TWI483070B - Radiation-sensitive composition, cured film and forming method thereof - Google Patents

Description

Radiation-sensitive composition and cured film and method of forming same

The present invention relates to a radiation-sensitive composition suitable as a material for forming a protective film or an interlayer insulating film of a display element, and a cured film formed of the radiation-sensitive composition and a method for forming the same.

A display element such as a liquid crystal display element, an integrated circuit element, a solid-state imaging device, or an organic electroluminescence (EL) is provided to prevent deterioration or damage of an electronic component represented by a touch panel. A protective film or a cured film such as an interlayer insulating film for maintaining insulation between wirings arranged in a layer. In order to form such a cured film, a radiation-sensitive composition is always used. For example, a coating film on which a radiation-sensitive composition can be formed on a substrate can be irradiated with radiation through a photo mask having a predetermined pattern (hereinafter referred to as " Exposure"), development is carried out using an organic alkali developing solution to dissolve and remove an unnecessary portion, and then post-bake, thereby forming a cured film.

The cured film used as the protective film of the touch panel is required to have high adhesion to the wiring of the touch panel element, smooth film, high hardness, excellent scratch resistance, and no discoloration under high temperature conditions. Transparency (heat-resistant transparency), no cracks (cracks) (heat-resistant cracking property) under high-temperature conditions, excellent sensitivity to radiation, and good pattern (developability) without developing a residual film can be formed.

On the other hand, in the cured film used as the interlayer insulating film, it is necessary to form a pattern of contact holes for wiring. Therefore, in addition to the required characteristics of the protective film, it is further required to be high-definition with high resolution. A pattern image (high resolution) or the like is formed.

In the past, the component of the radiation-sensitive composition was mainly made of an acrylic resin, but in recent years, a polyoxyalkylene-based material having more excellent heat resistance and transparency than the acrylic resin has been attracting attention (Patent Document 1 to Patent Literature) 3). However, since the polyoxyalkylene-based material has insufficient adhesion to an indium tin oxide (ITO) substrate and is likely to be cracked, it has a problem of being practical as a protective film. In addition, the material for forming an interlayer insulating film of a liquid crystal display element is being developed in the form of a negative-type radiation-sensitive composition which is advantageous in terms of cost (Patent Document 4). However, such a negative-type radiation-radiating composition is difficult to form and has practical use. A contact hole of a level aperture that can be used. Therefore, in order to form the interlayer insulating film of the display element, a positive-type radiation-sensitive composition is widely used in terms of the superiority of the formation of the contact hole (Patent Document 5).

Further, the following radiation sensitive composition has been proposed which is a composition comprising a copolymer containing an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride and another unsaturated compound, a polymerizable unsaturated compound, and a photopolymerization initiator. In the form of an additive, a trace amount of a oxirane oligomer having an oxiranyl group, an oxetanyl group or a fluorenyl group is contained in an extremely small amount, and the radiation-sensitive linear composition can be described. A spacer suitable for forming a display element is suitably used (Patent Document 6). However, the spacer of the display element is different from the use of the protective film or the interlayer insulating film, and thus it is difficult to sufficiently satisfy all the required characteristics of the protective film or the interlayer insulating film.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-001648

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2006-178436

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2008-248239

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2000-162769

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2001-354822

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2008-233518

The required characteristics of the protective film and the interlayer insulating film are as described above, and the number of repeating portions is large. However, the actual situation is that a wide variety of radiation sensitive compositions are used depending on the purpose or step. If a cured film such as a protective film or an interlayer insulating film can be formed by using a radiation sensitive composition, and the cured film can be used and the pattern transfer method is set to a negative type, it is extremely advantageous in terms of cost. Therefore, it has been strongly desired to develop a negative-type radiation-sensitive composition that can form both a protective film and an interlayer insulating film.

In addition, in the development, the alkali developer usually uses Tetramethyl Ammonium Hydroxide (TMAH), and it is desired to develop an inorganic alkali developing solution from the viewpoint of cost reduction and productivity improvement. Radiation-sensitive composition.

Accordingly, an object of the present invention is to provide a radiation sensitive composition which can form a cured film which has a high level and a good balance and which has the above-mentioned required characteristics for a protective film or an interlayer insulating film, and utilizes an inorganic alkali developing solution. Can also be developed. Further, another object of the present invention is to provide a cured film which has the above-mentioned required characteristics for a protective film and an interlayer insulating film at a high level and with a good balance, and a method for forming the same.

In order to solve the above problems, first, the present invention provides a radiation sensitive linear composition comprising the following components [A ¹ ], component [B], and component [C]:

[A ^1] that the tetraethyl orthosilicate or partial hydrolyzate thereof, the following formula (1) hydrolyzable alkoxy silicon compound represented by or its partial hydrolysis, and (2) an alkoxy hydrolyzable silicon compound represented by the following formula or a polyoxyalkylene obtained by partial hydrolysis of the hydrolyzate;

[B] a compound having two or more ethylenically unsaturated groups (excluding the component [A ¹ ]);

[C] Photoradical polymerization initiator.

[Chemical 1]

[Chemical 2]

In the formula (1), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and R ² represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms or a (meth)acryloxy group, m. An integer of 1 to 3 is represented, and n represents an integer of 0 to 6. In the formula (2), R ³ represents an alkyl group having 1 to 6 carbon atoms, x represents an integer of 1 to 3, y represents an integer of 1 to 6, and z represents an integer of 0 to 3]

Secondly, the present invention provides a radiation sensitive linear composition comprising the following components [A ² ], component [B] and component [C]:

[A ² ] a polyoxyalkylene having a SiO ₂ unit, a structural unit represented by the following formula (1a), and a structural unit represented by the following formula (2a);

[B] a compound having two or more ethylenically unsaturated groups (excluding the component [A ² ]);

[C] Photoradical polymerization initiator.

[Chemical 3]

[Chemical 4]

In the formula (1a), R ² represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms or a (meth)acryloxy group, wherein m represents an integer of 1 to 3, and n represents 0 to 6 The integer. In the formula (2a), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, x represents an integer of 1 to 3, y represents an integer of 1 to 6, and z represents an integer of 0 to 3]

Third, the present invention provides a cured film formed using the above-described radiation sensitive composition.

Fourth, the present invention provides a method for forming a cured film, comprising the following steps (1) to (4);

(1) a step of forming a coating film of the above-described radiation sensitive composition on a substrate;

(2) a step of irradiating at least a part of the coating film formed in the step (1) with radiation;

(3) a step of developing the radiation-coated coating film in the step (2) using an alkali developing solution;

(4) a step of heating the developed coating film in the step (3).

[Effects of the Invention]

According to the present invention, it is possible to provide a cured film which can effectively form various properties such as heat resistance, hardness, scratch resistance, heat crack resistance, adhesion, sensitivity and developability at a high level and with a good balance. The radiation sensitive composition. Further, since the radiation sensitive composition of the present invention has sufficient resolution, it can form fine contact holes, and can be developed by using an inorganic alkali developing solution.

Therefore, the cured film formed using the radiation sensitive composition of the present invention is extremely useful as a protective film of a touch panel of a display element and an interlayer insulating film of a display element.

Radiation-sensitive composition

The radiation sensitive composition of the present invention contains the component [A ¹ ] or the component [A ² ], the component [B], and the component [C]. Hereinafter, each component will be described in detail. In the following description, the component [A ¹ ] and the component [A ² ] are collectively described as the component [A].

Ingredient [A]

The component [A ¹ ] is a hydrolyzable decane compound represented by the following formula (1) or a partially hydrolyzed product thereof (hereinafter also referred to as "tetraethoxy decane" or a partial hydrolyzate thereof (hereinafter also referred to as "TEOS"). The "polycarbonate" obtained by hydrolysis-condensation of the hydrolyzable decane compound represented by the following formula (2) or a partially hydrolyzed product (hereinafter also referred to as "compound (2)"). By containing the component [A], the solubility in the alkali developer, particularly the inorganic alkali developer used in the development step can be improved, the developability can be improved, and the heat-resistant transparency and resistance of the obtained cured film can be improved. Scratch. Here, the "partially hydrolyzed substance" in the present specification means a siloxane compound having at least one, preferably two or more alkoxy groups remaining in a molecule formed by a hydrolysis condensation reaction of an alkoxy group ( The number of germanium atoms is from 2 to 100, preferably from about 2 to about 30, of a nonoxyl oligomer.

[Chemical 5]

[Chemical 6]

In the formula (1), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and R ² represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms or a (meth)acryloxy group, m. An integer of 1 to 3 is represented, and n represents an integer of 0 to 6.

In the formula (2), R ³ represents an alkyl group having 1 to 6 carbon atoms, x represents an integer of 1 to 3, y represents an integer of 1 to 6, and z represents an integer of 0 to 3. ]

First, the definitions of the symbols in the equations (1) and (2) will be described.

The alkyl group of R ¹ and R ³ may be any of a linear chain, a branched chain, and a cyclic chain. The alkyl group of R ¹ and R ³ has 1 to 6 carbon atoms, and the carbon number is preferably 1 to 4, more preferably 1 or 2, from the viewpoint of reactivity of hydrolysis condensation. Specific examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a secondary butyl group, a tertiary butyl group, a pentyl group, a hexyl group, a cyclohexyl group and the like. Among them, a methyl group or an ethyl group is particularly preferred. Furthermore, in the case where a plurality of R ¹ are present in the same molecule, the R ^{1 's} may be the same or different. The same is true for R ³ .

The alkyl group of R ² may be any of a linear chain, a branched chain, and a cyclic chain. The alkyl group of R ² has a carbon number of from 1 to 20, preferably from 1 to 10, more preferably from 1 to 6. Specifically, in addition to the alkyl group exemplified in R ¹ and R ³ , a n-heptyl group, an n-octyl group, a 2-ethylhexyl group, a n-decyl group, a n-decyl group, a n-undecyl group, and a positive tenthing may be mentioned. Dialkyl, n-tridecyl, n-tetradecyl, n-hexadecyl, cycloheptyl, cyclooctyl and the like.

The aryl group of R ² means a monocyclic to tricyclic aromatic hydrocarbon group having 6 to 14 carbon atoms, and specific examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthryl group. Among them, a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred.

The alkyl group and the aryl group of R ² may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, a nitro group, a cyano group, and an alkoxy group having 1 to 6 carbon atoms. Further, the position and the number of the substituents are arbitrary, and in the case of having two or more substituents, the substituents may be the same or different. The halogen atom may, for example, be a fluorine atom, a bromine atom, a chlorine atom or an iodine atom, and among them, a fluorine atom is preferred. The halogen atom may be substituted with a part or all of the hydrogen atom of the alkyl group and the aryl group, and is preferably all substituted. Specific examples of the halogen-substituted alkyl group include perfluoroalkyl groups such as a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, and a perfluorocyclopropyl group. Further, examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a n-propoxy group, and an isopropoxy group.

The (meth) propylene fluorenyl group of R ² is a concept including an acryloxy group and a methacryloxy group.

Among them, R ^{2 is} preferably an alkyl group having 1 to 6 carbon atoms, a phenyl group or a (meth)acryloxy group. Furthermore, in the case where a plurality of R ² are present in the same molecule, the R ² may be the same or different.

m is an integer of 1 to 3, preferably 1 or 2, more preferably 1.

n is an integer of 0 to 6, preferably an integer of 0 to 3, more preferably 0 or 3.

x is an integer of 1 to 3, preferably 1 or 2, more preferably 1.

y is an integer of 1 to 6, preferably an integer of 1 to 3, more preferably 3.

z is an integer of 0 to 3, preferably 0 or 1, more preferably 0.

Next, the constituent components of the polyoxyalkylene of the component [A ¹ ] will be described.

The component [A ¹ ] contains TEOS as an essential component. TEOS is a polyfunctional decane compound having four hydrolyzable groups. It is predicted that when the polyoxyalkylene contains a structural unit derived from TEOS, the adhesion to the substrate is increased by interaction with a hydroxyl group on the surface of a metal substrate such as ITO, and the crosslinking of the polyoxane can be further improved. With the joint density, the obtained cured film can have a higher hardness, but since it becomes brittle, it is liable to be cracked and has poor scratch resistance. In contrast to such a prediction, in the present invention, it has been found that the compound (1) and the compound (2) described later are combined in TEOS to form a polyoxyalkylene, and further contain the component [B], whereby even at a high concentration. In addition to TEOS, it is possible to unexpectedly obtain a cured film which is excellent in not only hardness but also substrate adhesion, and also excellent in scratch resistance and crack resistance. This situation is completely unpredictable based on previous insights.

From the viewpoint of improvement in hardness, adhesion, scratch resistance, and heat crack resistance, the TEOS addition ratio is preferably 5 mol% (% by mole) to 75 mol%, more preferably, based on the total amount of the raw material compounds. It is 10 mol% to 70 mol%, and more preferably 25 mol% to 65 mol%.

The component [A ¹ ] further contains the compound (1) as an essential component. Compound (1) suppresses an excessive increase in crosslink density caused by TEOS, maintains a moderate crosslink density, and contributes to an improvement in crack resistance and scratch resistance.

The compound (1) includes a decane compound in which m is 1, a decane compound in which m is 2, and a decane compound in which m is 3. Specific examples thereof include the following compounds. Further, the compound (1) may be used alone or in combination of two or more.

