KR101798014B1 - Radiation-sensitive composition, cured film of same, and method for forming cured film - Google Patents

Abstract

A radiation sensitive composition capable of forming a cured film in which required characteristics for a protective film or an interlayer insulating film are balanced at a high level and in a well balanced manner and which can be also developed with an inorganic alkali developer is provided. The radiation sensitive composition of the present invention comprises the following components [A ¹ ], [B] and [C]; [A ¹ ] A ^{process for} producing a hydrolyzable silane compound, which comprises reacting tetraethoxysilane or a partial hydrolyzate thereof, a hydrolyzable silane compound represented by the following formula (1) or a partial hydrolyzate thereof and a hydrolyzable silane compound or partial hydrolyzate thereof represented by the following formula (B) a compound having two or more ethylenically unsaturated groups (excluding the component [A ¹ ]), and [C] a photoradical polymerization initiator. Wherein R ¹ and R ³ represent an alkyl group having 1 to 6 carbon atoms, R ² represents an alkyl group having 1 to 20 carbon atoms, m represents an integer of 1 to 3, and n represents an integer of 0 to 6, , 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.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a radiation-sensitive composition, and a cured film and a method for forming the same.

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

Display elements such as liquid crystal display elements, integrated circuit elements, solid-state image pickup elements, organic EL elements, and the like include a protective film for preventing deterioration or damage of electronic components including a touch panel or a layer for interlayer insulation A cured film such as an insulating film is formed. For forming such a cured film, a radiation-sensitive composition is used. For example, a radiation-sensitive composition film is formed on a substrate and irradiated with radiation (hereinafter referred to as "exposure") through a photomask having a predetermined pattern ), Developed with an organic alkali developer to dissolve and remove unnecessary portions, and then post-baked to form 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, a film which is smooth and has a high hardness, an excellent image pickup resistance, (Heat resistance cracking) even under a high temperature condition (heat resistance cracking property), excellent sensitivity to radiation, good pattern without a developing residual film (Developing property) are required.

On the other hand, in the cured film used as the interlayer insulating film, since it is necessary to form a pattern of the contact hole for wiring, in addition to the required characteristics in the above-mentioned protective film, the pattern image (image) (High resolution) is required.

Acrylic resins are mainly used as the components of the radiation sensitive composition. In recent years, however, polysiloxane-based materials superior in heat resistance and transparency to acrylic resins are attracting attention (Patent Documents 1 to 3). However, since the polysiloxane-based material has insufficient adhesion with the ITO (indium tin oxide) substrate and cracks are likely to occur, there is a problem that the polysiloxane-based material can not withstand practical use as a protective film. In addition, a negative radiation-sensitive composition which is advantageous in terms of cost has been developed as a material for forming an interlayer insulating film of a liquid crystal display element (Patent Document 4). However, such a negative radiation- It is difficult to form the contact hole having the hole diameter of the contact hole. Therefore, a positive-tone radiation-sensitive composition is widely used to form an interlayer insulating film of a display element from the advantage of forming a contact hole (Patent Document 5).

Further, it is also possible to add a siloxane oligomer having an oxiranyl group, an oxetanyl group or a mercapto group to a composition containing a copolymer of an unsaturated carboxylic acid and / or an unsaturated carbonic acid anhydride with another unsaturated compound, a polymerizable unsaturated compound and a photopolymerization initiator A radiation-sensitive composition containing an extremely small amount of an additive agent has been proposed, and it has been described that the radiation-sensitive composition can be suitably used for forming a spacer of a display element (Patent Document 6). However, since the use of the spacer of the display element differs from that of the protective film and the interlayer insulating film, it is difficult to satisfy all the requirements for the protective film and the interlayer insulating film.

Japanese Patent Application Laid-Open No. 2000-001648 Japanese Laid-Open Patent Publication No. 2006-178436 Japanese Patent Application Laid-Open No. 2008-248239 Japanese Patent Application Laid-Open No. 2000-162769 Japanese Patent Application Laid-Open No. 2001-354822 Japanese Patent Application Laid-Open No. 2008-233518

As described above, the required characteristics for the protective film and the interlayer insulating film are many in overlapping portions. However, in spite of this, various radiation sensitive compositions have been used in many cases depending on the purpose or the process. It is possible to form a cured film such as a protective film or an interlayer insulating film from one kind of radiation sensitive composition and further to make the pattern transfer method negative by using it. Therefore, development of a negative-tone radiation-sensitive composition capable of forming both a protective film and an interlayer insulating film is urgently required.

Further, at the time of development, TMAH (tetramethylammonium hydroxide) is usually used as an alkali developer, but from the viewpoint of cost reduction and productivity improvement, development of a radiation-sensitive composition capable of being developed with an inorganic alkali developer is desired .

It is therefore an object of the present invention to provide a radiation sensitive composition which is capable of forming a cured film in which the required properties of the protective film and the interlayer insulating film are balanced in a high level and in a well balanced manner and which can be also developed with an inorganic alkali developer. Another object of the present invention is to provide a cured film in which the required characteristics of the protective film and the interlayer insulating film are both balanced to a high level and a method of forming the same.

In order to solve the above-mentioned problems, the present invention firstly relates to the following components [A ¹ ], [B] and [C];

[A ¹ ] A ^{process for} producing a hydrolyzable silane compound, which comprises reacting tetraethoxysilane or a partial hydrolyzate thereof, a hydrolyzable silane compound represented by the following formula (1) or a partial hydrolyzate thereof and a hydrolyzable silane compound or partial hydrolyzate thereof represented by the following formula The polysiloxane obtained by hydrolysis and condensation

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

[C] Photo radical polymerization initiator

A radiation-sensitive composition comprising:

Wherein R ¹ represents an alkyl group having 1 to 6 carbon atoms, 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, and m is an integer of 1 to 3 And n represents an integer of 0 to 6; 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.

The present invention, secondly, relates to the following components [A ² ], [B] and [C];

[A _^2] SiO ² units with the following formula (1a) a polysiloxane having the structural unit represented by the structural unit of the following formula (2a) represented by the

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

And [C] a photoradical polymerization initiator.

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 is an integer of 1 to 3, and n is an integer of 0 to 6 Lt; / RTI > 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 ].

The present invention thirdly provides a cured film formed using the radiation sensitive composition.

Fourthly, the present invention provides the following steps (1) to (4);

(1) a step of forming a coating film of the radiation sensitive composition on a substrate,

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

(3) a step of developing the coated film irradiated with the radiation in the step (2) with an alkaline developer, and

(4) A method for forming a cured film including a step of heating the developed coating film in the step (3).

According to the present invention, there is provided a radiation-sensitive composition which is effective for forming a cured film capable of balancing various properties such as heat-resistant transparency, hardness, image-capturing property, heat resistance cracking property, adhesion property, . Further, since the radiation sensitive composition of the present invention has a sufficient resolution, it is possible to form a fine contact hole, and furthermore, it can be developed with an inorganic alkali developer.

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

(Mode for carrying out the invention)

Sensitizing radiation property  Composition

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

Component [A]

The component [A ¹ ] can be obtained by reacting tetraethoxysilane or a partial hydrolyzate thereof (hereinafter simply referred to as "TEOS") and a hydrolyzable silane compound or partial hydrolyzate thereof represented by the following formula (1) 1) "), and a hydrolyzable silane compound represented by the following formula (2) or a partial hydrolyzate thereof (hereinafter also referred to as" compound (2) "). By containing such a component [A], solubility in an alkali developing solution used in a developing step, particularly, in an inorganic alkali developing solution is enhanced, and thus the developing property can be improved, and the heat resistance transparency and image-capturing property of the obtained cured film can be improved It becomes. Herein, the term "partial hydrolyzate" as used herein means a siloxane compound (having a silicon atom number of from 2 to 20) having at least one, preferably at least two alkoxy groups remaining in the molecule, produced by hydrolysis and condensation reaction of an alkoxy group 100, preferably from about 2 to about 30, siloxane oligomers)

Wherein R ¹ represents an alkyl group having 1 to 6 carbon atoms, 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, and m is an integer of 1 to 3 And n represents an integer of 0 to 6;

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

The alkyl group in R ¹ and R ³ may be linear, branched or cyclic. The number of carbon atoms of the alkyl group in R ¹ and R ³ is 1 to 6, but the number of carbon atoms is preferably 1 to 4, more preferably 1 or 2, from the viewpoint of reactivity of hydrolysis and condensation. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, , A methyl group or an ethyl group is particularly preferable. When a plurality of R < ¹ > exist in the same molecule, they may be the same or different. The same also applies to R ³ .

The alkyl group for R ² may be linear, branched or cyclic. The number of carbon atoms of the alkyl group in R ² is 1 to 20, preferably 1 to 10, and more preferably 1 to 6. Specifically, in addition to the alkyl exemplified for R ¹ and R ³ , an alkyl group such as an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, a n-nonyl group, Dodecyl group, n-tridecyl group, n-tetradecyl group, n-hexadecyl group, cycloheptyl group and cyclooctyl group.

The aryl group in 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 anthryl group and a phenanthryl group. Among them, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.

The alkyl group and aryl group in R ² may have a substituent. 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. The position and the number of the substituent may be any, and when the substituent is two or more, the substituent may be the same or different. Examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom and an iodine atom, and among them, a fluorine atom is preferable. The halogen atom may substitute a part or all of the hydrogen atoms of the alkyl group and the aryl group, but is preferably completely 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. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, and an iso-propoxy group.

The (meth) acryloxy group in 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. When a plurality of R < ² > exist in the same molecule, they may be the same or different.

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

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

z is an integer of 0 to 3, but 0 or 1 is preferable, and 0 is more preferable.

Next, the constituents of the polysiloxane of the component [A ¹ ] will be described.

The component [A ¹ ] contains TEOS as an essential component. TEOS is a multifunctional silane compound having four hydrolysable groups. When a structural unit derived from TEOS is contained in the polysiloxane, adhesion with the substrate is enhanced by interaction with the hydroxyl group on the surface of the metal substrate such as ITO, and the cross-linking density of the polysiloxane is further increased, and the resulting hardened film has a higher hardness But it is predicted that cracking easily occurs and the image-capturing property is poor. Contrary to this prediction, in the present invention, the polysiloxane is formed by combining the compound (1) and the compound (2) to be described later in TEOS, and further the component [B] is contained in the polysiloxane to contain TEOS at a high concentration The present inventors have found that a cured film excellent in image pickup property and heat crack resistance as well as high in hardness and substrate adhesion is obtained. This point can not be predicted at all from the conventional knowledge.

