.

（式（６）中、Ｒ^５は炭素数１〜１２のアルキル基である。ｗは１０〜３００の整数である。）上記式（６）で表される分散剤の市販品としては、アデカ（株）製アデカトールＳＰ／ＰＣシリーズ等が挙げられる。

(In formula (6), R ⁵ is an alkyl group having 1 to 12 carbon atoms. W is an integer of 10 to 300.) As a commercial product of the dispersant represented by the above formula (6), ADEKA Examples include Adecatol SP / PC series manufactured by Co., Ltd.

  As alkyl glucoside, what is represented by following formula (7) is preferable.

（式（７）中、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、各々独立して、水素又は炭素数１〜１２のアルキル基である。）

(In formula (7), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms.)

  As polyoxyethylene fatty acid ester, what is represented by following formula (8) is preferable.

（式（８）中、Ｒ^１１は、炭素数１〜２０のアルキル基である。Ｒ^１２は、水素又は炭素数２〜１３のアシル基である。ｙは１０〜３００の整数である。）Ｒ^１１としては、炭素数１〜１２のアルキル基が特に好ましい。上記式（８）で表される分散剤の市販品としては、アデカ（株）製アデカエストールＯＥＧシリーズ、アデカエストールＴＬシリーズ等が挙げられる。

(In Formula (8), R ¹¹ is an alkyl group having 1 to 20 carbon atoms. R ¹² is hydrogen or an acyl group having 2 to 13 carbon atoms. Y is an integer of 10 to 300.) R ¹¹ is particularly preferably an alkyl group having 1 to 12 carbon atoms. As a commercial item of the dispersing agent represented by the said Formula (8), Adeka Co., Ltd. Adeka Estor OEG series, Adeka Estor TL series, etc. are mentioned.

  As a sucrose fatty acid ester, what is represented by following formula (9) is preferable.

（式（９）中、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９及びＲ^２０は各々独立して、水素又は炭素数２〜１３のアシル基である。）

(In formula (9), R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each independently hydrogen or an acyl group having 2 to 13 carbon atoms.)

  As sorbitan fatty acid ester, what is represented by following formula (10) is preferable.

（式（１０）中、Ｒ^２１は、−（ＣＨ_２ＣＨ_２Ｏ）_ｚ−Ｈで表される基である。ｚは、１０〜３００の整数である。）上記式（１０）で表される分散剤の市販品としては、アデカ（株）製アデカエストールＳシリーズ等が挙げられる。

(In formula (10), R ²¹ is a group represented by — (CH ₂ CH ₂ O) _z —H. Z is an integer of 10 to 300.) Examples of commercially available dispersants include ADEKA ESTOR S series manufactured by ADEKA Corporation.

  As polyoxyethylene sorbitan fatty acid ester, what is represented by following formula (11) is preferable.

（式（１１）中、Ｒ^２２、Ｒ^２３、Ｒ^２４は、各々独立して、水素又は−（ＣＨ_２ＣＨ_２Ｏ）_ｋ−Ｈで表される基である。ｋは、１０〜３００の整数である。）

(In the formula ^{(11), R 22, R} 23, R 24 are each independently hydrogen or _- is _(CH 2 CH 2 _O) groups represented by k -H .k, 10 to 300 (It is an integer.)

  As fatty acid alkanolamide, what is represented by following formula (12) is preferable.

（式（１２）中、Ｒ^２５は、炭素数１〜２０のアルキル基である。）Ｒ^２５としては、炭素数１〜１２のアルキル基が特に好ましい。上記式（１２）で表される分散剤の市販品としては、アデカ（株）製アデカソールシリーズ等が挙げられる。

(In the formula ^{(12), R 25} is an alkyl group having 1 to 20 carbon ^atoms.) As ^{R 25} is particularly preferably an alkyl group having 1 to 12 carbon atoms. Examples of commercially available dispersants represented by the above formula (12) include Adekasol series manufactured by Adeka Corporation.