Examples of the decane compound having m of 1 include methyl trimethoxy silane, methyl triethoxy decane, methyl tri-isopropoxy decane, methyl tributoxy decane, and ethyl. Trimethoxy decane, ethyl triethoxy decane, ethyl tri-isopropoxy decane, ethyl tributoxy decane, butyl trimethoxy decane, decyl trimethoxy decane, etc. having one carbon number a hydrolyzable decane compound having 1 to 20 alkyl groups; a hydrolyzable decane compound having 1 halogen-substituted alkyl group having 1 to 20 carbon atoms such as trifluoropropyl trimethoxy silane; a hydrolyzable decane compound having one aryl group having 6 to 14 carbon atoms such as phenyl trimethoxy silane or phenyltriethoxysilane; 3-methylpropenyloxypropyltrimethoxydecane (3) -methacryloyloxy propyl trimethoxy silane), 3-methacryloxypropyltriethoxydecane, 3-methylpropenyloxypropyltripropoxydecane, 3-propenyloxypropyltrimethoxy Decane, 3-propenyloxypropyltriethoxydecane, 3-propenyloxypropyl Silane compound hydrolyzable silane-propoxy group and the like having a (meth) Bing Xixi group.

The decane compound in which m is 2 may, for example, be a hydrolyzable decane compound having two alkyl groups having 1 to 20 carbon atoms such as dimethyldimethoxydecane or dibutyldimethoxydecane; a hydrolyzable decane compound having two aryl groups having 6 to 14 carbon atoms such as oxydecane; 3-methylpropenyloxypropylmethyldimethoxydecane, 3-propenyloxypropylmethyldi An alkoxydecane compound having a (meth)acryloxycarbonyl group and an alkyl group having 1 to 20 carbon atoms such as methoxydecane; 3-methylpropenyloxypropylphenyldimethoxydecane, 3- An alkoxydecane compound having a (meth) propylene fluorenyloxy group and an aryl group having 6 to 14 carbon atoms such as acryloxypropyl phenyl dimethoxy decane; 3,3'-dimethyl propylene oxime An alkoxydecane compound having two (meth) propylene fluorenyloxy groups such as propyldimethoxydecane and 3,3'-dipropylenemethoxypropyldimethoxydecane.

Examples of the decane compound having m of 3 include three alkyl groups having 1 to 20 carbon atoms such as tributylmethoxydecane, trimethylmethoxydecane, trimethylethoxysilane, and tributylethoxysilane. Hydrolyzable decane compound having three aryl groups having 6 to 14 carbon atoms; 3,3',3"-trimethylpropenyloxypropyl group A hydrolyzable decane compound having three (meth) acryloxy groups, such as oxydecane or 3,3',3"-tripropylene methoxypropyl methoxy decane.

Among these compounds (1), a hydrolyzable decane compound having an alkyl group having 1 to 6 carbon atoms, a hydrolyzable decane compound having an aryl group having 6 to 14 carbon atoms, and (meth) propylene decyloxy group are preferable. The hydrolyzable decane compound is particularly preferably a decane compound in which m of the above formula (1) is 1.

Specific examples of a suitable compound (1) include methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, and butyltrimethoxydecane. An alkoxydecane compound having one alkyl group having 1 to 6 carbon atoms; an alkoxydecane compound having one aryl group having 6 to 14 carbon atoms such as phenyltrimethoxydecane; 3-propenyloxypropyl group Trimethoxy decane, 3-methacryloxypropyltrimethoxydecane, 3-propenyloxypropyltriethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, etc. An alkoxydecane compound having one (meth) propylene fluorenyloxy group.

From the viewpoint of improvement in heat-resistant transparency, hardness, scratch resistance, heat crack resistance, adhesion, sensitivity, resolution, and developability, the total addition ratio of the compound (1) is preferably based on the total amount of the raw material compounds. It is 10 mol% to 80 mol%, more preferably 10 mol% to 75 mol%, and still more preferably 15 mol% to 70 mol%.

In the present invention, in the above-mentioned suitable compound (1), a hydrolyzable decane compound selected from an alkyl group having a carbon number of 1 to 6 is preferably used from the viewpoint of further improving the scratch resistance and the heat-resistant crack resistance. And at least one decane compound (hereinafter also referred to as "decane compound (1b ¹ ))) of the hydrolyzable decane compound having an aryl group having 6 to 14 carbon atoms, particularly preferably those decane compounds (1b ¹ ) The decane compound in which m of the above formula (1) is 1.

Further, from the viewpoint of further improving the sensitivity and the developability, among the above-mentioned suitable compounds (1), a hydrolyzable decane compound having a (meth) acryloxy group is preferably used, and among the decane compounds, particularly preferred The decane compound in which m of the above formula (1) is 1. The hydrolyzable decane compound having a (meth) acryloxy group is preferably a hydrolyzable decane compound (hereinafter also referred to as "decane compound (1c ¹ )") having a methacryloxy group having a methoxy group, and having a propylene group. At least one of a hydrolyzable decane compound (hereinafter also referred to as "decane compound (1d ¹ )") of a decyloxy group is more preferably a decane compound (1c ¹ ) and a decane compound (1d ¹ ). Further, the hydrolyzable decane compound having a (meth) propylene fluorenyloxy group is preferably used together with the decane compound (1b ¹ ).

When the decane compound (1b ¹ ) is used as the compound (1), the total amount of the decane compound (1b ¹ ) is added to the total amount of the raw material compounds from the viewpoint of further improving the scratch resistance and the heat-resistant crack resistance. The ratio is preferably from 10 mol% to 80 mol%, more preferably from 15 mol% to 75 mol%, and still more preferably from 30 mol% to 70 mol%.

In view of the fact that the sensitivity and the resolution are further improved, the total addition ratio of the hydrolyzable decane compound having a (meth) propylene oxime group is preferably from 5 mol% to 25 mol%, based on the total amount of the raw material compounds. Preferably, it is 10 mol% to 20 mol%.

In the case where the decane compound (1c ¹ ) and the decane compound (1d ¹ ) are used in combination, the addition ratio (1c ¹ /1d ¹ ) of the two is further improved from the viewpoint of further improving the scratch resistance and the heat crack resistance. The molar ratio is preferably from 0.05 to 3, more preferably from 0.2 to 1.5, still more preferably from 0.3 to 1.

The component [A ¹ ] further contains the compound (2) as an essential component. The compound (2) is a component which suppresses an increase in excessive crosslinking density caused by TEOS, contributes to improvement of heat crack resistance and scratch resistance, and contributes to improvement in developability.

The compound (2) may, for example, be a decane compound in which x is 1, a decane compound in which x is 2, or a decane compound in which x is 3. Specific examples thereof include the following compounds. Further, the compound (2) may be used alone or in combination of two or more.

Examples of the decane compound wherein x is 1 include 2-trimethoxy silyl ethyl succinic anhydride, 3-trimethoxydecyl propyl succinic anhydride, and 3-triethoxy decane. Propyl succinic anhydride, 3-triphenoxy decyl propyl succinic anhydride, 3-trimethoxydecyl propyl glutaric anhydride, 3-triethoxy decyl propyl glutaric anhydride, 3-triphenyl Oxalyl propyl glutaric anhydride or the like.

The decane compound wherein x is 2 may, for example, be di-1-butoxy-bis[3-(dihydro-2,5-furanedone)propyl]decane (di-1-butoxy-bis[3- (dihydro-2,5-furandionyl)propyl]silane), bis[3-(dihydro-2,5-furandione)propyl]dimethoxydecane, bis[3-(dihydro-2H- Pyran-2,6(5H)-dione)propyl]dimethoxydecane (bis[3-(dihydro-2H-pyran-2,6(5H)-dionyl)propyl]dimethox y silane), etc. .

Examples of the decane compound in which x is 3 include tris[3-(dihydro-2,5-furandionary)propyl]methoxydecane.

Among these compounds (2), a decane compound wherein x is 1 is preferable, and specific examples of the suitable compound (2) include 3-trimethoxydecylpropyl succinic anhydride and 3-triethoxydecyl propylpropane. Base water succinic anhydride and the like.

From the viewpoint of improvement in heat-resistant transparency, hardness, scratch resistance, heat crack resistance, adhesion, sensitivity, resolution, and developability, the total addition ratio of the compound (2) is preferably based on the total amount of the raw material compounds. It is 15 mol% or less, more preferably 13 mol% or less, further preferably 10 mol% or less, further preferably 7 mol% or less. In addition, the lower limit of the total addition ratio of the compound (2) is preferably 0.5 mol%, more preferably 1 mol%, still more preferably 2 mol%, particularly preferably 3 mol%, based on the total amount of the raw material compounds. The total addition ratio of the compound (2) is preferably from 0.5 mol% to 15 mol%, more preferably from 1 mol% to 13 mol%, even more preferably from 2 mol% to 10 mol, based on the total amount of the raw material compounds. %, further preferably from 3 mol% to 7 mol%.

The method of subjecting TEOS, the compound (1) and the compound (2) to hydrolysis condensation is preferably carried out by mixing TEOS, the compound (1) and the compound (2) as a raw material compound in a solvent, and adding it to the mixed solution. Water, hydrolyzed and condensed. In this case, the reaction may be carried out in one step by adding each of the raw material compounds and water in one portion of the reaction system, or may be carried out in multiple stages by adding each raw material compound and water to the reaction system in multiple portions. Condensation reaction. Further, the hydrolysis-condensation product includes not only a product obtained by hydrolysis-condensation of all the hydrolyzable groups but also a product in which a part of the hydrolyzable group is not hydrolyzed or condensed.

In the hydrolysis condensation reaction, the acid anhydride group of the compound (2) is ring-opened as shown in the following scheme to form a carboxyl group. Further, the OR ⁴ group in the formula represents a hydroxyl group derived from a carboxyl group formed by hydrolysis or an alcoholation of an alcohol having 1 to 6 carbon atoms which is generated in the reaction system by hydrolysis. Alkoxy group.

[Chemistry 7]

In the formula, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and z has the same meaning as described above. The alkyl group of R ⁴ may be the same as those of R ¹ , and its specific constitution is as described in R ¹ .

The solvent used in the hydrolysis condensation reaction is not particularly limited, and a solvent similar to the solvent used for the preparation of the radiation sensitive composition is usually used. Such a solvent may, for example, be ethylene glycol monoalkylether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkylether, propylene glycol monoalkyl ether acetate Ester, propionate. These solvents may be used alone or in combination of two or more. 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, and 3-methoxypropionic acid are preferred. Methyl ester.

The water used in the hydrolysis condensation reaction 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 mol to 3 mol, more preferably from 0.3 mol to 2 mol, based on the total amount of hydrolyzable groups of TEOS, compound (1) and compound (2). More preferably, it is 0.5 mole to 1.5 moles. By using such an amount of water, the reaction rate of hydrolysis condensation can be optimized.

Further, the hydrolysis condensation reaction is carried out by self-catalyzing by a carboxylic acid produced by hydrolysis of the compound (2) without adding a catalyst, but an acid catalyst may be additionally added.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and polyphosphoric acid; organic acids such as formic acid, oxalic acid, acetic acid, trifluoroacetic acid, and trifluoromethane sulfonic acid; and acidic ion exchange resins. .

From the viewpoint of promoting the hydrolysis condensation reaction, the amount of the catalyst used is preferably 0.2 mol or less, more preferably 0.00001 mol, based on 1 mol of the total amount of TEOS, the compound (1) and the compound (2). 0.1 mol.

The reaction temperature and reaction time of the hydrolysis condensation reaction can be appropriately set, and for example, the following conditions can be employed. The reaction temperature is preferably from 40 ° C to 200 ° C, more preferably from 50 ° C to 150 ° C. The reaction time is preferably from 30 minutes to 24 hours, more preferably from 1 hour to 12 hours. By setting such a reaction temperature and reaction time, the hydrolysis condensation reaction can be carried out most efficiently.

After the hydrolysis condensation reaction, a dehydrating agent is added, followed by evaporation, whereby water and the produced alcohol are removed from the reaction system. The dehydrating agent used in this stage usually adsorbs or entraps excess water and the dehydration ability is completely consumed or removed by evaporation.

Ingredient [A ² ]

The component [A ² ] has a SiO ₂ unit derived from TEOS, a structural unit represented by the following formula (1a) derived from the compound (1) (hereinafter also referred to as "structural unit (1a)"), and a compound derived from the compound. (2) A structural unit represented by the following formula (2a) (hereinafter also referred to as "structural unit (2a)"). Each of the structural units of the SiO ₂ unit, the structural unit (1a), and the structural unit (2a) may be used alone or in combination of two or more.

[化8]

[Chemistry 9]

Wherein R ² , R ⁴ , m, n, x, y and z have the same meanings as described above]

Among these, in particular, in the formula (1a), m is preferably 1, and in the formula (2a), x is preferably 1.

The structural unit in the case where m is 1 in the formula (1a) and x is 1 in the formula (2a) is shown in the following formula (1-1a) and formula (2-1a), respectively.

[化10]

[11]

Wherein R ² , R ⁴ , n, y and z have the same meanings as described above]

Such a polyoxyalkylene can be obtained by subjecting TEOS, the compound (1) and the compound (2) to the above hydrolysis and condensation reaction, or by using two of TEOS, the compound (1) and the compound (2). The hydrolysis condensate of the compound is obtained by a hydrolysis condensation reaction with the remaining part of the compound. That is, the SiO ₂ unit, the structural unit (1a), and the structural unit (2a) may be contained in any of random copolymerization and block copolymerization, respectively.

SiO ₂ unit, structural unit (1a) and structure in the component [A ² ] from the viewpoints of improvement in heat-resistant transparency, hardness, scratch resistance, heat crack resistance, adhesion, sensitivity, resolution, and developability The respective contents of the unit (2a) are as follows.

In all the structural units of the component [A ² ], the SiO ₂ unit is preferably from 5 mol% to 75 mol%, more preferably from 10 mol% to 70 mol%, still more preferably from 25 mol% to 65 mol%.