The amount of TEOS to be added is preferably 5 to 75 mol%, more preferably 10 to 70 mol%, and still more preferably 10 to 70 mol%, relative to the total amount of the raw materials, from the viewpoints of improvement in hardness, adhesion, image- Is from 25 to 65 mol%.

The component [A ¹ ] further contains the compound (1) as an essential component. The compound (1) is a component that contributes to improvement of heat crack resistance and image-capturing property while maintaining an excessive cross-linking density by TEOS and maintaining a proper cross-link density.

Examples of the compound (1) include a silane compound having m = 1, a silane compound having m = 2, and a silane compound having m = 3. Specifically, the following compounds can be mentioned. The compound (1) may be used singly or in combination of two or more kinds.

As the silane compound having m = 1, for example,

Propyltriethoxysilane, methyltriethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriiso- propoxysilane, ethyltri- A hydrolyzable silane compound having one alkyl group having 1 to 20 carbon atoms such as butoxysilane, butyltrimethoxysilane and decyltrimethoxysilane;

A hydrolyzable silane compound having one halogen-substituted alkyl group having 1 to 20 carbon atoms such as trifluoropropyltrimethoxysilane;

Hydrolyzable silane compounds having one aryl group having 6 to 14 carbon atoms such as phenyltrimethoxysilane and phenyltriethoxysilane;

Methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3- A hydrolyzable silane compound having one (meth) acryloxy group such as methoxysilane, 3-acryloxypropyltripropoxysilane and the like.

As the silane compound having m = 2, for example,

Hydrolyzable silane compounds having two alkyl groups having 1 to 20 carbon atoms such as dimethyldimethoxysilane and dibutyldimethoxysilane;

A hydrolyzable silane compound having two aryl groups having 6 to 14 carbon atoms such as diphenyldimethoxysilane;

Alkoxysilane compounds having a (meth) acryloxy group such as 3-methacryloxypropylmethyldimethoxysilane and 3-acryloxypropylmethyldimethoxysilane and an alkyl group having 1 to 20 carbon atoms;

An alkoxysilane compound having a (meth) acryloxy group such as 3-methacryloxypropylphenyldimethoxysilane and 3-acryloxypropylphenyldimethoxysilane and an aryl group having 6 to 14 carbon atoms;

(Meth) acryloxy compounds such as 3,3'-dimethacryloxypropyldimethoxysilane and 3,3'-diacryloxypropyldimethoxysilane.

Examples of the silane compound having m = 3 include hydrolyzable silane compounds having three alkyl groups having 1 to 20 carbon atoms such as tributylmethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, and tributylethoxysilane;

A hydrolyzable silane compound having three aryl groups having 6 to 14 carbon atoms such as triphenylmethoxysilane;

There can be mentioned hydrolyzable silane compounds having three (meth) acryloxy groups such as 3,3 ', 3 "-trimethylacryloxypropylmethoxysilane and 3,3', 3" -triacryloxypropylmethoxysilane. have.

Of these compounds (1), preferred are a hydrolyzable silane compound having an alkyl group having 1 to 6 carbon atoms, a hydrolyzable silane compound having an aryl group having 6 to 14 carbon atoms, and a hydrolyzable silane compound having a (meth) acryloxy group, Is particularly preferably a silane compound having m = 1 according to the formula (1).

Specific examples of suitable compounds (1)

An alkoxysilane compound having one alkyl group having 1 to 6 carbon atoms such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane and butyltrimethoxysilane;

An alkoxysilane compound having one aryl group having 6 to 14 carbon atoms such as phenyltrimethoxysilane;

(Meth) acryloxy group such as 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane and 3-methacryloxypropyltriethoxysilane is substituted with 1 And the like.

The total amount of the compound (1) to be added is preferably 10 to 80 moles, more preferably 10 to 80 moles, more preferably 10 to 80 moles, %, More preferably 10 to 75 mol%, and still more preferably 15 to 70 mol%.

In the present invention, from the viewpoint of further improvement of the image-capturing property and the heat-resistant cracking property, the hydrolyzable silane compound having an alkyl group having 1 to 6 carbon atoms and the hydrolyzable silane compound having an aryl group having 6 to 14 carbon atoms It is preferable to use at least one silane compound selected from the decomposable silane compounds (hereinafter also referred to as "silane compound (1b ¹ )"). In these silane compounds (1b ¹ ) This silane compound is particularly preferable.

From the viewpoint of further improving the sensitivity and developability, it is preferable to use a hydrolyzable silane compound having a (meth) acryloxy group in the above-mentioned suitable compound (1), and the silane compound represented by the formula Lt; RTI ID = 0.0 > m = 1 < / RTI > As the hydrolyzable silane compound having a (meth) acryloxy group, a hydrolyzable silane compound having a methacryloxy group (hereinafter also referred to as "silane compound (1c ¹ )") and a hydrolyzable silane compound having an acryloxy group , And "silane compound (1d ¹ )"), and it is more preferable to use the silane compound (1c ¹ ) and the silane compound (1d ¹ ) in combination. Further, the hydrolyzable silane compound having a (meth) acryloxy group is preferably used together with the silane compound (1b ¹ ).

When the silane compound (1b ¹ ) is used as the compound ( ¹ ), the total amount of the silane compound (1b ¹ ) to be added is preferably in the range of Is preferably 10 to 80 mol%, more preferably 15 to 75 mol%, and still more preferably 30 to 70 mol%.

The total amount of the hydrolyzable silane compound having a (meth) acryloxy group is preferably 5 to 25 mol%, more preferably 10 to 20 mol% based on the total amount of the starting compounds, from the viewpoint of further improving sensitivity and resolution Mol%.

When the silane compound (1c ¹ ) and the silane compound (1d ¹ ) are used in combination, the charging ratio (1c ¹ / 1d ¹ ) of the silane compound (1c ¹ ) and the silane compound Is preferably 0.05 to 3, more preferably 0.2 to 1.5, still more preferably 0.3 to 1.

The component [A ¹ ] further contains the compound (2) as an essential component. The compound (2) contributes to the enhancement of developability while contributing to the improvement of the heat cracking resistance and the image-capturing property by suppressing the excessive crosslinking density increase by TEOS.

Examples of the compound (2) include a silane compound having x = 1, a silane compound having x = 2, and a silane compound having x = 3. Specifically, the following compounds can be mentioned. The compounds (2) may be used singly or in combination of two or more kinds.

Examples of the silane compound having x = 1 include 2-trimethoxysilylethylsuccinic anhydride, 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, Succinic acid, 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride and 3-tripenoxysilylpropylsuccinic anhydride.

Examples of the silane compound having x of 2 include di-1-butoxy-bis [3- (dihydro-2,5-furandionyl) propyl] silane, bis [3- (dihydro- (4-methyl-2-pyridinyl) propyl] dimethoxysilane and bis [3- (dihydro-2H-pyran-2,6 (5H) -dionyl) propyl] dimethoxysilane.

Examples of the silane compound having x = 3 include tris [3- (dihydro-2,5-furandionyl) propyl] methoxysilane.

Of these compounds (2), silane compounds having x = 1 are preferable. Specific examples of suitable compounds (2) include 3-trimethoxysilylpropylsuccinic anhydride and 3-triethoxysilylpropylsuccinic anhydride. have.

The total amount of the compound (2) to be added is preferably not more than 15 mol% with respect to the total amount of the starting compounds from the viewpoints of heat resistance transparency, hardness, image-taking property, heat resistance crack resistance, adhesion, sensitivity, , More preferably not more than 13 mol%, still more preferably not more than 10 mol%, further preferably not more than 7 mol%. The lower limit of the total amount of the compound (2) to be added is preferably 0.5 mol%, more preferably 1 mol%, still more preferably 2 mol%, and particularly preferably 3 mol% %to be. The total amount of the compound (2) to be added is preferably in the range of 0.5 to 15 mol%, more preferably 1 to 13 mol%, still more preferably 2 to 10 mol% Is 3 to 7 mol%.

Examples of the method of hydrolyzing and condensing TEOS, compound (1) and compound (2) include mixing TEOS, compound (1) and compound (2) as raw materials in a solvent, adding water to the mixed solution, Is preferably employed. In this case, each raw material compound and water may be added to the reaction system at one time to carry out the reaction in one step, or the raw material compounds and water may be added in several stages in the reaction system to effect the hydrolytic condensation reaction in multiple steps good. The hydrolysis-condensation product includes not only all the hydrolyzable groups hydrolyzed and condensed, but also some hydrolyzable groups remaining without hydrolysis or condensation.

In the hydrolysis and condensation reaction, the acid anhydride group of the compound (2) is ring-opened as shown in the following reaction formula to produce a carboxyl group. The OR ⁴ group in the formula represents a hydroxyl group derived from a carboxyl group generated by hydrolysis or an alkoxy group formed by alcoholysis with an alcohol having 1 to 6 carbon atoms formed in the reaction system by hydrolysis.

In the formulas, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and z is as defined above. Examples of the alkyl group for R ⁴ include the same groups as those for R ^1, and the specific structure thereof is as described for R ¹ .

The solvent to be used for the hydrolysis and condensation reaction is not particularly limited, but usually the same solvent as used for preparing the radiation sensitive composition is used. Examples of such a solvent include ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and propionic acid esters. These solvents may be used singly or in combination of two or more kinds. Among these, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate and methyl 3-methoxypropionate are preferable.

As the water used in the hydrolysis and condensation reaction, it is preferable to use water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment, distillation or the like. By using such purified water, it is possible to suppress the side reaction and improve the reactivity of hydrolysis.

The amount of water to be used is preferably 0.1 to 3 mol, more preferably 0.3 to 2 mol, and still more preferably 0.5 to 1.5 mol, per 1 mol of the total of hydrolysable groups of TEOS, compound (1) and compound (2) It is mall. By using such an amount of water, the reaction rate of hydrolysis and condensation can be optimized.