  The blending amount of the component [D] dispersant is not particularly limited, but is preferably 0.1 parts by mass or more and 100 parts by mass or less, and 10 parts by mass with respect to 100 parts by mass of the metal oxide particles of the [B] component. More preferred is 60 parts by mass or less. When the blending amount of the dispersant of the component [D] is less than 0.1 parts by mass, the applicability of the composition due to the decrease in the dispersibility of the metal particles is lowered, and the patterning property may be lowered. On the other hand, when the blending amount exceeds 100 parts by mass, the positive radiation sensitive characteristics may be deteriorated. Moreover, there exists a possibility that the adhesiveness of the hardened | cured material obtained may fall because there are too many compounding of a dispersing agent.

Other optional components In addition to the above-mentioned components [A] to [D], the radiation-sensitive composition of the present invention can be used as other optional components as necessary within the range not impairing the effects of the present invention. ] A dispersion medium, [F] surfactant and the like can be contained.

[E] Component: Dispersion Medium The dispersion medium of the [E] component is not particularly limited as long as the metal oxide particles of the [B] component can be uniformly dispersed. The dispersion medium of the [E] component can effectively function the nonionic dispersant of the [C] component and can uniformly disperse the metal oxide particles of the [B] component. Depending on the type of the dispersion medium, It also functions as a solvent for other components [A].

  Examples of the dispersion medium include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; ethylene Ethers such as glycol monomethyl ether, propylene glycol monomethyl ether and diethylene glycol monobutyl ether; Amides such as dimethylformamide, N, N-dimethylacetoacetamide and N-methylpyrrolidone; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene can be used. Among these, acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene, xylene, methanol, isopropyl alcohol, and propylene glycol monomethyl ether are preferable, and methyl ethyl ketone and propylene glycol monomethyl ether are more preferable. A dispersion medium can be used 1 type or in mixture of 2 or more types.

  [E] The amount of the dispersion medium of the component can be appropriately set according to the use, but is preferably 100 parts by mass or more and 100,000 parts by mass or less with respect to 100 parts by mass of the metal oxide particles of the component [B]. 200 parts by mass or more and 10,000 parts by mass or less is particularly preferable.

[F] Component: Surfactant The surfactant of the [F] component can be added to improve the coating property of the radiation-sensitive composition, reduce coating unevenness, and improve the developability of the radiation irradiated part. . The surfactant of [F] component does not include the nonionic dispersant of [C] component. Examples of preferable surfactants include fluorine-based surfactants and silicone-based surfactants.

  Examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octa Ethylene 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, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether and other fluoroethers; sodium perfluorododecylsulfonate; 1,1,2, 2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexa Fluoroalkanes such as lurodecane; sodium fluoroalkylbenzenesulfonates; fluoroalkyloxyethylene ethers; fluoroalkylammonium iodides; fluoroalkylpolyoxyethylene ethers; perfluoroalkylpolyoxyethanols; perfluoroalkylalkoxylates And fluorine-based alkyl esters.

  Commercially available products of these fluorosurfactants include F-top EF301, 303, 352 (manufactured by Shin-Akita Kasei Co., Ltd.), MegaFuck F171, 172, 173 (manufactured by Dainippon Ink Co., Ltd.), Florard FC430, 431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC-101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), FTX-218 (manufactured by Neos Co., Ltd.) Etc.

  Examples of silicone-based surfactants are commercially available under the trade names SH200-100cs, SH28PA, SH30PA, ST89PA, SH190, SH8400 FLUID (manufactured by Toray Dow Corning Silicone), organosiloxane polymer KP341 (Shin-Etsu) Chemical Industry Co., Ltd.).

  [F] The amount of the surfactant used is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.05 parts by mass or more and 5 parts by mass with respect to 100 parts by mass of the component [A]. It is as follows. [F] By making the usage-amount of surfactant into 0.01 mass part or more and 10 mass parts or less, the applicability | paintability of a radiation sensitive composition can be optimized.

Radiation sensitive composition The radiation sensitive composition of the present invention comprises the above-mentioned [A] component siloxane polymer, [B] component metal oxide particles, [C] component radiation sensitive acid generator or radiation sensitive. It is prepared by mixing a base generator, and if necessary, a dispersant for the [D] component and other optional components at a predetermined ratio. Usually, the radiation-sensitive composition is prepared by mixing the metal oxide particles of the [B] component, the dispersant of the [D] component, and the dispersion medium of the [E] component at a predetermined ratio to obtain a dispersion. In this dispersion, the siloxane polymer of the [A] component, the radiation sensitive acid generator or the radiation sensitive base generator of the [C] component, and optional components as necessary are mixed to form a dispersion state. The radiation sensitive composition can be prepared.