In all the structural units of the component [A ² ], the structural unit (1a) is preferably from 10 mol% to 80 mol%, more preferably from 10 mol% to 75 mol%, still more preferably from 15 mol% to 70 mol%. .

In all the structural units of the component [A ² ], the structural unit (2a) is preferably 15 mol% or less, more preferably 13 mol% or less, still more preferably 10 mol% or less, and further preferably 7 mol% or less. The lower limit thereof is preferably 0.5 mol%, more preferably 1 mol%, still more preferably 2 mol%, and particularly preferably 3 mol%. The configuration of the scope unit (2a) of the content ratio, in the component [A ^2] all the structural units, preferably 0.5 mol% ~ 15 mol%, more preferably 1 mol% ~ 13 mol%, and further more preferably 2 mol% to 10 mol%, and more preferably 3 mol% to 7 mol%.

In addition, it is preferable to contain one or more structural units represented by the following formula (1b) from the viewpoint of further improving heat-resistant cracking resistance and scratch resistance (hereinafter also referred to as "structural unit (1b)"). As a structural unit (1a).

[化12]

In the formula (1b), R ⁵ represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms, and m has the same meaning as described above.

The alkyl group of R ⁵ may be the same as the above R ¹ , and the aryl group of R ⁵ may be the same as the above R ² . The specific configuration is as described above.

Further, m is preferably 1. The structural unit in the case where m is 1 in the formula (1b) is shown in the following formula (1-1b).

[Chemistry 13]

[wherein R ⁵ has the same meaning as described above]

In all the structural units of the component [A ² ], the content of the structural unit (1b) is preferably from 10 mol% to 80 mol%, more preferably from 15 mol% to 75 mol%, and still more preferably 30 mol%. 70 mol%.

Furthermore, in the present invention, the structural unit (1a) preferably contains a structural unit selected from the following formula (1c) from the viewpoint of further improving sensitivity and developability (hereinafter also referred to as "structural unit" (1c)") and at least one of the structural unit represented by the following formula (1d) (hereinafter also referred to as "structural unit (1d)"), more preferably containing structural unit (1c) and structural unit (1d) Both. Furthermore, it is preferable to contain a structural unit (1b) and contain at least one selected from the structural unit (1c) and the structural unit (1d).

[Chemistry 14]

[化15]

In the formulae (1c) and (1d), m and n have the same meanings as described above, m is preferably 1, and n is preferably 3.

The structural unit in the case where m is 1 in the formula (1c) and the formula (1d) is shown in the following formula (1-1c) and formula (1-1d), respectively.

[Chemistry 16]

[化17]

[where n is the same as described above]

In terms of the sensitivity and the resolution, the total content of the structural unit (1c) and the structural unit (1d) is preferably 5 mol% to 25 mol% in all the structural units of the component [A ² ]. More preferably 10 mol% to 20 mo;%.

Further, in the case where the structural unit (1c) and the structural unit (1d) are contained, the content ratio of the structural unit (1c) to the structural unit (1d) is considered from the viewpoint of further improving the scratch resistance and the crack resistance ( 1c/1d) is preferably from 0.05 to 3, more preferably from 0.2 to 1.5, still more preferably from 0.3 to 1, in terms of a molar ratio.

Further, the structural unit (2a) may, for example, be a structural unit derived from the above compound (2), and preferably derived from 3-trimethoxydecylpropyl succinic anhydride or 3-triethoxydecylpropyl amber. A structural unit such as an acid anhydride.

The component [A] may be used singly or in combination of two or more.

The molecular weight of the component [A] can be measured by a gel permeation chromatograph (GPC) using a mobile phase using tetrahydrofuran in the form of a polystyrene-equivalent weight average molecular weight. The weight average molecular weight (Mw) of the component [A] is preferably from 500 to 10,000, more preferably from 1,000 to 7,000. When the value of the weight average molecular weight of the component [A] is 500 or more, the film formability of the coating film of the radiation sensitive composition can be improved. On the other hand, by setting the weight average molecular weight to 10,000 or less, it is possible to prevent the alkali developability of the radiation sensitive composition from deteriorating.

Further, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by the same conditions, that is, the degree of dispersion (Mw/Mn) is preferably from 1.0 to 15.0, more preferably from 1.1 to 10.0, and still more preferably. It is 1.1 to 5.0. By setting it as such a range, alkali developability, adhesiveness, and heat-resistant cracking property can be set.

Ingredient [B]

The component [B] is a compound having two or more ethylenically unsaturated groups, and is a polyfunctional monomer polymerized by irradiation with radiation in the presence of a component [C] photoradical polymerization initiator described later. Among them, the component [A] is excluded from the component [A].

From the viewpoint of improving the polymerizability and improving the strength of the obtained cured film, a bifunctional or trifunctional or higher (meth) acrylate can be preferably used as the compound.

The bifunctional (meth) acrylate may be a polyfunctional (methyl group) obtained by reacting a divalent aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol or polypropylene glycol with (meth)acrylic acid. )Acrylate. Specific examples thereof include ethylene glycol diacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, and diethylene glycol II. Methacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9 - decanediol diacrylate, 1,9-nonanediol dimethacrylate, and the like. Commercial products include, for example, Aronix M-210, Aronix M-240, Aronix M-6200 (above manufactured by Toagosei Co., Ltd.); KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 (above manufactured by Nippon Kayaku Co., Ltd.) ); Viscoat 260, Viscoat 312, Viscoat 335HP (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.); Light Acrylate 1, 9-NDA (manufactured by Kyoeisha Chemical Co., Ltd.), and the like.

The trifunctional or higher (meth) acrylate may be a trivalent or higher aliphatic polyhydroxy compound such as glycerine, trimethylol propane, pentaerythritol or dipentaerythritol. A polyfunctional (meth) acrylate obtained by the reaction of acrylic acid. Specific examples thereof include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, and dipentaerythritol. Pentaacrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol hexaacrylate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene oxide modified dipentaerythritol hexaacrylate Ester and the like. Commercial products include, for example, Aronix M-309, Aronix M-315, Aronix M-400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, Aronix TO- 1450 (above produced by East Asia Synthetic Company); KAY ARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD DPEA-12 (above manufactured by Nippon Kayaku Co., Ltd.) Viscoat 295, Viscoat 300, Viscoat 360, Viscoat GPT, Viscoat 3PA, Viscoat 400 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.).

In addition, in addition to tris(2-acryloyloxyethyl)phosphate, tris(2-methylpropenyloxyethyl)phosphate, succinic acid-modified pentaerythritol triacrylate In addition to succinic acid modified dipentaerythritol pentaacrylate and tri(acryloxyethyl)isocyanurate, it may also be used to have a linear alkyl group and an alicyclic structure. A polyfunctional acrylated polyurethane compound obtained by reacting a compound having two or more isocyanate groups with a compound having one or more hydroxyl groups in the molecule and having three, four or five (meth) acryloxy groups. Wait. Commercial products containing a polyfunctional urethane-based compound include New Frontier R-1150 (manufactured by Daiichi Kogyo Co., Ltd.), KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), and the like.

Among these, preferred are 1,9-nonanediol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate. Or a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid modified pentaerythritol triacrylate, succinic acid modified dipentaerythritol pentaacrylate, tris(propylene) A methoxyethyl) isomeric cyanurate or a commercially available product containing a polyfunctional urethane-based compound. Among them, a trifunctional or higher functional group, particularly a trifunctional to 6 functional (meth) acrylate, is preferable, and a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate is particularly preferred.

The component [B] may be used singly or in combination of two or more. The content of the component [B] is preferably from 5 parts by mass to 300 parts by mass, more preferably from 10 parts by mass to 200 parts by mass, even more preferably from 15 parts by mass to 100 parts by mass, per 100 parts by mass of the component [A]. Further more preferably, it is 20 mass parts - 80 mass parts. When the content of the component [B] is within the above range, hardness, heat resistance and sensitivity are further improved.

Ingredient [C]

The component [C] is a photoradical polymerization initiator. The photoradical polymerization initiator is a compound which can generate an active species which can initiate the curing reaction of the component [B] by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam or X-ray.

The photoradical polymerization initiator used in the present invention may, for example, be an O-acyl oxime compound, an acetophenone compound, an acyl phosphine oxide compound, or a combination. An imidazole compound or the like.

Specific examples of the O-indenyl hydrazine compound include ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-( O-ethyl-9-(2-methyl benzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), 1-[9- Ethyl-6-benzylidenyl-9.H.-oxazol-3-yl]-octane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2- Methyl benzhydryl)-9.H.-carbazol-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2- Ethyl benzhydryl)-9.H.-oxazol-3-yl]-ethane-1-one oxime-O-benzoate, ethyl ketone, 1-[9-ethyl-6-( 2-methyl-4-tetrahydrofuranylbenzylidene)-9.H.-carbazol-3-yl]-, 1-(O-ethenylhydrazine), ethyl ketone, 1-[9-ethyl -6-(2-methyl-4-tetrahydropyranylbenzylidene)-9.H.-carbazol-3-yl]-, 1-(O-ethylindenyl), ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzylidene)-9.H.-carbazol-3-yl]-,1-(O-ethylindenyl) Ethylketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene] -9.H.-carbazol-3-yl]-, 1-(O-ethylhydrazinyl), ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranyl) Oxylbenzylidene)-9.H.-carbazol-3-yl]-,1- (O-acetyl hydrazine), 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzylidene fluorenyl)], etc. O-indenyl hydrazine compound Use two or more types alone or in combination.

Among these compounds, preferred O-indenyl hydrazine compounds include ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazol-3-yl] -, 1-(O-ethylhydrazinyl), ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9.H.- Oxazol-3-yl]-, 1-(O-acetamidoxime), ethyl ketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl- 1,3-dioxolyl)methoxybenzylidene}-9.H.-carbazol-3-yl]-, 1-(O-ethylindenyl), 1,2-octyl Diketone, 1-[4-(phenylthio)-, 2-(O-benzhydrylhydrazine)].

Examples of the acetophenone compound include an α-amino ketone compound and an α-hydroxy ketone compound. The acetophenone compound may be used singly or in combination of two or more.

Specific examples of the α-amino ketone compound include 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one (2-benzyl-2- Dimethylamino-1-(4-morpholinophenyl)-butane-1-one), 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl - Butane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one, and the like.

Specific examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropane-1-one (1-phenyl-2-hydroxy-2-methyl propane-1-one), 1- (4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1 - Hydroxycyclohexyl phenyl ketone and the like.

Among the acetophenone compounds, an α-amino ketone compound is preferred, and particularly preferably 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4- Base-phenyl)-butan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one.

Specific examples of the fluorenylphosphine oxide compound include 2,4,6-trimethyl benzoyl-diphenyl-phosphine oxide and bis(2,6,6-trimethyl benzoyl-diphenyl-phosphine oxide). 4,6-Trimethylbenzylidene)-phenylphosphine oxide and the like. The fluorenylphosphine oxide compound may be used singly or in combination of two or more.

Among these fluorenylphosphine oxide compounds, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide is preferred.

Specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'- 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonyl phenyl)-1,2'-biimidazole, 2,2'-bis(2- Chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5 , 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1 , 2'-biimidazole and the like. The biimidazole compounds may be used singly or in combination of two or more.

Among these biimidazole compounds, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2' is preferred. - bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichloro Phenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and the like.

Further, in the case of using a biimidazole compound, at least one selected from the group consisting of an amine-based sensitizer and a hydrogen-donating compound may be added.

Examples of the amine-based sensitizer include N-methyl diethanolamine and 4,4'-bis(dimethylamino)benzophenone (4,4'-bis(dimethylamino). Benzophenone), 4,4'-bis(diethylamino)benzophenone, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, and the like. Among these amine-based sensitizers, particularly preferred is 4,4'-bis(diethylamino)benzophenone.

Examples of the hydrogen donor compound include a thiol compound. The thiol compound is preferably, for example, 2-mercaptobenzothiazole, 2-mercaptobenzooxazole, or 2-mercaptobenzoimidazole.

The component [C] may be used alone or in combination of two or more. In the present invention, it is preferred to contain an O-mercaptopurine compound as the component [C].

The content of the component [C] is preferably 0.05 parts by mass to 30 parts by mass, more preferably 0.1 parts by mass to 15 parts by mass, even more preferably 100 parts by mass based on 100 parts by mass of the total of the component [A] and the component [B]. 1 part by mass to 10 parts by mass. When the content of the component [C] is within the above range, a high radiation sensitivity can be exhibited even in the case of a low exposure amount, and a cured film having sufficient hardness can be formed.

In addition, when the biimidazole compound is selected as the component [C] and is used in combination with at least one selected from the group consisting of an amine-based sensitizer and a hydrogen-donating compound, the amine-based sensitization is obtained with respect to 100 parts by mass of the biimidazole compound. The amount of each of the agent and the hydrogen-donating compound is preferably from 0.1 part by mass to 50 parts by mass, more preferably from 1 part by mass to 20 parts by mass. By setting the amount to be used, the surface hardness of the obtained cured film can be improved.

Ingredient [D]

In the present invention, a structural unit containing (D ¹ ) a structural unit having a carboxyl group (hereinafter also referred to as "structural unit (D ¹ )") and (D ² ) having an epoxy group may be contained (hereinafter also referred to as "structural unit" The copolymer of (D ² )") was used as the component [D]. By containing the component [D], the sensitivity can be improved, and the solubility in the alkali developer, particularly the inorganic alkali developer used in the development step is excellent, so that the developability can be improved and the obtained cured film can be improved. Cracking.