The hydrolysis and condensation reaction may be carried out autocatalytically with carbonic acid produced by the hydrolysis of the compound (2) without addition of a catalyst, but a separate acid catalyst may be 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 trifluoromethanesulfonic acid, and acidic ion exchange resins .

The amount of the catalyst to be used is preferably 0.2 mol or less, more preferably 0.00001 to 0.1 mol, per 1 mol of the total amount of TEOS, the compound (1) and the compound (2) from the viewpoint of accelerating the hydrolysis and condensation reaction .

The reaction temperature and the reaction time in the hydrolysis and condensation reaction can be appropriately set. For example, the following conditions can be employed. The reaction temperature is preferably 40 to 200 占 폚, more preferably 50 to 150 占 폚. The reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours. By using such reaction temperature and reaction time, the hydrolysis and condensation reaction can be performed most efficiently.

After the hydrolysis and condensation reaction, water and the produced alcohol can be removed from the reaction system by adding a dehydrating agent and then blending the dehydrating agent. The dehydrating agent used in this step is generally completely depleted in dehydration ability by adsorbing or enclosing excess water, or is removed by this distribution.

Component [A ² ]

The component [A ² ] is a compound represented by the following formula (1), which is obtained by reacting an SiO ₂ unit derived from TEOS with a structural unit (hereinafter also referred to as "structural unit (1a)") (Hereinafter also referred to as " structural unit (2a) ") represented by the following formula (2a). The respective structural units of the SiO ₂ unit, the structural unit (1a) and the structural unit (2a) may be composed of two or more species,

Wherein R ² , R ⁴ , m, n, x, y and z are as defined above.

Among them, m is preferably 1 in formula (1a), and x is preferably 1 in formula (2a).

Structural units in the case where m is 1 in the formula (1a) and x is 1 in the formula (2a) are shown in the following formulas (1-1a) and (2-1a)

Wherein R ² , R ⁴ , n, y and z are as defined above.

Such a polysiloxane can be obtained by providing TEOS, compound (1) and compound (2) to the hydrolysis and condensation reaction described above, but it is also possible to use two kinds of compounds selected from TEOS, compound (1) And the hydrolysis-condensation reaction of the remaining compound with the hydrolysis-condensation product of That is, the SiO ₂ unit, the structural unit (1a) and the structural unit (2a) may be contained in any of the random copolymerization and block copolymerization.

Component [A ^2] of SiO ₂ units, and each content of the structural unit (1a) and the structural unit (2a) is a heat-resistant transparency, hardness, within the image pick-up property, heat crack resistance, adhesion, sensitivity, resolution and developing Castle From the point of view of improvement, it is as follows.

The SiO ₂ unit is preferably 5 to 75 mol%, more preferably 10 to 70 mol%, and still more preferably 25 to 65 mol% in the total structural units of the component [A ² ].

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

Structural units (2a), component [A ^2] in the total structural units, preferably 15 mol% or less, more preferably 13 mol% or less, more preferably 10 mol% or less, more preferably 7 mol of %, And the lower limit thereof is preferably 0.5 mol%, more preferably 1 mol%, still more preferably 2 mol%, particularly preferably 3 mol%. The content of the structural unit (2a) is preferably from 0.5 to 15 mol%, more preferably from 1 to 13 mol%, and still more preferably from 2 to 10 mol%, based on the total structural units of the component [A ² ] %, More preferably 3 to 7 mol%.

The structural unit (1a) preferably contains at least one structural unit represented by the following formula (1b) (hereinafter also referred to as "structural unit (1b)") from the viewpoint of further improving the heat resistant cracking property and the image- desirable.

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 is as defined above.

Examples of the alkyl group for R ⁵ include the same groups as those for R ^1. Examples of the aryl group for R ⁵ include the same groups as those for R ² . The concrete configuration thereof is as described above.

Also, m is preferably 1. The structural unit when m is 1 in the formula (1b) is shown in the following formula (1-1b): "

[Wherein R ⁵ is the same as defined above].

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

In the present invention, from the viewpoint of further improving the sensitivity and developability, the structural unit (1a) is a structural unit represented by the following formula (1c) (hereinafter also referred to as "structural unit (1c)") (Hereinafter also referred to as " structural unit (1d) ") represented by the structural unit (1c) desirable. Also, it is preferable to contain at least one member selected from the structural unit (1c) and the structural unit (1d) together with the structural unit (1b).

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

Structural units in the case where m is 1 in the formulas (1c) and (1d) are shown by the following formulas (1-1c) and (1-1d), respectively:

[Wherein n is the same as defined above].

The total content ratio of the structural unit (1c) and the structural unit (1d) is preferably 5 to 25 mol%, more preferably 5 to 20 mol%, and more preferably 5 to 20 mol%, based on the total structural units of the component [A ² ], from the viewpoint of further improving sensitivity and resolution Is 10 to 20 mol%.

When the structural unit (1c) and the structural unit (1d) are contained, the content ratio (1c / 1d) of the structural unit (1c) and the structural unit (1d) Preferably in the range of 0.05 to 3, more preferably in the range of 0.2 to 1.5, and still more preferably in the range of 0.3 to 1.

Examples of the structural unit (2a) include structural units derived from the above-mentioned compound (2). Among them, structures derived from 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride and the like Unit.

The component [A] may be used singly or in a mixture of two or more kinds.

The molecular weight of the component [A] can be measured as a weight average molecular weight in terms of polystyrene using GPC (gel permeation chromatography) using tetrahydrofuran as the mobile phase. 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 10000 or less, it is possible to prevent lowering of the alkali developing property of the radiation sensitive composition.

The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured under the same conditions is preferably 1.0 to 15.0, more preferably 1.1 to 10.0, More preferably 1.1 to 5.0. By making the content within such a range, alkali developability, adhesion, and crack resistance can be achieved.

Component [B]

The component [B] is a compound having two or more ethylenically unsaturated groups but is a multifunctional monomer polymerized by irradiation with radiation in the presence of a photo radical polymerization initiator of the component [C] described later. However, the component [B] excludes the component [A].

As such a compound, a bifunctional or trifunctional or more (meth) acrylic acid ester is preferably used from the viewpoint of good polymerizability and improved strength of the resulting cured film.

Examples of the bifunctional (meth) acrylic acid esters include multifunctional (meth) acrylates obtained by reacting (meth) acrylic acid with a divalent aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol or polypropylene glycol . Specific examples include ethylene glycol diacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate Hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,6-hexanediol dimethacrylate, And the like. Commercially available products include ARONIX M-210, Aronix M-240, Aronix M-6200 (trade names, manufactured by Toagosei Co., Ltd.); KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 (above, Nippon Kayakusa); Viscoat 260, Viscoat 312, Viscot 335HP (by Yuki Kagakuko, Osaka); And Light Acrylate 1,9-NDA (Kyoeisha Chemical Co., Ltd.).

Examples of the (meth) acrylic ester having three or more functional groups include multifunctional (meth) acrylates obtained by reacting a tri- or higher-valent aliphatic polyhydroxy compound such as glycerin, trimethylolpropane, pentaerythritol and dipentaerythritol with (meth) . Specific examples include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, di Pentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexaacrylate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate And ethylene oxide-modified dipentaerythritol hexaacrylate. Examples of commercially available products include Aronix M-309, Aronix M-315, Aronix M-400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M- Knicks M-8060, Aronix TO-1450 (available from Toagosei); KAYARAD DMPA-20, KAYARAD DPCA-20, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD DPEA-12 (above, Nippon Kayakusa); Viscot 295, Viscot 300, Viscot 360, Viscot GPT, Viscot 3PA, Viscot 400 (available from Osaka Yuki Kagakuko Co., Ltd.).

Further, it is also possible to use at least one compound selected from the group consisting of tri (2-acryloxyethyl) phosphate, tri (2-methacryloxyethyl) phosphate, succinic acid-modified pentaerythritol triacrylate, succinic acid-modified dipentaerythritol pentaacrylate, A compound having two or more isocyanate groups and at least one (meth) acryloxy group having at least one hydroxyl group in the molecule and having three, four or five (meth) acryloxy groups, A polyfunctional urethane acrylate-based compound obtained by reacting with a compound may be used. Examples of commercially available products containing a polyfunctional urethane acrylate compound include New Frontier R-1150 (Daiichi Kyoei Iyakusa) and KAYARAD DPHA-40H (Nippon Kayaku Co., Ltd.).

Among them, 1,9-nonanediol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, a mixture of ethylene oxide-modified dipentaerythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, succinic acid-modified dipentaerythritol pentaacrylate , Tris (acryloxyethyl) isocyanurate, and a commercially available product containing a polyfunctional urethane acrylate-based compound. Among them, a (meth) acrylic ester having three or more functional groups, particularly three to six functional groups is preferable, and a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate is particularly preferable.

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

Component [C]

Component [C] is a photo radical polymerization initiator. The photo radical polymerization initiator is a compound capable of generating an active species capable of initiating 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.

Examples of the photo radical polymerization initiator used in the present invention include O-acyloxime compounds, acetophenone compounds, acylphosphine oxide compounds, and imidazole compounds.

Specific examples of the O-acyloxime compound include ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -octan- Benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9H-carbazol- -9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -, 1- (O- 1- (9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H-carbazol-3-yl] -, 1- (O-acetyloxime) Ethanone, 1- (9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol- - [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -Acetyl oxime), ethanone, 1- [9-ethyl-6- (2-methyl-4- tetrahydrofuranylmethoxy) (O-benzoyloxymethyl) benzoyl) -9H-carbazol-3-yl] -, 1- And the like. O-acyloxime compounds may be used alone or in admixture of two or more.

Among these, preferable O-acyloxime compounds include ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- -9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl] -, 1- (O- acetyloxime), ethanone, Methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -, 1- O-acetyloxime), 1,2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)].

Examples of the acetophenone compound include an? -Amino ketone compound and? -Hydroxy ketone compound. The acetophenone compounds may be used alone or in admixture of two or more.

Specific examples of the? -amino ketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- - (4-morpholin-4-yl-phenyl) -butan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one.

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

Among these acetophenone compounds,? -Amino ketone compounds are preferred, and 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl- Methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one is particularly preferred.

Specific examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. The acylphosphine oxide compounds may be used alone or in combination of two or more.

Among these acylphosphine oxide compounds, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is preferable.