  Dispersion during the preparation of the above dispersion is usually continued at a peripheral speed of 5 to 15 m / s using a paint shaker, SC mill, annular mill, pin mill, etc. until no decrease in particle size is observed. It is good to be done by doing. This duration is usually several hours. In this dispersion, it is preferable to use dispersed beads such as glass beads. The bead diameter is not particularly limited, but is preferably 0.05 to 0.5 mm, more preferably 0.08 to 0.5 mm, and particularly preferably 0.08 to 0.2 mm.

Formation of cured film (protective film for liquid crystal display element, interlayer insulating film or spacer, protective film for semiconductor or interlayer insulating film, LED lens material, etc.) Next, using the above radiation sensitive composition, A method for forming a patterned transparent cured film (a protective film for a liquid crystal display element, an interlayer insulating film or a spacer, a semiconductor protective film or an interlayer insulating film, an LED lens material, or the like) on a substrate will be described. The method includes the following steps.

(1) The process of forming the coating film of the radiation sensitive composition of this invention on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A step of developing the coating film irradiated with radiation in step (2), and (4) A step of heating the coating film developed in step (3).

(1) Step of forming a coating film of a radiation sensitive composition on a substrate In the step (1), after applying the radiation sensitive composition of the present invention on a substrate, the coated surface is preferably heated (prebaked). By removing the solvent, a coating film is formed. Examples of the substrate that can be used include glass, quartz, silicon, and resin. Specific examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, a ring-opening polymer of cyclic olefin, and hydrogenated products thereof.

  The coating method of the composition dispersion is not particularly limited, and for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or the like can be adopted. it can. Among these coating methods, a spin coating method or a slit die coating method is particularly preferable. Prebaking conditions vary depending on the type of each component, the blending ratio, and the like, but can be preferably about 70 to 120 ° C. for about 1 to 10 minutes.

(2) Step of irradiating at least a part of the coating film In the step (2), at least a part of the formed coating film is exposed. In this case, when exposing to a part of coating film, it exposes normally through the photomask which has a predetermined pattern. As radiation used for exposure, visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like can be used, for example. Among these radiations, radiation having a wavelength in the range of 190 to 450 nm is preferable, and radiation containing ultraviolet light of 365 nm is particularly preferable.

The amount of exposure in this step is preferably 100 to 10,000 J / m ² , more preferably 500 to 500, as a value measured with a luminometer (OAI model 356, manufactured by OAI Optical Associates Inc.) at a wavelength of 365 nm. 6,000 J / m ² .

(3) Development step In the above step (3), the exposed coating film is developed, so that an unnecessary portion (in the case of a positive type, a portion irradiated with radiation. In the case of a negative type, a portion not irradiated with radiation). ) Is removed to form a predetermined pattern. The developer used in the development step is preferably an aqueous solution of an alkali (basic compound). Examples of alkalis include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. be able to.

  In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to such an alkaline aqueous solution. The concentration of the alkali in the alkaline aqueous solution is preferably from 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability. As a developing method, for example, an appropriate method such as a liquid filling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time varies depending on the composition of the radiation-sensitive composition, but is preferably about 10 to 180 seconds. Following such development processing, for example, washing with running water is performed for 30 to 90 seconds, and then a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.

(4) Heating step In the above step (4), the patterned thin film is heated at a relatively high temperature using a heating device such as a hot plate or an oven, thereby promoting the condensation reaction of the above [A] component. A cured product can be obtained. The heating temperature in the said process is 120-250 degreeC, for example. Although heating time changes with kinds of heating apparatus, for example, when performing a heating process on a hotplate, it can be set to 30 to 90 minutes when performing a heating process in an oven. The step baking method etc. which perform a heating process 2 times or more can also be used. In this way, a patterned thin film corresponding to the target cured product can be formed on the surface of the substrate.