The structural unit (D ¹ ) is preferably derived from at least (D ¹ -1) an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (hereinafter referred to as "compound (D ¹ -1)") A structural unit of a compound.

The compound (D ¹ -1) may, for example, be acrylic acid, methacrylic acid, crotonic acid, 2-acryloxy ethyl succinic acid, 2-methylpropene oxime a monocarboxylic acid such as oxyethyl succinic acid, 2-propenyloxyethyl hexahydrophthalic acid or 2-methylpropenyloxyethyl hexahydrophthalic acid; maleic acid (maleic) Acid), a dicarboxylic acid such as fumaric acid or citraconic acid; an acid anhydride of the dicarboxylic acid; Among these compounds (D ¹ -1), acrylic acid, methacrylic acid, 2-acryloxyloxy group B is preferable in terms of copolymerization reactivity and solubility of the obtained copolymer in an alkali developing solution. Succinic acid, 2-methylpropenyloxyethyl succinic acid, maleic anhydride.

The compound (D ¹ -1) may be used alone or in combination of two or more.

In all the structural units, the copolymerization ratio of the structural unit (D ¹ ) is preferably from 1% by mass (% by mass) to 40% by mass, more preferably from 2% by mass to 30% by mass, and still more preferably 3% by mass to ～ 25 mass%. By setting such a copolymerization ratio, it is possible to obtain a radiation-sensitive linear composition which optimizes various characteristics such as sensitivity, developability, and storage stability at a higher level.

The structural unit (D ² ) is preferably a structural unit derived from a radically polymerizable compound having an epoxy group (hereinafter also referred to as "compound (D ² - 2)").

Examples of the compound (D ² -2) include glycidyl acrylate, 2-methyl glycidyl acrylate, 3,4-epoxybutyl acrylate, and acrylic acid. Epoxyalkyl acrylate such as -6,7-epoxyheptyl ester, propylene-3,4-epoxycyclohexyl acrylate or 3,4-epoxycyclohexyl acrylate; glycidyl methacrylate, A 2-methylglycidyl acrylate, 3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate Epoxyalkyl methacrylate such as 3,4-epoxycyclohexylmethyl methacrylate; glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α-n-butyl acrylate Alpha-alkyl acrylate alkyl ester such as glycidyl ester, α-ethyl acrylate-6,7-epoxyheptyl; o-vinylbenzyl glycidyl ether, m-vinyl benzyl ether Vinyl benzyl glycidyl ether such as glycidyl ether or p-vinylbenzyl glycidyl ether.

Further, a polymerizable unsaturated compound containing an oxetanyl group can also be used as the compound (D ² -2). Specific examples of the oxetanyl group-containing polymerizable unsaturated compound include 3-(methacryloyloxymethyl)oxetane (3-(methacryloyloxymethyl)oxetane), 3- (methacryloxymethyl)-3-ethyloxetane, 3-(methacryloxymethyl)-2-methyloxetane, 3-(methacryl醯oxyethyl)oxetane, 3-(methacryloxyethyl)-3-ethyloxetane, 2-ethyl-3-(methacryloxyloxyethyl) Oxycyclobutane, 3-(acryloxymethyl)oxetane, 3-(acryloxymethyl)-3-ethyloxetane, 3-(acrylofluorene Oxymethyl)-2-methyloxetane, 3-(acryloxyethyl)oxetane, 3-(propyleneoxyethyl)-3-ethyloxocycle Butane, 2-ethyl-3-(acryloxyethyl)oxetane, 2-(methacryloxymethyl)oxetane, 2-methyl-2-( Methyl propylene methoxymethyl) oxetane, 3-methyl-2-(methacryloxymethyl) oxetane, 4-methyl-2-(methacryl oxime) Oxymethyl)oxetane, 2-(2-(2-methyl)methacrylate Heterocyclic butyl))ethyl ester, 2-(2-(3-methyloxetanyl)ethyl methacrylate, 2-(methacryloxyethyl)-2-methyl Oxetane, 2-(methacryloxyethyl)-4-methyloxetane, 2-(acryloxymethyl)oxetane, 2-methyl- 2-(Allyloxymethyl)oxetane, 3-methyl-2-(acryloxymethyl)oxetane, 4-methyl-2-(propyleneoxyl) Oxycyclobutane, 2-(2-(2-methyloxetanyl)ethyl methacrylate, 2-(2-(3-methyloxetan) methacrylate Base)) ethyl ester, 2-(acryloxyethyl)-2-methyloxetane, 2-(acryloxyethyl)-4-methyloxetane, etc. Heterocyclic butyl (meth) acrylate.

Among these compounds (D ² - 2), glycidyl methacrylate and methacrylic acid-2 can be preferably used in terms of high adhesion and heat crack resistance, and further improvement in reliability of the display element. -methylglycidyl ester, -3,4-epoxybutyl methacrylate, 3-(propylene methoxymethyl) oxetane, 3-(methacryloxymethyl) oxalate Cyclobutane, 3-(methacryloxymethyl)-3-ethyloxetane, 2-(methacryloxymethyl)oxetane, and the like.

The compound (D ² -2) may be used alone or in combination of two or more.

The copolymerization ratio of the structural unit (D ² ) in all the structural units is preferably from 10% by mass to 75% by mass, more preferably from 15% by mass to 70% by mass, even more preferably from 20% by mass to 65% by mass. By setting such a copolymerization ratio, especially the control of the molecular weight of the copolymer becomes easy, and the scratch resistance, the sensitivity, and the developability can be further improved.

The component [D] may have a structural unit other than the structural unit (D ¹ ) and the structural unit (D ² ). A compound which provides such a structural unit (hereinafter also referred to as "structural unit (D ³ )") (hereinafter also referred to as "compound (D ³ -3)") may, for example, be a (meth)acryloxypropyl group. a trialkoxy decane, an alkyl (meth) acrylate, an alicyclic alkyl (meth) acrylate, an unsaturated heterocyclic ring containing an oxygen atom or a six-membered ring (meth) acrylate, (a) Aryl acrylate, unsaturated dicarboxylic acid diester, maleimide compound, hydroxyalkyl (meth) acrylate, (meth) acrylamide, aromatic vinyl compound, 1 , 3-butadiene, etc.

Specific examples of (meth)acryloxypropyltrialkoxydecane include 3-methylpropenyloxypropyltrimethoxydecane, 3-propenyloxypropyltrimethoxydecane, and 3 Methyl propylene methoxy propyl triethoxy decane, 3-propenyl methoxy propyl triethoxy decane.

Specific examples of the alkyl (meth)acrylate include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, second butyl methacrylate, butyl methacrylate, and acrylic acid. Methyl ester, ethyl acrylate, n-butyl acrylate, second butyl acrylate, tert-butyl acrylate, and the like.

Specific examples of the (meth) acrylate cycloalkyl ester include cyclopentyl methacrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, and trimethyl methacrylate [5.2]. .1.0 ^2,6 ]decane-8-yl ester (hereinafter, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl is called "dicyclopentyl"), methacrylic acid-2-di Cyclopentyloxyethyl ester, isobornyl methacrylate, cyclopentyl acrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclohexyl acrylate [5.2.1.0 ^2,6 ]癸Alken-8-yl ester, 2-dicyclopentyloxyethyl acrylate, isobornyl acrylate, and the like.

Examples of the unsaturated heteroquinone ring or the six-membered ring methacrylate containing an oxygen atom include an unsaturated compound containing a tetrahydrofuran skeleton, an unsaturated compound containing a furan skeleton, and an unsaturated group containing a tetrahydropyran skeleton. a compound, an unsaturated compound containing a pyran skeleton, or the like. Specific examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl (meth)acrylate, 2-methylpropenyloxy-tetrahydrofurfuryl propionate, and 3-(A). Base) propylene decyloxytetrahydrofuran-2-one and the like. Specific examples of the unsaturated compound containing a furan skeleton include 2-methyl-5-(3-furyl)-1-penten-3-one (2-methyl-5-(3-furyl)-1- Pentene-3-one), decyl (meth) acrylate, 1-furan-2-butyl-3-en-2-one, 1-furan-2-butyl-3-methoxy-3-ene 2-keto, 6-(2-furyl)-2-methyl-1-hexen-3-one, 6-furan-2-yl-hex-1-en-3-one, acrylic acid-2- Furan-2-yl-1-methyl-ethyl ester, 6-(2-furyl)-6-methyl-1-hepten-3-one, and the like. Specific examples of the unsaturated compound containing a tetrahydropyran skeleton include (tetrahydropyran-2-yl)methyl methacrylate and 2,6-dimethyl-8-(tetrahydropyran-2- 2,6-dimethyl-8-(tetrahydropyran-2-yloxy)-oct-1-ene-3-one, 2-tetrahydropyridyl methacrylate Andy-2-ester, 1-(tetrahydropyran-2-yl)-butyl-3-en-2-one, and the like. Specific examples of the unsaturated compound containing a pyran skeleton include 4-(1,4-dioxa-5-oxo-6-heptenyl)-6-methyl-2-pyran (4-( 1,4-dioxa-5-oxo-6-heptenyl)-6-methyl-2-pyran), 4-(1,5-dioxa-6-oxo-7-octenyl)-6- Base-2-pyran and the like.

Specific examples of the hydroxyalkyl ester of (meth)acrylic acid include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. 3-hydroxypropyl methacrylate, 2,3-dihydroxypropyl (meth) acrylate, and the like.

Specific examples of the aryl (meth)acrylate include phenyl (meth)acrylate and benzyl (meth)acrylate.

Specific examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, and diethyl itaconate.

Specific examples of the maleimide compound include N-phenyl maleimide, N-cyclohexylmethyleneimine, and N-benzyl cis-butene. Equinone imine, N-(4-hydroxyphenyl) maleimide, N-(4-hydroxybenzyl) maleimide, N-butaneimine-3 -N-succinimidyl-3-maleimide benzoate, N-butyl succinimide-4-succinimide butyrate, N-butane Imino-6-maleimide hexanoate, N-butanediamine-3-butanediimide propionate, N-(9-acridinyl)-butane Ene diimine and the like.

Specific examples of the (meth)acrylamide may include acrylamide, methacrylamide, 4-hydroxyphenylpropenamide, 4-hydroxyphenylmethacrylamide, and 3-hydroxyphenylpropene oxime. Amine, 3-hydroxyphenylmethacrylamide, and the like.

Examples of the aromatic vinyl compound include styrene and α-methylstyrene.

Among these compounds (D ³ -3), preferred are (meth)acryloxypropyltrialkoxydecane, aromatic vinyl compound, maleimide compound, (meth)acrylic acid. An alicyclic alkyl ester or a (meth) acrylamide, particularly preferably a (meth) propylene methoxy propyl trialkoxy decane.

The compound (D ³ -3) may be used alone or in combination of two or more.

In all the structural units of the component [D], the copolymerization ratio of the structural unit (D ³ ) is preferably from 10% by mass to 70% by mass, more preferably from 15% by mass to 65% by mass. In the case where a structural unit derived from (meth)acryloxypropyl trialkoxysilane is used as the structural unit (D ³ ), the copolymerization ratio thereof is preferably from 10% by mass to 50% by mass, more preferably It is 20% by mass to 40% by mass. By setting such a copolymerization ratio, especially the control of the molecular weight of the copolymer becomes easy, and the developability, sensitivity, adhesion, and the like can be further improved.

The component [D] can be polymerized, for example, by subjecting the compound (D ¹ -1) and the compound (D ² -2), if necessary, the compound (D ³ -3) in a solvent in the presence of a radical polymerization initiator. And manufacturing.

Examples of the solvent used in the polymerization reaction include alcohols, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers, and propylene glycol monoalkyl ether acetates. A propylene glycol monoalkyl ether propionate, an aromatic hydrocarbon, a ketone, an ether other than the above, an ester other than the above, and the like.

The radical polymerization initiator can be appropriately selected depending on the kind of the compound to be used, and examples thereof include 2,2'-azobisisobutyronitrile (2,2'-azobisisobutyronitrile) and 2,2'-azobis. -(2,2'-azobis-(2,4-dimethyl valeronitrile), 2,2'-azobis-(4-methoxy-2,4- Dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), dimethyl-2,2'-azobis(2-methylpropionate), 2,2' An azo compound such as azobis(4-methoxy-2,4-dimethylvaleronitrile). Among these radical polymerization initiators, 2,2'-azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile) are preferable. The radical polymerization initiators may be used alone or in combination of two or more. The amount of the radical polymerization initiator to be used is usually from 0.1 part by mass to 50 parts by mass, preferably from 0.1 part by mass to 20 parts by mass, per 100 parts by mass of the total amount of the monomers.

Further, in the polymerization reaction, a molecular weight modifier may be used to adjust the molecular weight. Specific examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, and tri-dodecane sulfur; Mercaptans such as alcohols and thioglycolic acids; xanthogens such as dimethyl xanthogen sulfide and diisopropylxanthogen disulfide; terpinolene, α- Methylstyrene dimer, and the like. The amount of the molecular weight controlling agent used is usually 0.1 parts by mass to 50 parts by mass, preferably 0.2 parts by mass to 16 parts by mass, particularly preferably 0.4 parts by mass to 8 parts by mass, per 100 parts by mass of the total of the monomers.

Further, the polymerization temperature is usually from 0 ° C to 150 ° C, preferably from 50 ° C to 120 ° C, and the polymerization time is usually from 10 minutes to 20 hours, preferably from 30 minutes to 6 hours.