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

Among these imidazole compounds, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis , 4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) ', 5,5'-tetraphenyl-1,2'-biimidazole and the like are preferable.

When a nonimidazole compound is used, at least one selected from an amino-based sensitizer and a hydrogen donating compound may be added.

Examples of the amino-based sensitizer include N-methyldiethanolamine, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, ethyl p-dimethylaminobenzoate , p-dimethylaminobenzoic acid i-amyl, and the like. Of these amino-based sensitizers, 4,4'-bis (diethylamino) benzophenone is particularly preferable.

Examples of the hydrogen donating compound include thiol compounds. As the thiol compound, for example, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzoimidazole are preferable.

The component [C] may be used singly or as a mixture of two or more kinds. In the present invention, it is preferable that the component [C] contains an O-acyloxime compound.

The content of the component [C] is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 15 parts by mass, further preferably 1 to 10 parts by mass, relative to 100 parts by mass in total of the components [A] and [B] Mass part. By setting the content of the component [C] within the above range, a cured film having high radiation sensitivity and having sufficient hardness can be formed even at a low exposure dose.

When a non-imidazole compound is selected as the component [C] and is used in combination with at least one selected from an amino-based sensitizer and a hydrogen donor compound, the amount of each of the amino-based sensitizer and the hydrogen donor compound to be used is Is preferably from 0.1 to 50 parts by mass, and more preferably from 1 to 20 parts by mass, based on 100 parts by mass of the thiol compound. With such an amount being used, the surface hardness of the resulting cured film can be increased.

Component [D]

In the present invention, as the component [D], (D ^1), the structural unit having a carboxyl group (hereinafter referred to as "structural unit (D ^1)", also known as quot;) and (D ^2), the structural unit having an epoxy group (hereinafter referred to as "structural unit (D ² ) ").≪ / RTI > By containing such a component [D], the sensitivity can be increased and the solubility in an alkali developing solution used in a developing step, particularly, in an inorganic alkali developing solution is excellent. Therefore, the developing property can be improved, It is possible to improve the property.

As the structural unit (D ¹ ), a structure derived from at least one kind of compound selected from (D ¹ -1) unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (hereinafter also referred to as "compound (D ¹ -1) Unit.

Examples of the compound (D ¹ -1) include acrylic acid, methacrylic acid, crotonic acid, 2-acryloxyethylsuccinic acid, 2-methacryloxyethylsuccinic acid, 2-acryloxyethylhexahydrophthalic acid, 2- Mono-carbonic acid such as oxyethylhexahydrophthalic acid; Dicarboxylic acids such as maleic acid, fumaric acid and citraconic acid; And an acid anhydride of the dicarboxylic acid. Among these compounds (D ¹ -1), acrylic acid, methacrylic acid, 2-acryloxyethylsuccinic acid, 2-methacryloxyethylsuccinic acid, 2-methacryloxyethylsuccinic acid and maleic anhydride are preferable from the viewpoint of copolymerization reactivity and solubility of the obtained copolymer in an alkali developer desirable.

The compounds (D ¹ -1) can be used singly or in combination of two or more.

The copolymerization ratio of the structural unit (D ¹ ) is preferably from 1 to 40 mass%, more preferably from 2 to 30 mass%, and still more preferably from 3 to 25 mass% in the total structural units. With such a copolymerization ratio, a radiation-sensitive composition in which the properties such as sensitivity, developability and storage stability are optimized to a higher level is obtained.

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)").

Compound (D ² -2) as, for example, acrylic acid glycidyl acrylate, 2-methyl glycidyl acrylate, 3,4-epoxy-butyl acrylate, 6,7-epoxy-heptyl acrylate, 3,4-epoxycyclohexyl , Acrylic acid epoxy alkyl ester such as 3,4-epoxycyclohexylmethyl acrylate; Glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyhexyl methacrylate, 3,4-epoxycyclohexyl methacrylate, methacrylic Methacrylic acid epoxyalkyl esters such as acid-3,4-epoxycyclohexylmethyl; ? -alkylacrylic acid epoxy alkyl esters such as glycidyl? -ethyl acrylate, glycidyl? -n-propyl acrylate, glycidyl? -n-butyl acrylate,? -ethylacrylic acid, and 6,7-epoxyheptyl; vinyl benzyl glycidyl ether such as o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether.

As the compound (D ² -2), an oxetanyl group-containing polymerizable unsaturated compound may also be used. Specific examples of the oxetanyl group-containing polymerizable unsaturated compound include 3- (methacryloxymethyl) oxetane, 3- (methacryloxymethyl) -3-ethyloxetane, 3- (methacryloxymethyl) 3- (methacryloxyethyl) oxetane, 3- (methacryloxyethyl) -3-ethyloxetane, 2- (Acryloxymethyl) oxetane, 3- (acryloxymethyl) -3-ethyloxetane, 3- (acryloxymethyl) -2-methyloxetane, 3- (Methoxyethyl) oxetane, 2-methyl-2- (methacryloxymethyl) oxetane, 2- (Meth) acrylate, 2-methyl-2- (methoxycarbonylmethyl) oxetane, 2- 2- (methacryloxyethyl) -2-methyloxetane, 2- (methacryloxyethyl) -4-methyloctyl methacrylate, 2- (Acryloxymethyl) oxetane, 2-methyl-2- (acryloxymethyl) oxetane, 4-methyl-2- 2- (2-methyloxetanyl) ethyl methacrylate, 2- (2- (3-methyloxetanyl)) ethyl methacrylate, 2- (Meth) acrylic acid esters having an oxetanyl group such as 2-methyloxetane and 2- (acryloxyethyl) -4-methyloxetane.

Of these compounds (D ² -2), glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 3- (acryloxymethyl) oxetane, 3- (Methacryloyloxymethyl) oxetane, 3- (methacryloxymethyl) -3-ethyloxetane, 2- (methacryloxymethyl) oxetane and the like have high adhesiveness and heat crack resistance, And is preferably used in terms of enhancing reliability.

The compound (D ² -2) can be used singly or as a mixture of two or more kinds.

The copolymerization ratio of the structural unit (D ² ) is preferably from 10 to 75 mass%, more preferably from 15 to 70 mass%, and still more preferably from 20 to 65 mass%, in the total structural units. Such a copolymerization ratio makes it possible to more easily control the molecular weight of the copolymer, and further improve the image-capturing property, sensitivity and developability.

The component [D] may have a structural unit other than the structural units (D ¹ ) and (D ² ). Examples of the compound giving such a structural unit (hereinafter also referred to as "structural unit (D ³ )") (hereinafter also referred to as "compound (D ³ -3)") include (meth) acryloxypropyltrialkoxysilane (Meth) acrylic acid alkyl ester, (meth) acrylic acid alicyclic alkyl ester, unsaturated heterocyclic 5-membered or 6-membered (meth) acrylic acid ester containing oxygen atom, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid diester, maleimide Compounds, hydroxyalkyl esters of (meth) acrylic acid, (meth) acrylamides, aromatic vinyl compounds, 1,3-butadiene and the like.

 Specific examples of the (meth) acryloxypropyltrialkoxysilane include 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyl Triethoxysilane.

Specific examples of the alkyl (meth) acrylate include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, methyl acrylate, Butyl acrylate, sec-butyl acrylate, t-butyl acrylate and the like.

Specific examples of the (meth) acrylic acid alicyclic alkyl esters include cyclopentyl methacrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8 (Hereinafter also referred to as tricyclo [5.2.1.0 ^2,6 ] decan-8-yl as "dicyclopentanyl"), methacrylic acid-2-dicyclopentanyloxyethyl, isobornyl methacrylate, acrylic acid Cyclopentyl acrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, 2-dicyclopentanyloxyethyl acrylate and isobornyl acrylate. have.

Examples of the unsaturated complex 5-membered or 6-membered methacrylic acid ester containing an oxygen atom include unsaturated compounds containing a tetrahydrofuran skeleton, unsaturated compounds containing a furan skeleton, unsaturated compounds containing a tetrahydropyran skeleton, And an unsaturated compound containing a pyran skeleton. Specific examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloxytetrahydrofuran- And the like. Specific examples of the unsaturated compound containing a furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, Methyl-1-hexen-3-one, 6-furan-2-one, Methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-ene- And the like. Specific examples of the unsaturated compound containing the tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran- En-3-one, 2-methacrylic acid tetrahydropyran-2-yl ester and 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one. Specific examples of the unsaturated compound containing a pyran skeleton include 4- (1, 4-dioxa-5-oxo-6-heptenyl) -6- -Oxo-7-octenyl) -6-methyl-2-pyran.

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

Specific examples of (meth) acrylic acid aryl esters include phenyl (meth) acrylate and benzyl (meth) acrylate.

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

Specific examples of the maleimide compound include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) Maleimidobutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimidopropio (9-acridinyl) maleimide, and the like.

Specific examples of (meth) acrylamides include acrylamide, methacrylamide, 4-hydroxyphenylacrylamide, 4-hydroxyphenylmethacrylamide, 3-hydroxyphenylacrylamide, 3-hydroxyphenylmethacrylamide .

Examples of the aromatic vinyl compound include styrene and? -Methylstyrene.

Of these compounds (D ³ -3), (meth) acryloxypropyltrialkoxysilane, aromatic vinyl compound, maleimide compound, (meth) acrylic acid alicyclic alkyl ester and (meth) acrylamide are preferable, Particularly preferred is oxypropyl trialkoxysilane.

Compound (D ³ -3) is, at least can be used either individually or in combination of two or more.

The copolymerization ratio of the structural unit (D ³ ) is preferably 10 to 70 mass%, more preferably 15 to 65 mass%, in the total structural units of the component [D]. When the structural unit (D ³ ) contains a structural unit derived from (meth) acryloxypropyltrialkoxysilane, the copolymerization ratio thereof is preferably from 10 to 50 mass%, more preferably from 20 to 40 mass%. Such a copolymerization ratio makes it possible to more easily control the molecular weight of the copolymer, and further improve the developability, sensitivity, adhesion and the like.

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

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, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether pro Phononate, aromatic hydrocarbons, ketones, ethers other than the above, esters other than the above.