Cured film (protective film for liquid crystal display element, interlayer insulating film or spacer, protective film for semiconductor or interlayer insulating film, LED lens material, etc.)
The cured film thus formed has high transparency and a high refractive index. The refractive index of the cured film obtained from the composition of the present invention has a high value of 1.5 or more, and further 1.6 or more, although it varies depending on the blending ratio of each component.

  Further, the cured film thus patterned is suitably used as a protective film for a liquid crystal display element, an interlayer insulating film or spacer, a semiconductor protective film or interlayer insulating film, an LED lens material, and the like. The thickness of these cured films is preferably 0.1 to 8 μm, more preferably 0.1 to 6 μm, and still more preferably 0.1 to 4 μm. These cured films formed from the radiation-sensitive composition of the present invention have transparency and adhesion, and have a high refractive index, as will be apparent from the following examples.

  The radiation-sensitive composition of the present invention is not limited to the use of the above-described cured film formed by patterning, for example, a semiconductor sealing material, a semiconductor underfill material, a circuit substrate material, a planarizing material, It can be used as a circuit board protecting material, an etching resist material, a plating resist material, or a liquid crystal sealing material. These cured films can be obtained in a short time by being formed from the radiation-sensitive composition of the present invention, and are excellent in heat resistance, adhesion, electrical insulation and the like.

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

  The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the hydrolysis-condensation product obtained from the following synthesis examples were measured by gel permeation chromatography (GPC) according to the following specifications.

Apparatus: GPC-101 (made by Showa Denko KK)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 (manufactured by Showa Denko KK) combined Mobile phase: Tetrahydrofuran

[Synthesis Example 1]
In a vessel equipped with a stirrer, 144 parts by mass of propylene glycol monomethyl ether was charged, followed by 13 parts by mass of methyltrimethoxysilane (MTMS), 5 parts by mass of γ-glycidoxypropyltrimethoxysilane (GPTMS), phenyltrimethylsilane. 6 parts by mass of methoxysilane (PTMS) was charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 7 parts by mass of ion exchange water was charged, heated to 75 ° C., and held for 3 hours. Next, 25 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Further, the temperature of the solution was set to 40 ° C., and evaporation was performed while maintaining the temperature, thereby removing water and alcohol generated by hydrolysis condensation. Thus, a siloxane polymer (A-1) was obtained. The number average molecular weight (Mn) of the obtained hydrolysis-condensation product was 2,500, and the molecular weight distribution (Mw / Mn) was 2.

[Synthesis Example 2]
In a vessel equipped with a stirrer, 144 parts by mass of propylene glycol monomethyl ether was charged, followed by 13 parts by mass of methyltrimethoxysilane (MTMS) and 11 parts by mass of tetramethoxysilane (TMOS), and the solution temperature reached 60 ° C. Heated until. After the solution temperature reached 60 ° C., 7 parts by mass of ion exchange water was charged, heated to 75 ° C., and held for 3 hours. Next, 25 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Further, the temperature of the solution was set to 40 ° C., and evaporation was performed while maintaining the temperature, thereby removing water and alcohol generated by hydrolysis condensation. Thus, a siloxane polymer (A-2) was obtained. The number average molecular weight (Mn) of the obtained hydrolysis-condensation product was 2,500, and the molecular weight distribution (Mw / Mn) was 2.

Preparation of radiation sensitive composition [Example 1]
[D] Component (D-1) 3 parts by weight of polyoxyethylene alkyl phosphate ester as a dispersant, [E] component dispersion medium 90 parts by weight of methyl ethyl ketone are mixed and stirred with a homogenizer. As metal oxide particles, 7 parts by mass of (B-1) zirconium oxide particles (ZrO ₂ particles) were gradually added over about 10 minutes. Stir for about 15 minutes after adding the particles. The obtained slurry was dispersed using an SC mill to obtain a dispersion.

  In a solution containing the siloxane polymer obtained in the synthesis example as the [A] component (an amount corresponding to 100 parts by mass (solid content) of the siloxane polymer), 100 parts by mass of the dispersion and (C-1) as the [C] component A radiation-sensitive composition was prepared by adding 6 parts by mass of a photoacid generator and 0.3 parts by mass of SH8400 FLUID (manufactured by Toray Dow Corning Silicone Co., Ltd.), which is a silicon surfactant, as the [F] component.