The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw'") of the component [D] obtained by GPC using a mobile phase using tetrahydrofuran is preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably 5 × 10 ³ to 5 × 10 ⁴ . By setting the Mw' of the component [D] to 2 × 10 ³ or more, a sufficient development margin of the radiation sensitive composition can be obtained, and the residual film ratio of the formed coating film can be prevented (the pattern film is appropriate) The ratio of the remaining amount is lowered, and the pattern shape, heat resistance, and the like of the obtained insulating film are kept good. On the other hand, by setting the Mw' of the component [D] to 1 × 10 ⁵ or less, it is possible to maintain a high degree of radiation sensitivity and obtain a good pattern shape. Further, the molecular weight distribution of the component [D] (hereinafter referred to as "Mw'/Mn'") is preferably 5.0 or less, more preferably 3.0 or less. By setting Mw'/Mn' of the component [D] to 5.0 or less, the pattern shape of the obtained insulating film can be kept good. Further, the radiation-sensitive composition containing the component [D] having the preferred ranges of Mw' and Mw'/Mn' as described above has high developability, so that a predetermined pattern shape can be easily formed in the developing step. No development residue is produced.

The component [D] may be used alone or in combination of two or more.

The content of the component [D] is preferably from 1 part by mass to 45 parts by mass, more preferably from 2 parts by mass to 40 parts by mass, even more preferably from 3 parts by mass to 35 parts by mass, per 100 parts by mass of the component [A]. Further, it is more preferably 3 parts by mass to 30 parts by mass, and still more preferably 3 parts by mass to 25 parts by mass. By setting the content of the component [D] within the above range, the sensitivity and developability can be further improved.

Ingredient [E]

Further, in the present invention, at least one selected from the group consisting of organic particles and inorganic particles may be contained as the component [E]. By containing the component [E], scratch resistance, crack resistance, and the like can be improved.

As the organic particles, solid particles such as acrylic fine particles can be suitably used. Examples of the acrylic fine particles include a methyl methacrylate polymer, a copolymer of methacrylic acid and an alkyl compound, and the like. Commercial products of the organic particles include, for example, Zefiac F-320, Zefiac F-301, Zefiac F-340, Zefiac F-325, Zefiac F-351 (the above is manufactured by Ganz Chemical Co., Ltd.), and acrylic microparticles MP-300 ( Research Institute Chemical Co., Ltd.).

Further, the inorganic fine particles may be exemplified by silica, alumina, zirconia, titania, zinc oxide, magnesium oxide, calcium carbonate, magnesium carbonate, barium sulfate, talc, montmorillonite ( Particles as a main component such as montmorillonite) are preferably particles containing ceria and alumina as main components.

The shape of the inorganic fine particles may be any of a spherical shape, a rod shape, a plate shape, a fibrous shape, and an indefinite shape, and the inorganic fine particles may be solid, hollow, or porous.

Specific examples of such inorganic fine particles include: Admafine SO-E1, Admafine SO-E2, Admafine SO-E3, Admafine SO-E4, Admafine SO-E5, and Admafine SE3200-SEJ (manufactured by Admatechs Co., Ltd.). , SS01, SS03, SS15, SS35 (manufactured by Osaka Chemical Industry Co., Ltd.), methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST- OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL (manufactured by Nissan Chemical Industries, Ltd.). In addition, examples of the zirconia particles include HXU-110JC, HXU-210C, NZD-3101 (manufactured by Sumitomo Osaka Cement Co., Ltd.), ID191 (manufactured by Tayca Co., Ltd.), ZRPMA15WT%-E05 (manufactured by CIKasei Co., Ltd.), and the like, and further, titanium oxide. The particles can be listed as: MT-05, MT-100W, MT-100SA, MT-100HD, MT-300HD, MT-150A, ND138, ND139, ND140, ND154, ND165, ND177, TS-063, TS-103, TS- 159 (made by Tayca) and so on.

The inorganic fine particles may also be surface-treated by a decane coupling agent or the like. By performing such a surface treatment, compatibility with other components can be improved, and dispersibility or mechanical strength in the composition can be improved.

The average particle diameter of the organic particles and the inorganic particles is preferably in the range of 0.005 μm to 0.5 μm.

Regarding the component [E], the powdery particles may be directly added to and mixed with other components, or may be added as a solvent dispersion, added to and mixed with other components, and then the solvent may be distilled off.

The component [E] may be used alone or in combination of two or more.

The content of the component [E] is preferably from 1 part by mass to 600 parts by mass, more preferably from 10 parts by mass to 200 parts by mass, even more preferably from 50 parts by mass to 100 parts by mass, per 100 parts by mass of the component [A]. When the content of the component [E] is within the above range, the scratch resistance and heat crack resistance of the obtained protective film and interlayer insulating film can be further improved.

Ingredient [F]

In the present invention, a solvent may be contained as the component [F]. The radiation sensitive composition is usually prepared by formulating a solvent in the form of a liquid composition. The solvent can be appropriately selected and used as long as it disperses or dissolves each component constituting the radiation sensitive composition and does not react with the components and has moderate volatility.

As such a solvent, it is preferred to contain an alcohol solvent as a protic solvent. By using an alcohol-based solvent, the coating property of the radiation-sensitive composition on a large substrate can be improved, and the uneven coating (strip unevenness, unevenness of the needle marks, uneven haze, etc.) can be suppressed, and further Improve film thickness uniformity.

Examples of the alcohol solvent include 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1,6-hexanediol, 1,8-octanediol, and the like. Long-chain alkyl alcohol; aromatic alcohol such as benzyl alcohol; ethylene glycol monomethyl ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether; propylene glycol single a propylene glycol monoalkyl ether such as methyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether; diethylene glycol monoalkyl ether such as diethylene glycol monomethyl ether or diethylene glycol monoethyl ether; dipropylene glycol single Dipropylene glycol monoalkyl ether such as methyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether or dipropylene glycol monobutyl ether.

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

Among these alcohol-based solvents, propylene glycol monoalkyl ether is preferable, and propylene glycol monomethyl ether and propylene glycol monoethyl ether are particularly preferable from the viewpoint of improving coatability.

The component [F] may be used alone or in combination of two or more.

The content of the component [F] is preferably from 1 part by mass to 1,200 parts by mass, more preferably from 10 parts by mass to 900 parts by mass, per 100 parts by mass of the component [A]. When the content of the component [F] is within the above range, coating properties on a glass substrate or the like can be improved, and unevenness in coating (strip unevenness, unevenness of needle marks, uneven haze, etc.) can be suppressed. , can further improve the film thickness uniformity.

In the present invention, other solvents such as ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ether propionates, and aromatics may be contained together with the alcohol solvent. Hydrocarbons, ketones, esters, and the like.

additive

The radiation sensitive composition of the present invention may contain various additives as needed.

Examples of the additive include a radioactive acid generator such as a triphenylsulfonium salt or a tetrahydrothiophenium salt; and 2-nitrobenzylcyclohexyl carbamate. a radiation-sensitive linear base generator such as O-carbamoyl hydroxy amide; a surfactant such as a nonionic surfactant, a fluorine-based surfactant, and an anthrone-based surfactant; 2,2-thiobis(4-methyl-6-t-butyl phenol), 2,6-di-tertiary butyl Antioxidant such as phenol; 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole (2-(3-t-butyl-5-methyl-2) -hydroxy phenyl)-5-chloro benzotriazole), alkoxybenzophenone and other ultraviolet absorbers.

The content of these additives can be appropriately selected within the range not impairing the object of the present invention.

The radiation sensitive composition of the present invention can be produced by a suitable method, for example, by subjecting the component [A], the component [B] and the component [C] in a [F] solvent, and optionally the component [D], The component [E] or an additive or the like is mixed in a predetermined ratio to prepare a radiation-sensitive composition in a solution or dispersion state.

Hardened film and method of forming same

Next, a method of forming a cured film on a substrate using the radiation sensitive composition of the present invention will be described. The method comprises the following steps (1) to (4).

(1) a step of applying the radiation sensitive composition of the present invention onto a substrate to form a coating film;

(2) a step of irradiating at least a part of the coating film formed in the step (1) with radiation;

(3) a step of developing the radiation-coated coating film in the step (2) using an alkali developing solution;

(4) a step of heating the developed coating film in the step (3).

step 1)

In the step (1), after applying the solution or dispersion of the radiation sensitive composition of the present invention on the substrate, it is preferred to remove the solvent by heating (prebaking) the coated surface to form a coating. membrane. Examples of the material of the substrate that can be used include glass, quartz, rhodium, and resin. Specific examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimine, and cyclic olefin. Ring-opening polymers and their hydrides, and the like.

The method of applying the solution or dispersion of the radiation sensitive composition is not particularly limited, and for example, a spray method, a roll coating method, a spin coating method, a slit die coating method, or a bar coating method may be employed. Appropriate methods such as law. Among these coating methods, a spin coating method or a slit die coating method is particularly preferred. The pre-baking conditions vary depending on the type of each component, the blending ratio, and the like, and it is preferably set to 70 ° C to 120 ° C for about 1 minute to 10 minutes.

Step (2)

In the step (2), at least a part of the coating film formed in the step (1) is exposed. Usually, when a part of the coating film is exposed, exposure is performed through a photomask having a predetermined pattern. For the radiation used for the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used. Among these radiations, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation containing ultraviolet rays of 365 nm is particularly preferable.

The exposure amount in this step is a value obtained by measuring the intensity at a wavelength of 365 nm of the radiation by an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.), preferably 10 mJ/cm ² to 1,000 mJ/ cm ^2, more preferably ^{20 mJ / cm 2 ~ 700 mJ} / cm 2.

Step (3)

In the step (3), the exposed coating film is developed with an alkali developing solution, whereby the unexposed portion is removed to form a predetermined pattern. As described above, the radiation sensitive composition of the present invention is a negative type in which the non-irradiated portion of the radiation is removed.

Examples of the alkali developing solution include inorganic alkali developing solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and ammonia, and organic bases such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Developer solution. Among them, from the viewpoint of cost and productivity, an inorganic alkali developer is preferred, and a developer of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is particularly preferred. When the inorganic radiation developing solution is used in the radiation sensitive composition of the present invention, the pattern image can be formed with high resolution with high resolution.

Further, in the alkali developing solution, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added and used. The developing method can be, for example, an appropriate method such as a liquid-filling method, a dipping method, a shaking dipping method, or a shower method. The development time varies depending on the composition of the radiation sensitive composition, and is preferably from about 10 seconds to about 180 seconds. After such development treatment, for example, after running for 30 seconds to 90 seconds, the air is dried, for example, with compressed air or compressed nitrogen, whereby a desired pattern can be formed.

Step (4)

In the step (4), the developed coating film is heated by using a heating device such as a hot plate or an oven to obtain a cured film having a desired pattern. The heating temperature is, for example, 120 ° C to 250 ° C. The heating time varies depending on the type of the heating apparatus. For example, when the heating step is performed on the hot plate, the heating time can be set to 5 minutes to 30 minutes, and when the heating step is performed in the oven, the temperature can be set to 30 minutes to 90 minutes. A step-by-step baking method or the like which performs a heating step of 2 or more times may also be used.

The film thickness of the cured film thus formed is preferably from 0.1 μm to 10 μm, more preferably from 0.1 μm to 6 μm, still more preferably from 0.1 μm to 4 μm.

By the above-described steps, it is possible to form a cured film having excellent adhesion to a substrate, excellent heat-resistant transparency, hardness, scratch resistance, heat crack resistance, sensitivity, and developability, and can be high. The resolution is high-precision to form a pattern image. Moreover, this pattern can be developed using an inorganic alkali developer. Further, since the obtained cured film has such characteristics, it can be suitably used as, for example, a protective film of a touch panel of a display element or an interlayer insulating film of a display element.

Suitable aspects of the invention are as follows.

[1] A radiation sensitive composition comprising the following components [A ¹ ], component [B] and component [C]:

[A ^1] that the tetraethyl orthosilicate or partial hydrolyzate thereof, (1) a hydrolyzable silicon compound represented alkoxy or a partial hydrolyzate thereof, and the hydrolyzable silicon alkoxy compound represented by the above formula the formula (2) or a portion thereof a polyoxane obtained by hydrolyzing and condensing a hydrolyzate;

[B] a compound having two or more ethylenically unsaturated groups (excluding the component [A ¹ ]);

[C] Photoradical polymerization initiator.

[2] The radiation sensitive composition according to the above [1], wherein the tetraethoxy decane or a partial hydrolyzate thereof is preferably added in an amount of from 5 mol% to 75 mol% based on the total amount of the raw material compound. More preferably, it is 10 mol% to 70 mol%, and more preferably 25 mol% to 65 mol%.

[3] The radiation-sensitive linear composition according to the above [1] or [2], wherein the total amount of the hydrolyzable decane compound represented by the above formula (1) or a partial hydrolyzate thereof is added to the total amount of the raw material compound. The ratio is preferably from 10 mol% to 80 mol%, more preferably from 10 mol% to 75 mol%, and still more preferably from 15 mol% to 70 mol%.

[4] The radiation sensitive linear composition according to any one of the above [1] to [3] comprising a hydrolyzable decane compound selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, and having a carbon number of 6 to 14 At least one decane compound (hereinafter also referred to as decane compound (1b ¹ )) of the aryl hydrolyzable decane compound is a hydrolyzable decane compound represented by the above formula (1).

[5] The radiation sensitive composition according to the above [4], wherein the decane compound (1b ¹ ) is a hydrolyzable decane compound selected from an alkyl group having 1 to 6 carbon atoms, and has 1 carbon. At least one of the hydrolyzable decane compounds of 6 to 14 aryl groups.

[6] The radiation-sensitive composition according to the above [4] or [5], wherein the total addition ratio of the above decane compound (1b ¹ ) is preferably 10 mol% to 80 mol based on the total amount of the raw material compounds. % is more preferably 15 mol% to 75 mol%, and still more preferably 30 mol% to 70 mol%.