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'-azobis- (2,4-dimethylvaleronitrile) Azo compounds such as 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), dimethyl-2,2'-azobis (2-methylpropionate), and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile). Of these radical polymerization initiators, 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile) are preferred. The radical polymerization initiator may be used alone or in combination of two or more. The amount of the radical polymerization initiator to be used is usually 0.1 to 50 parts by mass, preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the total of the monomers.

In the polymerization reaction, a molecular weight adjuster may be used to adjust the molecular weight. Specific examples of the molecular weight regulator include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and thioglycolic acid; Azetidine derivatives such as dimethylzantogen sulfide and diisopropylzantogen disulfide; Terpinolene, alpha -methylstyrene dimer, and the like. The amount of the molecular weight control agent to be used is generally 0.1 to 50 parts by mass, preferably 0.2 to 16 parts by mass, particularly preferably 0.4 to 8 parts by mass, based on 100 parts by mass of the total of the monomers.

The polymerization temperature is usually 0 to 150 占 폚, preferably 50 to 120 占 폚, and the polymerization time is usually 10 minutes to 20 hours, preferably 30 minutes to 6 hours.

The component [D] preferably has a weight average molecular weight (hereinafter referred to as "Mw") in terms of polystyrene by GPC using tetrahydrofuran as the mobile phase, preferably from 2 × 10 ^{3 to} 1 × 10 ⁵ , Is 5 x 10 ^{3 to} 5 x 10 ⁴ . By setting the Mw 'of the component [D] to 2 × 10 ³ or more, a sufficient developing margin of the radiation sensitive composition is obtained, and a reduction in the residual film ratio (proportion of the patterned thin film remaining properly) The pattern shape and heat resistance of the obtained insulating film can be maintained favorably. On the other hand, by setting the Mw 'of the component [D] to 1 x 10 < ⁵ > or less, it is possible to maintain and maintain a high radiation sensitivity and obtain a good pattern shape. 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 the Mw '/ Mn' of the component [D] to 5.0 or less, the pattern shape of the obtained insulating film can be well maintained. Further, the radiation-sensitive composition containing the component [D] having the above-mentioned preferable ranges of Mw 'and Mw' / Mn 'has a high developing property, and therefore, It is possible to easily form a predetermined pattern shape.

The component [D] may be used singly or in a mixture of two or more.

The content of the component [D] is preferably from 1 to 45 parts by mass, more preferably from 2 to 40 parts by mass, still more preferably from 3 to 35 parts by mass, further preferably from 3 to 30 parts by mass, Is 3 to 30 parts by mass, more preferably 3 to 25 parts by mass. When the content of the component [D] is within the above range, the sensitivity and developability can be further improved.

Component [E]

Further, in the present invention, the component [E] may contain at least one kind selected from organic particles and inorganic particles. By containing the component [E], it is possible to enhance the image-capturing property, heat crack resistance and the like.

As the organic particles, those having a solid form such as acrylic fine particles are 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. Examples of commercial products of organic particles include ZEFIAC F-320, F-301, F-340, F-325 and F-351 (manufactured by Gansu Chemical Industry Co., Ltd.), acrylic fine particles MP- Manufactured by Kagaku Co., Ltd.).

Examples of the inorganic fine particles include particles mainly composed of silica, alumina, zirconium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium carbonate, magnesium carbonate, barium sulfate, talc and montmorillonite, Are preferable.

The shape of the inorganic fine particles may be spherical, rod-like, plate-like, fibrous or indefinite, and they may be solid, hollow, or porous .

As specific examples of such inorganic fine particles, admaffine SO-E1, SO-E2, SO-E3, SO-E4, SO-E5, SE3200-SEJ (manufactured by Admatechs Co.) ST-OUP, ST-20, ST-20, ST-20, ST-20, ST- 40, ST-C, ST-N, ST-O, ST-50 and ST-OL (manufactured by Nissan Kagaku Kogyo Co., Ltd.). Examples of the zirconia particles include HXU-110JC, HXU-210C, NZD-3101 (manufactured by Sumitomo Osaka Cement Co., Ltd.), ID191 (manufactured by Teika), ZRPMA15WT% -E05 MT-100H, MT-300HD, MT-150A, ND138, ND139, ND140, ND154, ND165, ND177, TS-063, TS-103, TS-159 (Manufactured by Teika Ltd.).

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

The average particle size of the organic particles and the inorganic particles is preferably in the range of 0.005 to 0.5 mu m.

The component [E] may be added directly or mixed with other components in the form of a powder, and the solvent may be added and mixed with the other component in a solvent dispersion to distill off the solvent.

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

The content of the component [E] is preferably 1 to 600 parts by mass, more preferably 10 to 200 parts by mass, and still more preferably 50 to 100 parts by mass with respect to 100 parts by mass of the component [A]. By setting the content of the component [E] within the above-described range, the image-capturing property and the heat-resistant crack resistance of the resulting protective film and interlayer insulating film can be further enhanced.

Component [F]

In the present invention, as the component [F], a solvent may be contained. The radiation-sensitive composition is usually formulated as a liquid composition by blending a solvent. The solvent may be appropriately selected and used as long as it disperses or dissolves the components constituting the radiation-sensitive composition and does not react with these components and has appropriate volatility.

As such a solvent, it is preferable to contain an alcoholic solvent as a protonic solvent. The use of an alcoholic solvent makes it possible to improve the coating property of a radiation sensitive composition on a large substrate and to suppress the occurrence of coating unevenness (stripe pattern irregularity, pin irregularity, irregular irregularity, etc.) Can be further improved.

As the alcoholic solvent, for example,

Long-chain alkyl alcohols such as 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1,6-hexanediol and 1,8-octanediol;

Aromatic alcohols such as benzyl alcohol;

Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether;

Diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;

And dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether. These alcoholic solvents may be used alone or in combination of two or more.

Among these alcoholic solvents, propylene glycol monoalkyl ether is preferable, and propylene glycol monomethyl ether and propylene glycol monoethyl ether are particularly preferable from the viewpoint of improvement of coating performance.

As the component [F], one type may be used alone, or two or more types may be used in combination.

The content of the component [F] is preferably 1 to 1,200 parts by mass, more preferably 10 to 900 parts by mass, per 100 parts by mass of the component [A]. By making the content of the component [F] fall within the above range, it is possible to improve the coating property on a glass substrate or the like and to suppress the occurrence of uneven coating (streak-like unevenness, pin marks or uneven unevenness) Can be further improved.

In the present invention, in addition to the alcohol solvent, other solvents such as ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ether propionates, aromatic hydrocarbons, ketones, Esters and the like.

additive

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

Examples of the additive include radiation sensitive acid generators such as triphenylsulfonium salts and tetrahydrothiophenium salts; 2-nitrobenzylcyclohexylcarbamate, O-carbamoylhydroxyamide, and the like; Surfactants such as nonionic surfactants, fluorinated surfactants and silicone surfactants; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; And ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones.

The content of these additives can be appropriately selected within a range that does not impair the object of the present invention.

The radiation sensitive composition of the present invention can be prepared by an appropriate method. For example, the components [A], [B] and [C], and optionally the components [D] [E] or an additive or the like may be mixed at a predetermined ratio to prepare a radiation-sensitive composition in the form of a solution or dispersion.

Curing membrane  And a method for forming the 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 includes 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)

(3) a step of developing the coated film irradiated with the radiation in the step (2) with an alkaline developer, and

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

Step (1)

In the step (1), after the solution or dispersion of the radiation sensitive composition of the present invention is applied onto the substrate, the solvent is preferably removed by heating (prebaking) the application surface to form a coating film. As a material of the usable substrate, for example, glass, quartz, silicon, resin and the like can be given. Specific examples of the resin include a ring-opening polymer of polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, cyclic olefin, and hydrogenated products thereof.

The method of applying the solution or dispersion of the radiation-sensitive composition is not particularly limited, and suitable methods such as spraying, roll coating, spin coating (coating method), slit die coating, Can be adopted. Among these coating methods, a spin coating method or a slit die coating method is particularly preferable. The conditions for prebaking vary depending on the kind of each component, blending ratio, and the like, but can be preferably about 70 to 120 DEG C for about 1 to 10 minutes.

Step (2)

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

The exposure dose in this process is a value measured by a light meter (OAI model 356, manufactured by OAI Optical Associates Inc.) at a wavelength of 365 nm of radiation, preferably 10 to 1,000 mJ / cm 2, more preferably Lt; 2 > / m < 2 >

Step (3)

In the step (3), the exposed film is developed with an alkali developer to remove unexposed portions to form a predetermined pattern. Thus, the radiation sensitive composition of the present invention is of a negative type because the non-irradiated portion of the radiation is removed.

Examples of the alkali developing solution include inorganic alkaline developing solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and ammonia, organic alkali developing solutions such as tetramethylammonium hydroxide and tetraethylammonium hydroxide . Among them, from the viewpoints of cost and productivity, an inorganic alkali developer is preferable, and a developer of an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide and the like is particularly preferable. The radiation sensitive composition of the present invention can form a pattern image with high resolution and high resolution even when an inorganic alkali developer is used.

Further, a water-soluble organic solvent such as methanol, ethanol or the like and a surfactant may be added to such an alkaline developing solution in an appropriate amount. As the developing method, for example, a suitable method such as a liquid method, a dipping method, a swing dipping method, or a shower method can be used. The developing time varies depending on the composition of the radiation sensitive composition, but is preferably about 10 to 180 seconds. Following this development processing, for example, water-repellent cleaning is performed for 30 to 90 seconds, and then air is blown with compressed air or compressed nitrogen, for example, to form a desired pattern.

Step (4)

In the step (4), a cured film having a desired pattern can be obtained by heating the developed and patterned coating film using a heating apparatus such as a hot plate or an oven. The heating temperature is, for example, 120 to 250 캜. The heating time varies depending on the type of the heating apparatus. For example, the heating time may be 5 to 30 minutes in the case of performing the heating process on the hot plate, and 30 to 90 minutes in the case of performing the heating process in the oven. A step baking method in which the heating step is performed twice or more, or the like may be used.

The film thickness of the cured film thus formed is preferably 0.1 to 10 占 퐉, more preferably 0.1 to 6 占 퐉, and still more preferably 0.1 to 4 占 퐉.