[Examples 2 to 18 and Comparative Examples 1 to 4]
A radiation-sensitive composition was prepared in the same manner as in Example 1 except that the types and amounts of the components [A] to [F] were as shown in Tables 1 and 2. In addition, the component in Table 1 and Table 2 is as follows.

(C-1) Photoacid generator: 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate (C-2) Photobase generator: 2-nitrobenzylcyclohexylcarbamate (D- 1) Polyoxyethylene alkyl phosphate ester: a compound in which p = about 9, q = about 13, x = about 3 in the above formula (2) (D-2) amidoamine salt: in the above formula (3), number average Amidoamine salt of high molecular weight polycarboxylic acid with molecular weight of 40,000 (Plaad ED211 manufactured by Enomoto Kasei Co., Ltd.)
(D-3) Ethylenediamine PO-EO condensate: ethylenediamine PO-EO condensate of the above formula (4) (Adeka Pluronic TR-702, manufactured by Asahi Denka Kogyo Co., Ltd.)
(D-4) Polyoxyethylene alkyl ether: a compound in which R ⁴ is a methyl group in the above formula (5), and v = about 200. (D-5) Polyoxyethylene alkyl phenyl ether: In the above formula (6), R ⁵ Is a methyl group, n = about 200 compound (D-6) alkyl glucoside: In the above formula (7), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are n-butyl groups (D- 7) Polyoxyethylene fatty acid ester: a compound in which R ¹¹ is an ethyl group, R ¹² is an acetyl group, and y = about 200 in the above formula (8). (D-8) Sucrose fatty acid ester: in the above formula (9) compound ^R 13 ^{to R 20} is an ethyl group (D-9) sorbitan fatty acid esters: in the above formula (10), z = compound is about 100 (D-10) polyoxyethylene In ^{R 22} in the formula (11) is ^H, the compound ^{R 23} and ^{R 24} is k = approximately 100 groups (D-11) fatty acid alkanolamide: Nsorubitan fatty acid esters ^{R 25} in formula (12) Compounds that are hexyl groups

Evaluation of Physical Properties Using the radiation-sensitive composition prepared as described above, various properties as the composition and a cured film were evaluated as follows. The results are shown in Tables 1 and 2.

[Evaluation of coating properties of radiation-sensitive resin composition]
After the prepared composition solution is applied on a silicon substrate using a spinner, it is pre-baked on a hot plate at 100 ° C. for 2 minutes to form a coating film, and the film thickness on the silicon substrate is 4 μm. Formed.

  The surface of the film was illuminated with a sodium lamp, and the coated film surface was visually confirmed. If streaky unevenness or haze unevenness (cloud-like unevenness) can be confirmed clearly, it is indicated as “X”, if it is slightly confirmed, “△”, and if it is hardly confirmed, it is indicated as “◯”.

[Evaluation of patterning property of radiation-sensitive composition]
A mask having a 6.0 μm line-and-space (one-to-one) pattern is applied to the coating film obtained above using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. Then, exposure was performed while changing the exposure time, and then development was performed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 80 seconds by a puddle method. Next, running water was washed with ultrapure water for 1 minute and dried to form a pattern on the silicon substrate. After the pattern is formed, if the exposed portion is patterned, it is a negative type. If the unexposed portion is patterned, it can be determined as a positive type. Further, the patterning property was evaluated with ◎ when the pattern was formed very clearly, ◯ when the pattern was clear, Δ when the pattern was slightly unclear, and x when the pattern was unclear. In addition, in the table, those that cannot be determined whether the pattern is unclear or positive type or negative type are indicated by "-".

[Evaluation of light transmittance (transparency) of cured film]
A coating film was formed on the glass substrate in the same manner except that a glass substrate (“Corning 7059” (manufactured by Corning)) was used in place of the silicon substrate in the “evaluation of patterning”. Then, the cured film was obtained by heating at 220 degreeC in a clean oven for 1 hour. The light transmittance of the glass substrate on which this cured film was formed was measured at a wavelength in the range of 400 to 800 nm using a spectrophotometer “150-20 type double beam” (manufactured by Hitachi, Ltd.). When the minimum light transmittance is 92% or more, it can be said that the light transmittance is good. In the evaluation of the light transmittance, since the patterning of the film to be formed is unnecessary, the development process was omitted, and only the coating film forming process, the radiation irradiation process, and the heating process were performed.