[7] The radiation sensitive composition according to any one of the above [1] to [6], which contains a hydrolyzable decane compound having a (meth) acryloxy group as the hydrolysis represented by the above formula (1) A decane compound.

[8] The radiation-sensitive linear composition according to the above [7], wherein the hydrolyzable decane compound having a (meth) acryloxy group has a hydrolyzable decane compound selected from the group consisting of methacryloxy groups (hereinafter also It is called at least one of a decane compound (1c ¹ )) and a hydrolyzable decane compound having an acryloxy group (hereinafter also referred to as a decane compound (1d ¹ )).

[9] The radiation-sensitive linear composition according to the above [7] or [8], wherein the total addition ratio of the hydrolyzable decane compound having a (meth) acryloxy group is preferable with respect to the total amount of the raw material compounds. It is 5 mol% to 25 mol%, more preferably 10 mol% to 20 mol%.

[10] The radiation sensitive composition according to [8] or [9] above, comprising a decane compound (1c ¹ ) and a decane compound (1d ¹ ) as a hydrolyzable decane compound having a (meth) propylene fluorenyloxy group; The addition ratio (1c ¹ /1d ¹ ) of the two is preferably 0.05 to 3, more preferably 0.2 to 1.5, still more preferably 0.3 to 1 in terms of a molar ratio.

[11] The radiation-sensitive linear composition according to any one of the above [1], wherein the hydrolyzable decane compound represented by the above formula (2) or a partial hydrolysis thereof is used with respect to the total amount of the raw material compound. The addition ratio of the substance is 15 mol% or less, more preferably 13 mol% or less, further preferably 10 mol% or less, further preferably 7 mol% or less.

[12] The radiation-sensitive linear composition according to any one of the above [1], wherein the hydrolyzable decane compound represented by the above formula (2) or a partial hydrolysis thereof is used with respect to the total amount of the raw material compound. The addition ratio of the substance is preferably from 0.5 mol% to 15 mol%, more preferably from 1 mol% to 13 mol%, still more preferably from 2 mol% to 10 mol%, still more preferably from 3 mol% to 7 mol%.

[13] The radiation sensitive composition according to any one of the above [1], wherein the hydrolyzable decane compound represented by the above formula (2) is 3-trimethoxydecylpropyl succinic anhydride. Or 3-triethoxydecylpropyl succinic anhydride.

[14] A radiation sensitive composition comprising the following components [A ² ], component [B] and component [C]:

[A ² ] a polyoxyalkylene having a SiO ₂ unit, a structural unit represented by the above formula (1a), and a structural unit represented by the above formula (2a);

[B] a compound having two or more ethylenically unsaturated groups (excluding the component [A ² ]);

[C] Photoradical polymerization initiator.

[15] The radiation sensitive composition according to the above [14], wherein the content of the SiO ₂ unit is preferably from 5 mol% to 75 mol%, more preferably in all the structural units of the component [A ² ]. It is 10 mol% to 70 mol%, and more preferably 25 mol% to 65 mol%.

[16] The radiation sensitive composition according to [14] or [15], wherein, in all the structural units of the component [A ² ], the content of the structural unit (1a) is preferably from 10 mol% to 80%. Mol% is more preferably 10 mol% to 75 mol%, and still more preferably 15 mol% to 70 mol%.

[17] The radiation sensitive composition according to any one of [14] to [16] wherein, in all the structural units of the component [A ² ], the content ratio of the structural unit (2a) is preferably 15 The mol% or less is more preferably 13 mol% or less, further more preferably 10 mol% or less, and further preferably 7 mol% or less.

[18] The radiation sensitive composition according to any one of [14] to [16] wherein, in all the structural units of the component [A ² ], the content ratio of the structural unit (2a) is preferably 0.5. Mol% to 15 mol%, more preferably 1 mol% to 13 mol%, still more preferably 2 mol% to 10 mol%, still more preferably 3 mol% to 7 mol%.

[19] The radiation sensitive composition according to any one of the above [14] to [18], comprising one or more structural units represented by the above formula (1b) (hereinafter also referred to as a structural unit (1b) ) as a structural unit (1a).

[20] The radiation sensitive composition according to the above [19], wherein, in all the structural units of the component [A ² ], the content of the structural unit (1b) is preferably from 10 mol% to 80 mol%, more preferably Preferably, it is 15 mol% to 75 mol%, and more preferably 30 mol% to 70 mol%.

[21] The radiation sensitive composition according to any one of the above [14] to [20], which comprises a structural unit selected from the above formula (1c) (hereinafter also referred to as "structural unit (1c)" And at least one of the structural unit (hereinafter also referred to as "structural unit (1d)") represented by the above formula (1d) is used as the structural unit (1a).

[22] The radiation sensitive composition according to the above [21], wherein, in all the structural units of the component [A ² ], the total content ratio of the structural unit (1c) to the structural unit (1d) is preferably 5 mol. % to 25 mol%, more preferably 10 mol% to 20 mol%.

[23] The radiation sensitive composition according to [21] or [22] above, comprising the structural unit (1c) and the structural unit (1d) as the structural unit (1a), the structural unit (1c) and the structural unit (1d) The content ratio (1c/1d) is preferably from 0.05 to 3, more preferably from 0.2 to 1.5, still more preferably from 0.3 to 1, in terms of a molar ratio.

[24] The radiation sensitive composition according to any one of [14] to [23] wherein the structural unit (2a) is derived from 3-trimethoxydecylpropyl succinic anhydride or 3-triethyl A structural unit of oxydecylpropyl succinic anhydride.

[25] The radiation sensitive composition according to any one of the above [1] to [13] wherein the carbon number of R ¹ of the above formula (1) and the alkyl group of R ³ of the above formula (2) is higher Preferably, it is 1 to 4, more preferably 1 or 2.

[26] The radiation sensitive composition according to any one of the above [1] to [25] wherein the alkyl group of R ² of the formula (1) and the formula (1a) has a carbon number of preferably 1 to 1 10, more preferably 1 to 6.

[27] The radiation sensitive composition according to any one of the above [1] to [26] wherein the aryl group of R ² of the above formula (1) and formula (1a) is preferably a phenyl group or a naphthyl group. More preferably, it is a phenyl group.

[28] The radiation sensitive composition according to any one of [1] to [27] wherein the above formula (1), formula (1a), formula (1b), formula (1c), and formula (1d) m is preferably 1 or 2, more preferably 1.

[29] The radiation sensitive composition according to any one of the above [1], wherein the formula (1), the formula (1a), the formula (1b), the formula (1c), and the formula (1d) n is preferably an integer of 0 to 3, more preferably 0 or 3.

[30] The radiation sensitive composition according to any one of the above [1] to [29] wherein x of the above formula (2) and formula (2a) is preferably 1 or 2, more preferably 1.

[31] The radiation sensitive composition according to any one of the above [1] to [30], wherein y of the above formula (2) and formula (2a) is preferably an integer of from 1 to 3, more preferably 3.

[32] The radiation sensitive composition according to any one of the above [1] to [31] wherein Z of the above formula (2) and formula (2a) is preferably 0 or 1, more preferably 0.

[33] The radiation sensitive composition according to any one of [1] to [32] wherein the weight average molecular weight (Mw) of the component [A ¹ ] and the component [A ² ] is preferably 500 to 10,000. More preferably, it is 1000 to 7000.

[34] The radiation sensitive composition according to any one of [1] to [33] wherein the dispersion degree (Mw/Mn) of the component [A ¹ ] and the component [A ² ] is preferably 1.0 to ～. 15.0, more preferably 1.1 to 10.0, still more preferably 1.1 to 5.0.

[35] The radiation sensitive composition according to any one of the above [1], wherein the component [B] is preferably a bifunctional or trifunctional or higher (meth) acrylate, more preferably The trifunctional or higher functional (meth) acrylate is more preferably a trifunctional to hexafunctional (meth) acrylate.

[36] The radiation sensitive composition according to any one of the above [1], wherein the content of the component [B] is preferably 5 parts by mass to 300 parts by mass based on 100 parts by mass of the component [A]. The mass part is more preferably 10 parts by mass to 200 parts by mass, still more preferably 15 parts by mass to 100 parts by mass, still more preferably 20 parts by mass to 80 parts by mass.

[37] The radiation sensitive composition according to any one of the above [1] to [36], wherein the O-mercaptopurine compound is contained as the component [C].

The radiosensitive linear composition according to any one of the above [1] to [37], wherein the content of the component [C] is 100 parts by mass based on the total amount of the component [A] and the component [B]. It is preferably 0.05 parts by mass to 30 parts by mass, more preferably 0.1 parts by mass to 15 parts by mass, still more preferably 1 part by mass to 10 parts by mass.

[39] The radiation sensitive composition according to any one of the above [1] to [38] further comprising (D ¹ ) a structural unit having a carboxyl group (hereinafter also referred to as structural unit D ¹ ) and (D) ² ) A copolymer of a structural unit having an epoxy group (hereinafter also referred to as structural unit D ² ) as a component [D].

[40] The radiation sensitive composition according to the above [39], wherein the structural unit (D ¹ ) is derived from an unsaturated carboxylic acid selected from the group consisting of (D ¹ -1) and an unsaturated carboxylic anhydride (hereinafter also these The compound is a structural unit of at least one compound of the "compound (D ¹ -1)").

[41] The radiation sensitive composition according to the above [39] or [40] wherein the structural unit (D ² ) is derived from a radically polymerizable compound having an epoxy group (hereinafter also referred to as "a compound (D) ² -2)") structural unit.

[42] As the above-mentioned [39] to [41] radiation-sensitive composition according to any one of claims, wherein all the structural units, the structural units (D ¹⁾ copolymerization ratio is preferably 1 to 40% by mass The mass% is more preferably 2% by mass to 30% by mass, still more preferably 3% by mass to 25% by mass.

[43] The radiation sensitive composition according to any one of the above [39], wherein the copolymerization ratio of the structural unit (D ² ) is preferably 10% by mass to 75 in all the structural units. The mass % is more preferably 15% by mass to 70% by mass, still more preferably 20% by mass to 65% by mass.

[44] As the above-mentioned [39] to [43] radiation-sensitive composition according to any one of claims, wherein the component [D] more (D ³⁾ derived from a (meth) Bing Xixi propyl trialkoxy a structural unit of oxoxane.

[45] The radiation sensitive composition according to any one of the above [39], wherein the content of the component [D] is preferably 1 part by mass based on 100 parts by mass of the polysiloxane. 45 parts by mass, more preferably 2 parts by mass to 40 parts by mass, still more preferably 3 parts by mass to 35 parts by mass, still more preferably 3 parts by mass to 30 parts by mass, still more preferably 3 parts by mass to 25 parts by mass.

[46] The radiation sensitive composition according to any one of the above [1] to [45] further comprising at least one selected from the group consisting of organic particles and inorganic particles as the component [E].

[47] The radiation-sensitive linear composition according to the above [45], wherein the content of the component [E] is preferably from 1 part by mass to 600 parts by mass, more preferably 10%, based on 100 parts by mass of the polysiloxane. The mass part is -200 parts by mass, and more preferably 50 parts by mass to 100 parts by mass.

[48] The radiation sensitive composition according to any one of the above [1] to [47] further comprising a solvent as the component [F].

[49] The radiation sensitive composition according to the above [48], which preferably contains a protic solvent, more preferably an alcohol solvent as the component [F].

[50] The radiation sensitive composition according to the above [48], wherein the content of the component [F] is preferably from 1 part by mass to 1,200 parts by mass based on 100 parts by mass of the polysiloxane. More preferably, it is 10 mass parts - 900 mass parts.

[51] The radiation sensitive composition according to any one of the above [1] to [50], which is used for forming a protective film of a touch panel or an interlayer insulating film of a display element.

[52] A cured film formed by using the radiation sensitive composition according to any one of the above [1] to [51].

[53] A method for forming a cured film, comprising the following steps (1) to (4);

(1) a step of applying a radiation-sensitive composition according to any one of claims 1 to 13 to a substrate to form a coating film;

(2) a step of irradiating at least a part of the coating film formed in the step (1) with radiation;

(3) a step of developing the radiation-coated coating film in the step (2) using an alkali developing solution;

(4) a step of heating the developed coating film in the step (3).

[54] The formation method according to [53] above, wherein the radiation in the step (2) comprises radiation preferably having a wavelength of from 190 nm to 450 nm, more preferably ultraviolet light having a wavelength of 365 nm.

[55] The method according to the above [53] or [54], wherein an inorganic alkali developer is used as the alkali developer in the step (3).

[Example]

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

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyoxyalkylene obtained in each of the following Synthesis Examples were measured by Gel Permeation Chromatography (GPC) of the following specifications.

Device: GPC-101 (made by Showa Denko (share))

Pipe column: Link GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 (made by Showa Denko)

Mobile phase: tetrahydrofuran

Synthesis example of polyoxyalkylene of component [A]

[Synthesis Example 1]

20 parts by mass of propylene glycol monomethyl ether was added to a container equipped with a stirrer, and then 41 parts by mass of methyltrimethoxydecane (hereinafter referred to as "MTMS"), 12 parts by mass of tetraethoxydecane (TEOS), and 3- were added. 5 parts by mass of (trimethoxydecyl)propyl succinic anhydride (hereinafter referred to as "TMSPS") (MTMS/TEOS/TMSPS = 80/15/5), and heated to a solution temperature of 60 °C. After the solution temperature reached 60 ° C, 0.1 part by mass of phosphoric acid and 19 parts by mass of ion-exchanged water were added, and the mixture was heated to 75 ° C for 3 hours. After cooling to 45 ° C, 28 parts by mass of methyl orthoformate as a dehydrating agent was added, and the mixture was stirred for 1 hour. Further, the temperature of the solution was adjusted to 40 ° C, and evaporation was carried out while maintaining the temperature, thereby removing ion-exchanged water and methanol produced by hydrolysis condensation. Polyoxyalkylene (A-1) was obtained by the above operation. The polysiloxane (A-1) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 2,500, and a degree of dispersion (Mw/Mn) of 2.2. In the present specification, the term "solid content" means a residual component obtained by drying a sample with a hot plate at 175 ° C for 1 hour to remove volatile substances.