By the above process, a cured film having good adhesion to a substrate and excellent in properties such as heat-resistant transparency, hardness, image-capturing property, heat crack resistance, sensitivity and developability can be formed, It is possible to form the image with high resolution and high resolution. In addition, such a pattern can be developed with an inorganic alkali developer. Since the obtained cured film has such characteristics, it can be suitably used, for example, as a protective film of a touch panel of a display element or an interlayer insulating film of a display element.

A suitable embodiment of the present invention is as follows.

[1] The following components [A ¹ ], [B] and [C];

[A ¹ ] A ^{process for} producing a hydrolyzable silane compound, which comprises reacting tetraethoxysilane or a partial hydrolyzate thereof, a hydrolyzable silane compound represented by the formula (1) or a partial hydrolyzate thereof, and a hydrolyzable silane compound represented by the formula (2) The polysiloxane obtained by hydrolysis and condensation

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

[C] a radiation-sensitive composition containing a photo radical polymerization initiator.

[2] The amount of the tetraethoxysilane or partial hydrolyzate thereof added is preferably 5 to 75 mol%, more preferably 10 to 70 mol%, and still more preferably 25 to 75 mol%, based on the total amount of the starting materials. And 65 mol% of the total weight of the composition.

[3] The total amount of the hydrolyzable silane compound represented by the formula (1) or the partial hydrolyzate thereof is preferably 10 to 80 mol%, more preferably 10 to 75 mol% , More preferably 15 to 70 mol%, based on the total weight of the composition.

[4] The hydrolyzable silane compound represented by the above formula (1), wherein at least one silane selected from a hydrolyzable silane compound having an alkyl group having 1 to 6 carbon atoms and a hydrolyzable silane compound having an aryl group having 6 to 14 carbon atoms The radiation sensitive composition according to any one of [1] to [3], which further contains a compound (hereinafter also referred to as a silane compound (1b ¹ )).

Wherein the silane compound (1b ¹ ) is at least one selected from a hydrolyzable silane compound having one alkyl group having 1 to 6 carbon atoms and a hydrolyzable silane compound having one aryl group having 6 to 14 carbon atoms, The radiation sensitive composition according to [4].

[6] The total amount of the silane compound (1b ¹ ) added is preferably 10 to 80 mol%, more preferably 15 to 75 mol%, and still more preferably 30 to 70 mol%, based on the total amount of the starting compounds %, Based on the total weight of the composition. [4] or [5].

[7] The radiation sensitive composition according to any one of [1] to [6], wherein the hydrolyzable silane compound represented by the formula (1) contains a hydrolyzable silane compound having a (meth) acryloxy group.

The hydrolyzable silane compound having a (meth) acryloxy group is preferably a hydrolyzable silane compound having a methacryloxy group (hereinafter also referred to as a silane compound (1c ¹ )) and a hydrolyzable silane compound having an acryloxy group (Hereinafter also referred to as a silane compound (1d ¹ )).

The total amount of the hydrolyzable silane compound having a (meth) acryloxy group is preferably 5 to 25 mol%, more preferably 10 to 20 mol%, relative to the total amount of the starting compounds, ] Or [8].

The hydrolyzable silane compound having a (meth) acryloxy group, which contains a silane compound (1c ¹ ) and a silane compound (1d ¹ ), has a molar ratio (1c ¹ / 1d ¹ ) Is in the range of 0.05 to 3, more preferably 0.2 to 1.5, and still more preferably 0.3 to 1. The radiation sensitive composition according to the above [8] or [9]

[11] The addition ratio of the hydrolyzable silane compound represented by the formula (2) or its partial hydrolyzate is 15 mol% or less, preferably 13 mol% or less, more preferably 10 mol% or less, The composition according to any one of the above [1] to [10], wherein the proportion is at most% by mole, more preferably at most 7% by mole.

[12] The addition ratio of the hydrolyzable silane compound or partial hydrolyzate thereof represented by the formula (2) is preferably 0.5 to 15 mol%, more preferably 1 to 13 mol% The radiation-sensitive composition according to any one of the above [1] to [10], which further comprises 2 to 10 mol%, and more preferably 3 to 7 mol%.

[13] The process according to any one of [1] to [12], wherein the hydrolyzable silane compound represented by the above formula (2) is 3-trimethoxysilylpropylsuccinic anhydride or 3-triethoxysilylpropylsuccinic anhydride. ≪ / RTI >

[14] the following components [A ² ], [B] and [C];

(A ² ) a polysiloxane having an SiO ₂ unit, a structural unit represented by the formula (1a) and a structural unit represented by the formula (2a)

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

[C] a radiation-sensitive composition containing a photo radical polymerization initiator.

The content of the SiO ₂ units is preferably 5 to 75 mol%, more preferably 10 to 70 mol%, and still more preferably 25 to 65 mol%, based on the total structural units of the component [A ² ] %, Based on the total weight of the composition.

[16] The content of the structural unit (1a) is preferably 10 to 80 mol%, more preferably 10 to 75 mol%, and still more preferably 15 to 70 mol%, based on the total structural units of the component [A ² ] Mol%, based on the total weight of the composition.

[17] The content of the structural unit (2a), components in the total structural unit of [A ^2], preferably 15 mol% or less, more preferably 13 mol% or less, more preferably 10 mol% or less, , More preferably not more than 7 mol%, based on the total weight of the composition.

[18] The content of the structural unit (2a) is preferably 0.5 to 15 mol%, more preferably 1 to 13 mol%, and still more preferably 2 to 10 mol%, based on all structural units of the component [A ² ] The composition of any of the above-mentioned [14] to [16], wherein the proportion of the repeating unit represented by the formula

[19] The resin composition according to any one of [14] to [18], wherein the structural unit (1a) contains at least one structural unit represented by the formula (1b) Radiation composition.

[20] The content of the structural unit (1b) is preferably 10 to 80 mol%, more preferably 15 to 75 mol%, and still more preferably 30 to 70 mol% in the total structural units of the component [A ² ] Mol%, based on the total weight of the composition.

The structural unit represented by the formula (1c) (hereinafter also referred to as "structural unit (1c)") and the structural unit represented by the formula (1d) ) &Quot;). The radiation sensitive composition according to any one of < 14 > to < 20 >

[22] in which the total content of the ingredient in the total structural unit of [A ^2], preferably from 5 to 25 mol%, more preferably 10 to 20 mol% of the structural unit (1c) and the structural unit (1d) , And the radiation sensitive composition according to [21] above.

The content ratio (1c / 1d) of the structural unit (1c) and the structural unit (1d) containing the structural unit (1c) and the structural unit (1d) as the structural unit (1a) Sensitive adhesive composition according to the above [21] or [22], wherein the weight-average molecular weight is from 0.05 to 3, more preferably from 0.2 to 1.5, and still more preferably from 0.3 to 1.

[24] The resin composition according to any one of [14] to [23], wherein the structural unit (2a) is a structural unit derived from 3-trimethoxysilylpropylsuccinic anhydride or 3-triethoxysilylpropylsuccinic anhydride. Sensitive composition.

The alkyl group according to R ^{1 in} the formula (1) and R ³ in the formula (2) is preferably an alkyl group having 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms. Sensitive composition according to any one of < 1 >

The alkyl groups according to R ² in the formulas (1) and (1a) preferably have 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Sensitive composition according to any one of < 1 >

The aryl group according to R ² in the formulas (1) and (1a) is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. / RTI >

[1] to [27], wherein m in the formulas (1), (1a), (1b), (1c) and (1d) is preferably 1 or 2, Sensitive composition according to any one of < 1 >

The n in the above formulas (1), (1a), (1b), (1c) and (1d) is preferably an integer of 0 to 3, more preferably 0 or 3. [ To (28) above.

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

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

The radiation sensitive composition according to any one of [1] to [31], wherein z in the formulas (2) and (2a) is preferably 0 or 1,

The weight average molecular weight (Mw) of the components [A ¹ ] and [A ² ] is preferably 500 to 10000, more preferably 1000 to 7000. In any one of [1] to [32] ≪ / RTI >

The dispersity (Mw / Mn) of the components [A ¹ ] and [A ² ] is preferably 1.0 to 15.0, more preferably 1.1 to 10.0, To (33) above.

[35] The thermoplastic resin composition according to the above item [1], wherein the component [B] is a (meth) acrylic acid ester having a bifunctional or trifunctional or more functional group and more preferably a Sensitive composition according to any one of the above [1] to [34], which is an ester.

The content of the component [B] is preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, further preferably 15 to 100 parts by mass, per 100 parts by mass of the component [A] Sensitive adhesive composition according to any one of the above [1] to [35], which further comprises 20 to 80 parts by mass.

[37] The radiation sensitive composition according to any one of [1] to [36], wherein the component [C] contains an O-acyloxime compound.

[38] The content of the component [C] is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 15 parts by mass, more preferably 0.1 to 15 parts by mass, relative to 100 parts by mass in total of the components [A] and [B] Sensitive adhesive composition according to any one of [1] to [37], wherein the amount of the water-soluble polymer is 1 to 10 parts by mass.

(D ¹ ) a structural unit having a carboxyl group (hereinafter also referred to as a structural unit D ¹ ) and (D ² ) a structural unit having an epoxy group (hereinafter also referred to as a structural unit D ² ) The radiation-sensitive composition according to any one of [1] to [38], wherein the radiation-sensitive composition contains a copolymer having a hydroxyl group.

The structural unit (D ¹ ) is at least one compound selected from (D ¹ -1) unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter also referred to as "compound (D ¹ -1)") Sensitive composition according to < 39 >

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

The copolymerization ratio of the structural unit (D ¹ ) is preferably 1 to 40 mass%, more preferably 2 to 30 mass%, and still more preferably 3 to 25 mass% in the total structural units. The radiation sensitive composition according to any one of [39] to [41].

The copolymerization ratio of the structural unit (D ² ) is preferably 10 to 75% by mass, more preferably 15 to 70% by mass, and still more preferably 20 to 65% by mass in the total structural units. The radiation sensitive composition according to any one of [39] to [42].

[44] The radiation sensitive composition according to any one of [39] to [43], wherein the component [D] further has a structural unit derived from (D ³ ) (meth) acryloxypropyltrialkoxysilane.

[45] The content of the component [D] is preferably 1 to 45 parts by mass, more preferably 2 to 40 parts by mass, still more preferably 3 to 35 parts by mass, still more preferably 3 to 30 parts by mass with respect to 100 parts by mass of the polysiloxane Sensitive composition as described in any one of the above items [39] to [44], wherein the amount is 3 to 30 parts by mass, and more preferably 3 to 25 parts by mass.