[Evaluation of refractive index of cured film]
Using an Abbe refractometer, the refractive index at 25 ° C. and 633 nm of the cured film obtained by the method of “Evaluation of light transmittance (transparency) of the cured film” was measured.

[Evaluation of adhesion of cured film to ITO (indium tin oxide) substrate]
A cured film was formed in the same manner as in “Evaluation of light transmittance” except that a substrate with ITO was used, and a pressure cooker test (120 ° C., humidity 100%, 4 hours) was performed. Thereafter, the 8.5.3 adhesive cross-cut tape method of JIS K-5400-1990 was performed to determine the number of cross-cuts remaining in 100 cross-cuts, and the ITO adhesion of the protective film was evaluated. When the number of grids remaining in 100 grids is 80 or less, it can be said that the ITO adhesion is poor.

  As is apparent from the results of Tables 1 and 2, the radiation-sensitive compositions of Examples 1 to 18 containing the components [A] to [C] are excellent in patterning property and exhibit positive radiation-sensitive characteristics. The obtained cured film had a high refractive index and adhesiveness. In particular, the compositions of Examples 1 to 17 containing a nonionic dispersant as the [D] component had extremely high patterning properties and excellent coating properties.

  As described above, the radiation-sensitive composition of the present invention has high coatability and patternability, and the obtained cured product has a high refractive index in addition to high transparency and adhesion. Therefore, the radiation-sensitive composition of the present invention can be used as a protective film for liquid crystal display elements, an interlayer insulating film or spacer, a semiconductor protective film or interlayer insulating film, an LED lens material, and the like. The radiation-sensitive composition of the present invention further includes a semiconductor sealing material, a semiconductor underfill material, a circuit substrate material, a planarizing material, a circuit board protecting material, an etching resist material, and a plating resist. It can be used as a material for sealing, a liquid crystal sealing material, and the like.

Claims (5)

A radiation-sensitive composition for forming a transparent cured film, comprising [A] a siloxane polymer,
[B] metal oxide particles ,
[C] a radiation sensitive acid generator or a radiation sensitive base generator ; and
[D] a nonionic dispersant ,
The [B] metal oxide particles, di- Rukoniumu, at least one oxide particles radiation-sensitive composition is a metal selected from titanium and zinc or Ranaru group. [A] The radiation-sensitive composition according to claim 1, wherein the siloxane polymer is a hydrolysis-condensation product of a hydrolyzable silane compound represented by the following formula (1).
_{^{(R 1) n -Si- (OR}} 2) 4-n (1)
(In formula (1), each R ¹ is independently hydrogen or a non-hydrolyzable organic group having 1 to 20 carbon atoms. R ² is each independently hydrogen or alkyl having 1 to 6 carbon atoms. Group, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, n is an integer of 0 to 3). [D] The nonionic dispersant is a compound represented by the following formula (2), formula (3) or formula (4), polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, alkyl glucoside, polyoxyethylene fatty acid ester The radiation-sensitive composition according to claim 1, which is sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester or fatty acid alkanolamide.

(In the formula (2), ^{R 3} is, _{independently, C q H 2q + 1 -CH} 2 O- (CH 2 CH 2 O) p -CH 2 CH 2 O- in which .p is 8 to 10, q is 12-16, x is an integer of 1-3.)

(In Formula (3), r and s are numbers selected so that the polystyrene-equivalent number average molecular weight determined by gel permeation chromatography is 10,000 to 40,000.)

(In formula (4), t and u are numbers selected such that the polystyrene-equivalent number average molecular weight determined by gel permeation chromatography is 1,000 to 30,000.) (1) The process of forming the coating film of the radiation sensitive composition of Claim 1, Claim 2 or Claim 3 on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A process for developing the coating film irradiated with radiation in step (2), and (4) a method for forming a transparent cured film, comprising the step of heating the coating film developed in step (3). The transparent cured film formed from the radiation sensitive composition of Claim 1, Claim 2 or Claim 3 .