[Synthesis Example 2]

In addition to MTMS, TEOS and TMSPS, 3-methylpropenyloxypropyltrimethoxydecane (hereinafter referred to as "MPTMS") is MTMS/TEOS/MPTMS/TMSPS (Morby)=68/15/ Polypyroxyline (A-2) was obtained by the same operation as in Synthesis Example 1, except that the ratio of 15/2 was used. The polysiloxane (A-2) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 2,300, and a degree of dispersion (Mw/Mn) of 2.1.

[Synthesis Example 3]

Polyoxane (A-3) was obtained by the same operation as in Synthesis Example 2 except that the ratio of MTMS/TEOS/MPTMS/TMSPS (Mohr ratio) was changed to 62/15/15/8. The polysiloxane (A-3) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 2,200, and a degree of dispersion (Mw/Mn) of 2.1.

[Synthesis Example 4]

Polyoxane (A-4) was obtained by the same operation as in Synthesis Example 2, except that the ratio (mol ratio) of MTMS/TEOS/MPTMS/TMSPS was changed to 55/15/15/15. The polysiloxane (A-4) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 2,200, and a degree of dispersion (Mw/Mn) of 2.3.

[Synthesis Example 5]

In addition to MTMS, TEOS and TMSPS, MPTMS and Phenyltrimethoxydecane (hereinafter referred to as "PTMS") are MTMS/TEOS/PTMS/MPTMS/TMSPS (Morby)=50/15/15/15/ Polypyroxyline (A-5) was obtained by the same operation as in Synthesis Example 1, except that the ratio of 5 was used. The polysiloxane (A-6) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 1,900, and a degree of dispersion (Mw/Mn) of 1.9.

[Synthesis Example 6]

In addition to MTMS, TEOS and TMSPS, 3-acryloxypropyltrimethoxydecane (hereinafter referred to as "APTMS") is MTMS/TEOS/APTMS/TMSPS (Morby)=65/15/15/ Polypyroxyline (A-6) was obtained by the same operation as in Synthesis Example 1, except that the ratio of 5 was used. The polysiloxane (A-6) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 2,400, and a degree of dispersion (Mw/Mn) of 2.3.

[Synthesis Example 7]

Polyoxyalkylene (A-7) was obtained by the same operation as in Synthesis Example 6, except that the ratio (mol ratio) of MTMS/TEOS/APTMS/TMSPS was changed to 50/30/15/5. The polysiloxane (A-7) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 3,500, and a degree of dispersion (Mw/Mn) of 2.4.

[Synthesis Example 8]

In addition to MTMS, TEOS and TMSS, MPTMS and APTMS are used in the ratio of MTMS/TEOS/MPTMS/APTMS/TMSPS (Morby)=77/7/1/10/5, in addition to The same operation as in Example 1 gave polyoxyalkylene (A-8). The polysiloxane (A-8) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 2,000, and a degree of dispersion (Mw/Mn) of 2.0.

[Synthesis Example 9]

Polyoxane (A-9) was obtained by the same operation as in Synthesis Example 8, except that the ratio (mol ratio) of MTMS/TEOS/MPTMS/APTMS/TMSPS was changed to 50/30/5/10/5. ). The polysiloxane (A-9) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 3,400, and a degree of dispersion (Mw/Mn) of 2.3.

[Synthesis Example 10]

Polyoxane (A-10) was obtained by the same operation as in Synthesis Example 8, except that the ratio (mol ratio) of MTMS/TEOS/MPTMS/APTMS/TMSPS was changed to 15/62/8/10/5. ). The polysiloxane (A-10) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 5,400, and a degree of dispersion (Mw/Mn) of 2.6.

[Synthesis Example 11]

Polyoxane (A-11) was obtained by the same operation as in Synthesis Example 8, except that the ratio (mol ratio) of MTMS/TEOS/MPTMS/APTMS/TMSPS was changed to 50/30/10/5/5. ). The polysiloxane (A-11) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 3,100, and a degree of dispersion (Mw/Mn) of 2.3.

[Synthesis Example 12]

Polyoxane (A-12) was obtained by the same operation as in Synthesis Example 2 except that the ratio (mol ratio) of MTMS/TEOS/MPTMS/TMSPS was changed to 50/30/15/5. The polysiloxane (A-12) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 5,000, and a degree of dispersion (Mw/Mn) of 2.0.

[Synthesis Example 13]

Polyoxane (A-13) was obtained by the same operation as in Synthesis Example 6, except that the ratio (mol ratio) of MTMS/TEOS/APTMS/TMSPS was changed to 50/30/15/5. The polysiloxane (A-13) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 5,000, and a degree of dispersion (Mw/Mn) of 2.3.

[Synthesis Example 14]

Polyoxane (A-14) was obtained by the same operation as in Synthesis Example 1, except that the ratio (mol ratio) of MTMS/TEOS/TMSPS was changed to 60/30/10. The polysiloxane (A-14) had a solid content concentration of 28% by mass, a weight average molecular weight (Mw) of 5,000, and a degree of dispersion (Mw/Mn) of 2.0.

[Comparative Synthesis Example 1]

Polyphenylene oxide (a-1) was obtained by the same operation as in Synthesis Example 1, except that APTMS was used instead of TEOS and set to a ratio of MTMS/APTMS/TMSPS (Morby) = 80/15/5. ). The polysiloxane (a-1) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 2,000, and a degree of dispersion (Mw/Mn) of 1.9.

[Comparative Synthesis Example 2]

Polyphenylene was obtained by the same operation as in Synthesis Example 1 except that MPTMS and APTMS were used instead of TEOS and set to a ratio of MTMS/MPTMS/APTMS/TMSPS (Morby)=80/5/10/5. Oxyalkane (a-2). The polysiloxane (a-2) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 2,000, and a degree of dispersion (Mw/Mn) of 1.9.

[Comparative Synthesis Example 3]

Polyphenylene oxide (a-3) was obtained by the same operation as in Synthesis Example 1, except that ATMMS was used instead of TMSPS and set to a ratio of MTMS/TEOS/APTMS (Morby) = 70/15/15. ). The polysiloxane (a-3) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 2,400, and a degree of dispersion (Mw/Mn) of 2.1.

[Comparative Synthesis Example 4]

TMSPS is not used, and phenyltrimethoxydecane (hereinafter referred to as "PTMS") is used instead of TEOS, and is set to a ratio of MTMS/PTMS (mole ratio) = 70/30, and by the synthesis example 6 The same operation was carried out to obtain polyoxyalkylene (a-4). The polysiloxane (a-4) had a solid content concentration of 29% by mass, a weight average molecular weight (Mw) of 6,000, and a degree of dispersion (Mw/Mn) of 2.0.

[Comparative Synthesis Example 5]

In a 500 mL three-necked flask, 27.2 g of MTMS and 39.2 g of 3-mercaptopropyltrimethoxydecane (MEPTMS) were placed, and 100 g of propylene glycol methyl ether was added thereto and dissolved, and the obtained mixed solution was magnetically applied. The stirrer (magnetic stirrer) was heated to 60 ° C while stirring. MTMS/MEPTMS = 50/50. 8.6 g of ion-exchanged water containing 1% by mass of oxalic acid was continuously added thereto over 1 hour. Then, after reacting at 60 ° C for 4 hours, the resulting reaction solution was cooled to room temperature. Then, the alcohol component as a by-product of the reaction was distilled off from the reaction liquid under reduced pressure. The polyoxyalkylene (a-5) was obtained by the above operation. The polysiloxane (a-5) had a solid content concentration of 45% by mass, a weight average molecular weight (Mw) of 1,900, and a degree of dispersion (Mw/Mn) of 2.3.

Synthesis of copolymer of component [D] [Synthesis Example 15]

To the flask equipped with a condenser and a stirrer, 5 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were added. Then, 18 parts by mass of styrene (hereinafter referred to as "ST") and 20 parts by mass of methacrylic acid (hereinafter referred to as "MA") and N-cyclohexylmethyleneimine (hereinafter referred to as "CHMI") are added. 40 parts by mass and 40 parts by mass of glycidyl methacrylate (hereinafter referred to as "GMA") were replaced with nitrogen, stirred slowly, and the temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to carry out polymerization. This gave a solution containing the copolymer (D-1). The obtained copolymer solution had a solid content concentration of 31%, the copolymer (D-1) had a weight average molecular weight (Mw') of 12,500, and a degree of dispersion (Mw'/Mn') of 2.5.

[Synthesis Example 16]

Instead of CHMI, dicyclopentanyl methacrylate (hereinafter referred to as "DCM") and p-hydroxymethyl acrylonitrile (hereinafter referred to as "HMAd") are set to ST/GMA/MA/DCM/HMAd (weight ratio). The copolymer (D-2) was obtained by the same operation as in Synthesis Example 15 except for the ratio of = 20/14/5/21/40. The copolymer (D-2) had a solid content concentration of 32% by mass, a weight average molecular weight (Mw') of 13,000, and a degree of dispersion (Mw'/Mn') of 2.0.

[Synthesis Example 17]

3-methylpropenyloxypropyltrimethoxydecane (MPTMS) was used instead of ST and CHMI, and was set to a ratio of MA/GMA/MPTMS (weight ratio) = 5/65/30, in addition to The copolymer (D-3) was obtained in the same manner as in Synthesis Example 15. The solid content concentration of the copolymer (D-3) was 31.5% by mass, the weight average molecular weight (Mw') was 12,000, and the degree of dispersion (Mw'/Mn') was 2.3.

[Synthesis Example 18]

A copolymer (D- was obtained by the same operation as in Synthesis Example 15 except that MPTMS was used instead of CHMI and set to a ratio of ST/GMA/MA/MPTMS (weight ratio) = 10/55/5/30. 4). The copolymer (D-4) had a solid content concentration of 31.3% by mass, a weight average molecular weight (Mw') of 11,500, and a degree of dispersion (Mw'/Mn') of 2.3.

[Synthesis Example 19]

In addition to ST, CHMI, GMA, and MA, MPTMS is used and set to a ratio of ST/GMA/MA/CHMI/MPTMS (weight ratio) = 10/45/5/10/30, in addition to The same operation as in Synthesis Example 15 was carried out to obtain a copolymer (D-5). The copolymer (D-5) had a solid content concentration of 31.7% by mass, a weight average molecular weight (Mw') of 12,000, and a degree of dispersion (Mw'/Mn') of 2.0.

[Synthesis Example 20]

In a flask equipped with a condenser and a stirrer, 4.0 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 245 parts by mass of diethylene glycol methyl ethyl ether were added, followed by addition of MA. 18 parts by mass, 38 parts by mass of GMA, 5 parts by mass of ST, and 34 parts by mass of DMC, and after nitrogen substitution, 5 parts by mass of 1,3-butadiene (hereinafter referred to as "BD") was gradually stirred and obtained. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 4 hours to carry out polymerization to obtain a copolymer (D-6). The copolymer (D-6) had a solid content concentration of 29.3% by mass, a weight average molecular weight (Mw') of 20,000, and a degree of dispersion (Mw'/Mn') of 2.0.

Preparation of a radiation sensitive linear composition, and formation of a protective film and an interlayer insulating film

[Example 1]

(B-1) dipentaerythritol hexaacrylate as component [B] was added to the solution containing the polysiloxane (A-1) obtained in Synthesis Example 1 (100 parts by mass in terms of solid content). 20 parts by mass of a mixture of dipentaerythritol pentaacrylate (mole ratio 50/50), (C-1) ethyl ketone as component [C], 1-[9-ethyl-6-(2-methylbenzene) 3 parts by mass of the methylidene)-9H-carbazol-3-yl]-, 1-(O-ethenylhydrazine), and further, propylene glycol monomethyl ether and ethylene glycol are added so that the solid content concentration is 25% by mass. A mixed solvent of monobutyl ether (mixing ratio of 80/20 w/w%) was used to prepare a radiation sensitive composition.

Then, the radiation sensitive composition was applied onto a SiO ₂ -impregnated glass substrate using a spinner, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a coating film (evaluation of ITO adhesion described later) A substrate with ITO attached is used. Then, the obtained coating film was exposed to ultraviolet rays at an exposure amount of 300 mJ/cm ² . Subsequently, it was developed by using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 25 ° C for 60 seconds, then washed with pure water for 1 minute, and further heated in an oven at 230 ° C for 60 minutes, thereby forming a protective film having a film thickness of 2.0 μm. membrane.

In addition, the rotation speed of the rotator at the time of forming the coating film was adjusted so that the film thickness after heating was 3.0 μm, and a mask having a contact hole pattern having a size of 20 μm, 30 μm, 40 μm, or 50 μm was interposed therebetween. An interlayer insulating film is formed in the same manner as the above-described protective film, except that the exposure gap of μm (the distance between the substrate and the mask) is exposed.

The obtained protective film and interlayer insulating film were evaluated for the following physical properties. The results are shown together in Table 1.