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

[47] The positive resist composition as described in any of [1] to [3], wherein the content of the component [E] is preferably 1 to 600 parts by mass, more preferably 10 to 200 parts by mass, and still more preferably 50 to 100 parts by mass relative to 100 parts by mass of the polysiloxane. 45].

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

[49] The radiation sensitive composition according to the above [48], wherein the component [F] preferably contains a protonic solvent, more preferably an alcoholic solvent.

[50] The photosensitive resin composition according to the above [48] or [49], wherein the content of the component [F] is preferably 1 to 1,200 parts by mass, more preferably 10 to 900 parts by mass relative to 100 parts by mass of the polysiloxane. / RTI >

[51] The radiation sensitive composition according to any one of [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 using the radiation sensitive composition according to any one of [1] to [51].

[53] the following steps (1) to (4);

(1) a step of applying the radiation sensitive composition described in any one of [1] to [51] above 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)

(3) a step of developing the coated film irradiated with the radiation in the step (2) with an alkaline developer, and

(4) A method for forming a cured film, comprising the step of heating the developed coating film in the step (3).

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

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

Example

Hereinafter, Synthesis Examples and Examples are given to illustrate the present invention in more detail, but the present invention is not limited to the following Examples.

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

Apparatus: GPC-101 (manufactured by Showa Denko K.K.)

Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 (manufactured by Showa Denko K.K.)

Mobile phase: tetrahydrofuran

Synthesis Example of Polysiloxane of Component [A]

[Synthesis Example 1]

20 parts by mass of propylene glycol monomethyl ether was placed in a container equipped with a stirrer and then 41 parts by mass of methyltrimethoxysilane (hereinafter referred to as " MTMS "), 12 parts by mass of tetraethoxysilane (TEOS) 5 parts by mass (MTMS / TEOS / TMSPS (molar ratio) = 80/15/5) of - (trimethoxysilyl) propyl succinic anhydride (hereinafter referred to as TMSPS) And heated. After the solution temperature reached 60 占 폚, 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 占 폚 and stored for 3 hours. After cooling to 45 캜, 28 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Further, the solution temperature was adjusted to 40 캜, and while this was maintained, the ion-exchanged water and methanol generated by hydrolysis and condensation were removed. Thus, a polysiloxane (A-1) was obtained. The polysiloxane (A-1) had a solid concentration of 30 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 residue obtained by removing a volatile substance by drying the sample on a hot plate at 175 DEG C for 1 hour.

[Synthesis Example 2]

Methacryloxypropyltrimethoxysilane (hereinafter referred to as " MPTMS ") in addition to MTMS, TEOS and TMSPS in a ratio of MTMS / TEOS / MPTMS / TMSPS (molar ratio) = 68/15/15/2 (A-2) was obtained in the same manner as in Synthesis Example 1. The results are shown in Table 1. < tb > < TABLE > The polysiloxane (A-2) had a solid concentration of 30 mass%, a weight average molecular weight (Mw) of 2,300, and a degree of dispersion (Mw / Mn) of 2.1.

[Synthesis Example 3]

A polysiloxane (A-3) was obtained in the same manner as in Synthesis Example 2 except that the ratio (molar ratio) of MTMS / TEOS / MPTMS / TMSPS was changed to 62/15/15/8. The polysiloxane (A-3) had a solid 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]

A polysiloxane (A-4) was obtained in the same manner as in Synthesis Example 2 except that the ratio (molar ratio) of MTMS / TEOS / MPTMS / TMSPS was changed to 55/15/15/15. The polysiloxane (A-4) had a solid 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 phenyltrimethoxysilane (hereinafter referred to as " PTMS ") and MTMS / TEOS / PTMS / MPTMS / TMSPS (molar ratio) = 50/15/15/15/5 (A-5) was obtained in the same manner as in Synthesis Example 1, except that the polysiloxane The polysiloxane (A-5) had a solid 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]

(Hereinafter referred to as " APTMS ") in a ratio of MTMS / TEOS / APTMS / TMSPS (molar ratio) of 65/15/15/5, in addition to MTMS, TEOS and TMSPS (A-6) was obtained in the same manner as in Synthesis Example 1, except that the polysiloxane (A-6) was used. The polysiloxane (A-6) had a solid concentration of 30 mass%, a weight average molecular weight (Mw) of 2,400, and a degree of dispersion (Mw / Mn) of 2.3.

[Synthesis Example 7]

A polysiloxane (A-7) was obtained in the same manner as in Synthesis Example 6 except that the ratio (molar ratio) of MTMS / TEOS / APTMS / TMSPS was changed to 50/30/15/5. The polysiloxane (A-7) had a solid 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]

Was the same as Synthesis Example 1 except that MPTMS and APTMS were used at a ratio of MTMS / TEOS / MPTMS / APTMS / TMSPS (molar ratio) = 77/7 / 1/10/5 in addition to MTMS, TEOS and TMSPS By operation, a polysiloxane (A-8) was obtained. The polysiloxane (A-8) had a solid concentration of 30 mass%, a weight average molecular weight (Mw) of 2,000, and a degree of dispersion (Mw / Mn) of 2.0.

[Synthesis Example 9]

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

[Synthesis Example 10]

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

[Synthesis Example 11]

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

[Synthesis Example 12]

A polysiloxane (A-12) was obtained in the same manner as in Synthesis Example 2 except that the ratio (molar ratio) of MTMS / TEOS / MPTMS / TMSPS was changed to 50/30/15/5. The polysiloxane (A-12) had a solid 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]

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

[Synthesis Example 14]

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

[Comparative Synthesis Example 1]

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

[Comparative Synthesis Example 2]

(A-2) was obtained in the same manner as in Synthesis Example 1 except that MPTMS and APTMS were used in place of TEOS and MTMS / MPTMS / APTMS / TMSPS (molar ratio) = 80/5/10 / ). The polysiloxane (a-2) had a solid concentration of 30 mass%, a weight average molecular weight (Mw) of 2,000, and a degree of dispersion (Mw / Mn) of 1.9.

[Comparative Synthesis Example 3]

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

[Comparative Synthesis Example 4]

Except that TMSPS was not used and phenyl trimethoxysilane (hereinafter referred to as "PTMS") was used instead of TEOS, and the ratio of MTMS / PTMS (molar ratio) = 70/30 was used. By the same procedure, a polysiloxane (a-4) was obtained. The polysiloxane (a-4) had a solid concentration of 29 mass%, a weight average molecular weight (Mw) of 6,000, and a degree of dispersion (Mw / Mn) of 2.0.

[Comparative Synthesis Example 5]

27.2 g of MTMS and 39.2 g of 3-mercaptopropyltrimethoxysilane (MEPTMS) were added to a 500-mL three-necked flask, and 100 g of propylene glycol methyl ether was added to dissolve the mixture. The resulting mixed solution was stirred in a magnetic stirrer Lt; / RTI > MTMS / MEPTMS (molar ratio) = 50/50. To this, 8.6 g of ion-exchanged water containing 1 mass% oxalic acid was continuously added over 1 hour. After reacting at 60 DEG C for 4 hours, the obtained reaction solution was cooled to room temperature. Thereafter, the alcohol component as the reaction by-product was distilled off under reduced pressure from the reaction solution. Thus, a polysiloxane (a-5) was obtained. The polysiloxane (a-5) had a solid concentration of 45 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]

A cooling tube 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 placed. Subsequently, 18 mass parts of styrene (hereinafter referred to as "ST"), 20 mass parts of methacrylic acid (hereinafter referred to as "MA"), 22 mass parts of N-cyclohexylmaleimide (hereinafter referred to as "CHMI" And 40 parts by mass of glycidyl methacrylate (hereinafter referred to as " GMA ") were charged and replaced with nitrogen. The temperature of the solution was raised to 70 DEG C while gently stirring, To obtain a solution containing the copolymer (D-1). The solid content concentration of the obtained copolymer solution was 31%, the weight average molecular weight (Mw ') of the copolymer (D-1) was 12,500 and the dispersion degree (Mw' / Mn ') was 2.5.

[Synthesis Example 16]

MA / DCM / HMAd (ratio by mass / mass ratio) using dicyclopentyl methacrylate (hereinafter referred to as "DCM") and p-hydroxy methacrylanilide ) Was 20/14/5/21/40, the copolymer (D-2) was obtained in the same manner as in Synthesis Example 15. The copolymer (D-2) had a solid concentration of 32 mass%, a weight average molecular weight (Mw ') of 13,000 and a degree of dispersion (Mw' / Mn ') of 2.0.

[Synthesis Example 17]

Except that 3-methacryloxypropyltrimethoxysilane (MPTMS) was used instead of ST and CHMI and the ratio of MA / GMA / MPTMS (mass ratio) = 5/65/30 was used To obtain a copolymer (D-3). The copolymer (D-3) had a solid concentration of 31.5% by weight, a weight average molecular weight (Mw ') of 12,000, and a degree of dispersion (Mw' / Mn ') of 2.3.

[Synthesis Example 18]

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

[Synthesis Example 19]

Except that MPTMS was further used in addition to ST, CHMI, GMA and MA, and the ratio was ST / GMA / MA / CHMI / MPTMS (mass ratio) = 10/45/5/10/30. , A copolymer (D-5) was obtained. The copolymer (D-5) had a solid concentration of 31.7% by weight, a weight average molecular weight (Mw ') of 12,000 and a degree of dispersion (Mw' / Mn ') of 2.0.

[Synthesis Example 20]

4.0 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 245 parts by mass of diethylene glycol methyl ethyl ether were placed in a flask equipped with a cooling tube and a stirrer, followed by 18 parts by mass of MA, GMA 38 , 5 parts by mass of ST and 34 parts by mass of DMC were charged and replaced with nitrogen. Then, 5 parts by mass of 1,3-butadiene (hereinafter referred to as "BD") was added with gentle stirring, The temperature was raised to 70 占 폚, and this temperature was maintained for 4 hours to polymerize to obtain a copolymer (D-6). The copolymer (D-6) had a solid 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 composition, formation of a protective film and an interlayer insulating film

[Example 1]

(B-1) dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (B-1) were added to a solution (100 parts by mass in terms of solid content) containing the polysiloxane (A- 20 parts by mass of a mixture (molar ratio: 50/50) of (C-1) ethanone, 1- [9-ethyl-6- -, and 1- (O-acetyloxime) were further added, and a mixed solvent of propylene glycol monomethyl ether and ethylene glycol monobutyl ether (mixing ratio 80/20 w / w%) was further added so that the solid content concentration became 25 mass% To prepare a radiation-sensitive composition.