Physical property evaluation

1) Heat-resistant transparency of the protective film

The substrate having the protective film formed as described above was heated in a clean oven at 250 ° C for 1 hour, and a wavelength of 400 before and after heating was measured using a spectrophotometer (150-20 type double beam manufactured by Hitachi, Ltd.). The light transmittance (%) at nm was measured, and then heat-resistant transparency (%) was calculated according to the following formula. When the value is 4% or less, it is judged that the heat-resistant transparency of the protective film is good.

Heat-resistant transparency (%) = light transmittance before heating (%) - light transmittance after heating (%)

2) Pencil hardness of the protective film

The pencil hardness (surface hardness) of the protective film was measured on the substrate having the protective film formed as described above by "8.4.1 pencil scratch test of JIS K-5400-1990". When the value is 4H or more, it is judged that the surface hardness of the protective film is good.

3) Scratch resistance of protective film

For the substrate having the protective film formed as described above, a weight of 200 g was applied to the steel wool #0000 using a vibration-type wear tester and reciprocated 10 times. The condition of the scratch was evaluated by the naked eye according to the following criteria. When the score is ◎ or ○, it is judged to have good scratch resistance.

Benchmark

◎: completely unaffected,

○: There are 1 to 3 scars,

△: There are 4 to 10 scars,

×: There are more than 10 scars.

4) Heat-resistant cracking of the protective film

The substrate having the protective film formed as described above was additionally calcined at 300 ° C for 30 minutes, and then left at 23 ° C for 24 hours, and a laser microscope (VK-manufactured by Keyence) was used according to the following criteria. 8500) to confirm whether cracks have occurred on the surface of the protective film. When the score was ◎ or ○, it was judged that the heat-resistant crack was good.

Benchmark

◎: No cracks,

○: There are 1 to 3 cracks,

△: There are 4 to 10 cracks,

×: There are more than 10 cracks.

5) ITO adhesion of protective film

A protective film was formed by the same operation as above except that the ITO-coated substrate was used instead of the SiO ₂ -impregnated glass substrate, and a pressure cooker test (120 ° C, humidity: 100%, 4 hours) was performed. Then, the "8.5.3 Adhesive Mesh Tape Method of JIS K-5400-1990" was carried out, and the number of meshes remaining in 100 meshes was determined, and the ITO adhesion of the protective film was evaluated. When the number of meshes remaining in 100 meshes is 80 or less, it is judged that the ITO adhesion is bad.

6) The sensitivity of the protective film

A coating film formed by the same operation as above was exposed using a exposure machine (TME-400PRJ, manufactured by Topcon), with a pattern having a line and space of 10 μm/30 μm. After the exposure amount was changed and exposed, the film was developed by a dipping method at 25 ° C for 60 seconds using a 0.04% by mass aqueous KOH solution. Then, it was washed with ultrapure water for 1 minute, and dried to form a pattern on the glass substrate. At this time, the minimum exposure amount required for the pattern of the line and the gap of 10 μm/30 μm to be not peeled off was measured. This minimum exposure amount was evaluated as the radiation sensitivity. When the minimum exposure amount is 100 mJ/cm ² or less, the sensitivity is judged to be good. Furthermore, the case where the pattern could not be formed was evaluated as ×.

7) Resolution of interlayer insulating film

In the formation of the above interlayer insulating film, the size of the resolvable contact hole pattern was measured. When the contact hole pattern of 30 μm or less can be analyzed, it is judged that the resolution is good. Furthermore, the case where the pattern could not be formed was evaluated as ×.

8) KOH developability of protective film

A coating film of 3.0 μm was formed on the substrate having the protective film formed as described above, and developed by a dipping method at 25° C. for 60 seconds using a 0.04% by mass aqueous KOH solution. Then, it was washed with water, and the presence or absence of the film residue remaining on the substrate was observed with an optical microscope, and evaluated according to the following criteria. In the case where the film residue was not observed, it was judged that the KOH developability was good. On the other hand, when the film residue was confirmed on the entire substrate, it was judged that there was no KOH developability, which was a problem.

Benchmark

○: No film residue was confirmed

△: A slight film residue was confirmed.

×: Film residue was confirmed on the entire substrate

[Example 2 to Example 15 and Comparative Example 1 to Comparative Example 4]

A radiation sensitive composition was prepared in the same manner as in Example 1 except that the types and the amounts (mass parts) of the respective components to be formulated were as described in Table 1. Then, a protective film and an interlayer insulating film were formed in the same manner as in Example 1 using the obtained radiation sensitive composition. The obtained protective film and interlayer insulating film were subjected to the same physical property evaluation as in Example 1. The results are shown together in Table 1.

[Examples 16 to 26 and Comparative Examples 5 to 7]

A radiation sensitive composition was prepared in the same manner as in Example 1 except that the types and the amounts (parts by mass) of the respective components to be formulated were as described in Table 2. Then, a protective film and an interlayer insulating film were formed in the same manner as in Example 1 using the obtained radiation sensitive composition. The obtained protective film and interlayer insulating film were subjected to the same physical property evaluation as in Example 1. The results are shown together in Table 1.

In Tables 1 and 2, the respective symbols of the component [A], the component [B], the component [C], the component [D], and the component [E] respectively represent the following articles.

Ingredient [A]

A-1: MTMS/TEOS/TMSPS=80/15/5 (mol%)

A-2: MTMS/TEOS/MPTMS/TMSPS=68/15/15/2 (mol%)

A-3: MTMS/TEOS/MPTMS/TMSPS=62/15/15/8 (mol%)

A-4: MTMS/TEOS/MPTMS/TMSPS=55/15/15/15 (mol%)

A-5: MTMS/TEOS/PTMS/MPTMS/TMSPS=50/15/15/15/5 (mol%)

A-6: MTMS/TEOS/APTMS/TMSPS=65/15/15/5 (mol%)

A-7: MTMS/TEOS/APTMS/TMSPS=50/30/15/5 (mol%)

A-8: MTMS/TEOS/MPTMS/APTMS/TMSPS=77/7/1/10/5 (mol%), 1c ¹ /1d ¹ =0.1

A-9: MTMS/TEOS/MPTMS/APTMS/TMSPS=50/30/5/10/5 (mol%), 1c ¹ /1d ¹ =0.5

A-10: MTMS/TEOS/MPTMS/APTMS/TMSPS=15/62/8/10/5 (mol%), 1c ¹ /1d ¹ =0.8

A-11: MTMS/TEOS/MPTMS/APTMS/TMSPS=50/30/10/5/5 (mol%), 1c ¹ /1d ¹ =2.0

A-12: MTMS/TEOS/MPTMS/TMSPS=50/30/15/5 (mol%)

A-13: MTMS/TEOS/APTMS/TMSPS=50/30/15/5 (mol%)

A-14: MTMS/TEOS/TMSPS=60/30/10 (mol%)

A-1: MTMS/APTMS/TMSPS=80/15/5 (mol%)

A-2: MTMS/MPTMS/APTMS/TMSPS=80/5/10/5 (mol%)

A-3: MTMS/TEOS/APTMS=70/15/15 (mol%)

A-4: MTMS/PTMS=70/30 (mol%)

A-5: MTMS/MEPTMS=50/50 (mol%)

Ingredient [B]

B-1: a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (mole ratio 50/50), (trade name: DPHA, manufactured by Nippon Kayaku Co., Ltd.)

B-2: Pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

B-3: succinic acid-modified dipentaerythritol pentaacrylate (trade name: Aronix M-520, manufactured by Toagosei Co., Ltd.)

B-4: tris(propylene methoxyethyl) isocyanate (trade name: Aronix M-315, manufactured by Toagosei Co., Ltd.)

B-5: Commercial product containing a polyfunctional urethane-based compound (trade name: KAYRAD DPHA-40H, manufactured by Nippon Kayaku Co., Ltd.)

Ingredient [C]

C-1: ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl) ( Product name: IRGACURE OX02, manufactured by BASF)

C-2: bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide

(trade name: IRGACURE 819, manufactured by BASF)

C-3: 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzhydrylhydrazine)] (trade name: IRGACURE OXE01, manufactured by BASF Corporation)

C-4: 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one

C-5: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole

C-6: 4,4'-bis(diethylamino)benzophenone

C-7: 2-mercaptobenzothiazole

Ingredient [D]

D-1: ST/GMA/MA/CHMI=18/40/20/22 (wt%)

D-2: ST/GMA/MA/DCM/HMAd=20/14/5/21/40 (wt%)

D-3: MA/GMA/MPTMS=5/65/30 (wt%)

D-4: ST/GMA/MA/MPTMS=10/55/5/30 (wt%)

D-5: ST/GMA/MA/CHMI/MPTMS=10/45/5/10/30 (wt%)

D-6: ST/GMA/MA/DCM/BD=5/38/18/34/5 (wt%)

Ingredient [E]

E-1: Polymethyl methacrylate microparticles (trade name: MP-300, manufactured by Amika Chemical Co., Ltd.)

E-2: Organic bismuth sol (trade name: IPA-ST, manufactured by Nissan Chemical Industries Co., Ltd.)

E-3: ZrO ₂ sol (trade name: ID191, manufactured by Tayca Co., Ltd.)

E-4: TiO ₂ sol (trade name: TS-103, manufactured by Tayca Co., Ltd.)

Claims (16)

A radiation sensitive composition comprising the following component [A ¹ ], component [B], and component [C]: [A ¹ ] wherein tetraethoxy decane or a partial hydrolyzate thereof is represented by the following formula (1) a hydrolyzable decane compound or a partial hydrolyzate thereof, and a polyoxyalkylene obtained by hydrolysis-condensation of a hydrolyzable decane compound represented by the following formula (2) or a partially hydrolyzed product thereof; [B] having two or more ethylene a compound having an unsaturated group (excluding the component [A ¹ ]); [C] a photoradical polymerization initiator; [Chemical 1] [Chemical 2] In the formula (1), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and R ² represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms or a (meth)acryloxy group, m. An integer of 1 to 3 is represented, n represents an integer of 0 to 6; in the formula (2), R ³ represents an alkyl group having 1 to 6 carbon atoms, x represents an integer of 1 to 3, and y represents an integer of 1 to 6, z Indicates an integer from 0 to 3.]. The radioactive linear composition according to claim 1, wherein the hydrolyzable decane compound represented by the above formula (2) or a partially hydrolyzed product thereof is added in an amount of 15 mol% or less based on the total amount of the raw material compound. . The radiation-sensitive linear composition having the carbon number of 1 to 6 or an aryl group having 6 to 14 carbon atoms as the above-mentioned formula (1), is a radioactive linear composition according to the first or second aspect of the invention. The hydrolyzable decane compound represented. The radiation sensitive composition according to claim 1 or 2, comprising at least one selected from the group consisting of a hydrolyzable decane compound having a methacryloxy group and a hydrolyzable decane compound having a propylene methoxy group. The hydrolyzable decane compound represented by the above formula (1). A radiation sensitive linear composition comprising the following components [A ² ], component [B], and component [C]: [A ² ] having a SiO ₂ unit, a structural unit represented by the following formula (1a), and the following a polyoxyalkylene of the structural unit represented by the formula (2a); [B] a compound having two or more ethylenically unsaturated groups (excluding the component [A ² ]); [C] photoradical polymerization initiator ;[化3] [Chemical 4] In the formula (1a), R ² represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms or a (meth)acryloxy group, wherein m represents an integer of 1 to 3, and n represents 0 to 6 In the formula (2b), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, x represents an integer of 1 to 3, y represents an integer of 1 to 6, and z represents an integer of 0 to 3]. The radiation-sensitive linear composition according to claim 5, wherein the content ratio of the structural unit represented by the above formula (2a) is 15 mol% or less in all the structural units. The radiation-sensitive linear composition according to the fifth or sixth aspect of the invention, comprising a structural unit represented by the following formula (1b) as a structural unit represented by the above formula (1a), [Chemical 5] In the formula (1b), R ⁵ represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms, and m has the same meaning as described above. The radiation sensitive composition according to the fifth or sixth aspect of the invention, comprising at least one selected from the structural unit represented by the following formula (1c) and the structural unit represented by the following formula (1d); As a structural unit represented by the above formula (1a), [Chem. 6] [Chemistry 7] [In the formulae (1c) and (1d), m and n have the same meanings as described above]. The radiation sensitive composition according to any one of the first aspect, the second aspect, the fifth aspect, and the sixth aspect, further comprising (D ¹ ) a structural unit having a carboxyl group and (D ² ) A copolymer of structural units of an epoxy group is used as the component [D]. The radiation sensitive composition according to claim 9, wherein the component [D] further has (D ³ ) a structural unit derived from (meth) propylene methoxy propyl trialkoxy decane. The radiation-sensitive linear composition according to claim 9, wherein the content of the component [D] is from 1 part by mass to 45 parts by mass based on 100 parts by mass of the polysiloxane. The radiation sensitive composition according to any one of the first aspect, the second aspect, the fifth aspect, and the sixth aspect, further comprising at least one selected from the group consisting of organic particles and inorganic particles. As component [E]. The radiation-sensitive linear composition according to any one of claims 1, 2, 5, and 6, which is used for forming a protective film of a touch panel or an interlayer insulating film of a display element. A cured film formed by using the radiation sensitive composition according to any one of claims 1 to 13. A method for forming a cured film, comprising the following steps (1) to (4); (1) applying the radiation-sensitive composition according to any one of claims 1 to 13 to a substrate a step of forming a coating film thereon; (2) a step of irradiating at least a part of the coating film formed in the step (1) with radiation; (3) developing a coating film irradiated with radiation in the step (2) by using an alkali developing solution And (4) a step of heating the developed coating film in the step (3). The method for forming a cured film according to claim 15, wherein an inorganic alkali developing solution is used as the alkali developing solution.