Next, this radiation-sensitive composition was applied to a SiO ₂ dip glass substrate using a spinner and then pre-baked on a hot plate at 90 ° C for 2 minutes to form a coating film (in the later-described ITO adhesion evaluation, . Subsequently, ultraviolet rays were exposed to the obtained coating film at an exposure amount of 300 mJ / cm 2. Subsequently, the resist film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 25 deg. C for 60 seconds, washed with pure water for 1 minute, and further heated in an oven at 230 deg. C for 60 minutes to form a protective film having a thickness of 2.0 m .

Further, the number of revolutions of the spinner at the time of forming the coating film was adjusted so that the film thickness after heating was 3.0 占 퐉, and through the photomask having contact hole patterns of sizes 20 占 퐉, 30 占 퐉, 40 占 퐉 and 50 占 퐉, (The distance between the substrate and the photomask) was 150 [micro] m, an interlayer insulating film was formed in the same manner as the above-mentioned protective film formation.

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

Property evaluation

1) Heat-resistant transparency of protective film

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

Heat resistance transparency (%) = Light transmittance before heating (%) - Light transmittance (%) after heating

2) Pencil hardness of protective film

With respect to the substrate having the protective film formed as described above, the pencil hardness (surface hardness) of the protective film was measured by "8.4.1 Pencil scratch test of JIS K-5400-1990". When this value was 4H or larger, it was judged that the surface hardness of the protective film was good.

3) Intra-image pickup property of the protective film

With respect to the substrate having the protective film formed as described above, the substrate was subjected to a reciprocating ten times by applying a load of 200 g onto a steel wool # 0000 using a trained abrasion tester. The state of image pick-up was visually evaluated based on the following criteria. When the rating is ⊚ or ◯, it is determined that the image has good image-capturing ability.

Criteria

?: No scratches at all,

○: 1 to 3 scratches were formed,

?: 4 to 10 scratches were formed,

X: More than 10 scratches were formed

4) Thermal cracking resistance of the protective film

The substrate having the protective film thus formed was subjected to additional firing at 300 캜 for 30 minutes and then left at 23 캜 for 24 hours to determine whether or not cracks were generated on the protective film surface. And confirmed using a laser microscope (VK-8500, manufactured by Keyence Corporation). When the rating was ⊚ or ◯, it was judged that the heat crack resistance was good.

Criteria

?: No cracks at all,

O: 1 to 3 cracks,

?: 4 to 10 cracks were present,

X: 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-attached substrate was used in place of the SiO ₂ deep glass substrate, and a pressure cooker test (120 ° C, 100% humidity, 4 hours) was performed. Thereafter, "8.5.3 Adhesive Cross-Cut Tape Method of JIS K-5400-1990" was carried out, and the number of cross cuts remaining in 100 cross cuts was determined to evaluate the ITO adhesion of the protective film. When the number of the remaining crosscuts among the 100 crosscuts was 80 or less, it was judged that the ITO adhesion was poor.

6) Sensitivity of the protective film

The coating film formed by the above operation was changed in exposure amount through a mask having a line-and-space pattern of 10 mu m / 30 mu m using an exposure machine (TME-400PRJ, manufactured by Topcon Co., Ltd.) After exposure, the resist film was developed with a 0.04 mass% aqueous solution of KOH at 25 캜 for 60 seconds by a dipping method. Subsequently, the substrate was subjected to water washing with ultra pure water for 1 minute and dried to form a pattern on the glass substrate. At this time, the minimum amount of exposure required to leave a pattern of 10 μm / 30 μm line-and-space without peeling was measured. This minimum exposure dose was evaluated as radiation sensitivity. When the minimum exposure amount was 100 mJ / cm 2 or less, it was judged that the sensitivity was good. The case where a pattern could not be formed was evaluated as " X ".

7) Resolution of the interlayer insulating film

In the formation of the interlayer insulating film, the size of the contact hole pattern that could be resolved was measured. When the contact hole pattern of 30 탆 or less can be resolved, it is determined that the resolution is good. The case where a pattern could not be formed was evaluated as " X ".

8) KOH developability of protective film

A coating film having a thickness of 3.0 탆 was formed on the substrate having the protective film formed as described above, and developed with a 0.04% by mass aqueous KOH solution at 25 캜 for 60 seconds by the dipping method. Thereafter, the presence of film residue remained on the substrate was observed with an optical microscope, and evaluated according to the following criteria. When the film residue is not confirmed, it is determined that the KOH developability is good. On the other hand, if the film residue is found on the entire surface of the substrate, there is no KOH developability and it can be judged to be defective.

Criteria

○: The membrane residue was not confirmed

△: Some film residue was confirmed

X: Film residue was observed on the entire surface of the substrate

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

A radiation-sensitive composition was prepared in the same manner as in Example 1, except that the kinds and blending amounts (parts by mass) of the respective blending components were changed as shown in Table 1. Subsequently, 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 also shown 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 kinds and blending amounts (parts by mass) of each compounding ingredients were changed as shown in Table 2. Subsequently, 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 also shown in Table 2.

The symbols in the components [A], [B], [C], [D] and [E] in Tables 1 and 2 indicate the following.

Component [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 (㏖%), 1c 1 / 1d 1 = 0.1

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

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

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

Component [B]

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

B-2: Pentaerythritol triacrylate (Shin-Nakamura Kagakuko Co., Ltd.)

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

B-4: Tris (acryloxyethyl) isocyanurate (Aronix M-315, manufactured by Toagosei Co., Ltd.)

B-5: A commercially available product (trade name: KAYRAD DPHA-40H, manufactured by Nippon Kayaku Co., Ltd.) containing a polyfunctional urethane acrylate-

Component [C]

(Trade name: IRGACURE OX02, produced by BASF Corp.), and the like, in the same manner as in Example 1, except that 1-ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- Produce)

C-2: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: IRGACURE 819, manufactured by BASF)

C-3: 1,2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)] (trade name: IRGACURE OXE01,

C-4: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-

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

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

C-7: 2-Mercaptobenzothiazole

Component [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%)

Component [E]

E-1: Polymethyl methacrylate-based fine particles (trade name: MP-300, manufactured by Soken Kagaku Co., Ltd.)

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

E-3: ZrO ₂ sol (trade name: ID191, manufactured by Teika)

E-4: TiO ₂ sol (trade name: TS-103, manufactured by Teika)

Claims (16)

The following components [A ¹ ], [B] and [C];
[A ¹ ] A ^{process for} producing a hydrolyzable silane compound, which comprises reacting tetraethoxysilane or a partial hydrolyzate thereof, a hydrolyzable silane compound represented by the following formula (1) or a partial hydrolyzate thereof and a hydrolyzable silane compound or partial hydrolyzate thereof represented by the following formula The polysiloxane obtained by hydrolysis and condensation
[B] a compound having two or more ethylenic unsaturated groups (excluding the component [A ¹ ]),
[C] Photo radical polymerization initiator
A radiation-sensitive composition comprising:

[In the formula (1)
R ¹ represents an alkyl group having 1 to 6 carbon atoms,
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 represents an integer of 1 to 3,
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]. The method according to claim 1,
Wherein the feed rate of the hydrolyzable silane compound represented by the formula (2) or its partial hydrolyzate is from 0 mol% to 15 mol% with respect to the total amount of the raw material compounds. The method according to claim 1,
A radiation-sensitive composition comprising a hydrolyzable silane compound having an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms as the hydrolyzable silane compound represented by the formula (1). The method according to claim 1,
A radiation-sensitive composition comprising at least one member selected from the group consisting of a hydrolyzable silane compound having a methacryloxy group and a hydrolyzable silane compound having an acryloxy group as the hydrolyzable silane compound represented by the formula (1). The following components [A ² ], [B] and [C];
[A _^2] SiO ² units with the following formula (1a) a polysiloxane having the structural unit represented by the structural unit of the following formula (2a) represented by the
[B] a compound having two or more ethylenic unsaturated groups (excluding the component [A ² ]),
[C] Photo radical polymerization initiator
A radiation-sensitive composition comprising:

[Wherein, in 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,
m represents an integer of 1 to 3,
n represents an integer of 0 to 6;
In 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]. 6. The method of claim 5,
Wherein the content ratio of the structural unit represented by the formula (2a) is more than 0 mol% and not more than 15 mol% of the total structural units. 6. The method of claim 5,
A radiation-sensitive composition containing a structural unit represented by the following formula (1b) as a structural unit represented by the formula (1a):

[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 is as defined above]. 6. The method of claim 5,
A radiation-sensitive composition comprising, as a structural unit represented by the formula (1a), at least one selected from a structural unit represented by the following formula (1c) and a structural unit represented by the following formula (1d):

[In the formulas (1c) and (1d), m and n have the same meanings as defined above]. The method according to claim 1,
Further, a radiation-sensitive composition containing as a component [D] a copolymer having a structural unit having (D ¹ ) a carboxyl group and a structural unit having (D ² ) an epoxy group. 10. The method of claim 9,
Wherein the component [D] further has a structural unit derived from (D ³ ) (meth) acryloxypropyltrialkoxysilane. 10. The method of claim 9,
Wherein the content of the component [D] is 1 to 45 parts by mass with respect to 100 parts by mass of the polysiloxane. 12. The method according to any one of claims 1 to 11,
Further, as the component [E], at least one member selected from the group consisting of organic particles and inorganic particles is contained. 12. The method according to any one of claims 1 to 11,
A radiation-sensitive composition for use in 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 11. The following steps (1) to (4)
(1) a step of applying the radiation sensitive composition according to any one of claims 1 to 11 on 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)
(3) a step of developing the coated film irradiated with the radiation in the step (2) with an alkaline developer, and
(4) a step of heating the developed coating film in the step (3)
To form a cured film. 16. The method of claim 15,
A method of forming a cured film using an inorganic alkali developer as an alkaline developer.