JP2009223293A - Radiation-sensitive resin composition, interlayer dielectric and microlens, and method for forming those - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive composition having high radiation sensitivity and such a development margin as to form a good pattern shape even by development for over an optimum developing time in a developing step, the composition easily forming a patterned thin film excellent in adhesion and being suitable for forming an interlayer dielectric or microlenses. <P>SOLUTION: The radiation-sensitive resin composition includes a polysiloxane having a polymerizable unsaturated bond and a 1,2-quinonediazide compound. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a radiation-sensitive resin composition, an interlayer insulating film, a microlens, and a method for forming them.

Thin film transistor (hereinafter referred to as “TFT”) type liquid crystal display elements, organic EL display elements, magnetic head elements, integrated circuit elements, solid-state image sensors and other electronic components are generally insulated between wirings arranged in layers. In order to do so, an interlayer insulating film is provided. As a material for forming an interlayer insulating film, a material having a small number of steps for obtaining a required pattern shape and having sufficient flatness is preferable, and therefore, a radiation-sensitive resin composition is widely used (patent) Reference 1 and Patent Document 2).
Among the electronic components, for example, a TFT type liquid crystal display element is manufactured through a process of forming a transparent electrode film on the interlayer insulating film and further forming a liquid crystal alignment film on the interlayer insulating film. Since the film is exposed to high temperature conditions in the transparent electrode film forming step or exposed to a resist stripping solution used for electrode pattern formation, sufficient resistance to these is required.

In recent years, TFT-type liquid crystal display elements tend to have larger screens, higher brightness, higher definition, faster response, thinner thickness, etc., and high sensitivity as a composition for forming an interlayer insulating film used therefor. Therefore, the interlayer insulating film to be formed is required to have higher performance than ever in terms of low dielectric constant and high transmittance.
As such an interlayer insulating film having a low dielectric constant and a high transmittance, a combination of an acrylic resin and a quinone diad (Patent Document 3) and a combination of a phenol resin and a quinone diazide (Patent Document 4) are known. However, these materials have problems such as outgassing due to a heating process after film formation and a decrease in transparency.

Furthermore, in the development process when forming an interlayer insulating film from a conventionally known radiation-sensitive resin composition, if the development time is slightly longer than the optimum time, the pattern may be peeled off.
From the viewpoint of improving the production yield and reliability of liquid crystal display elements, there is a need to improve display defects of liquid crystal display elements called “burn-in”. “Burn-in” is a problem in which impurities and uncured substances are eluted from the cured film inside the liquid crystal display element to the liquid crystal, causing problems in the response of the liquid crystal when a voltage is applied, and causing an afterimage in the liquid crystal display element. It is. Such a problem is a big problem that decreases the productivity of the liquid crystal display element and impairs the reliability.
As described above, in forming the interlayer insulating film from the radiation-sensitive resin composition, the composition is required to have high sensitivity, and the developing time in the developing process during the forming process becomes excessive beyond a predetermined time. In this case, the pattern does not peel off and shows good adhesion, and the interlayer insulating film formed therefrom has high heat resistance, high solvent resistance, low dielectric constant, high transmittance, high voltage holding ratio, etc. Although required, a radiation-sensitive resin composition that satisfies such a requirement has not been conventionally known.

On the other hand, a microlens having a lens diameter of about 3 to 100 μm or an optical system material for an on-chip color filter such as a facsimile, an electronic copying machine, or a solid-state image sensor, or an optical fiber connector is defined. An array of microlenses is used.
To form a microlens or microlens array, a resist pattern corresponding to the lens is formed and then melt-flowed by heat treatment and used as it is as a lens, or by using the melt-flowed lens pattern as a mask and drying. A method of transferring a lens shape to a base by etching is known. For the formation of the lens pattern, a radiation-sensitive resin composition is widely used (see Patent Document 5 and Patent Document 6).

By the way, the element in which the microlens or the microlens array as described above is formed is then applied with a planarizing film and an etching resist film in order to remove various insulating films on the bonding pad which is a wiring forming portion. Exposure and development are performed using a desired mask to remove the etching resist in the bonding pad portion, and then the step is performed to remove the planarizing film and various insulating films by etching to expose the bonding pad portion. Therefore, the microlens or the microlens array requires solvent resistance and heat resistance in the flattening film and etching resist coating film forming process and the etching process.
The radiation-sensitive resin composition used to form such a microlens has high sensitivity, and the microlens formed therefrom has a desired radius of curvature, and has high heat resistance and high transmittance. The rate is required.

In addition, microlenses obtained from conventionally known radiation-sensitive resin compositions can be developed between the pattern and the substrate if the development time is slightly longer than the optimum time in the development process for forming them. Since the liquid permeates and peels easily, it is necessary to strictly control the development time, which causes a problem in terms of product yield.
As described above, in forming the microlens from the radiation-sensitive resin composition, the composition is required to have high sensitivity, and the development time in the development process during the formation process is excessive for a predetermined time. Even when the pattern is not peeled off, it exhibits good adhesion and requires a good melt shape as a microlens, that is, a melt shape with a desired radius of curvature, high heat resistance, high solvent resistance, and high transmittance. However, a radiation-sensitive resin composition that satisfies such requirements has not been known.

  A siloxane polymer is known as a material having high heat resistance, high transparency, and low dielectric constant, and it is also known to use this for an interlayer insulating film (see Patent Document 7). For this purpose, high-temperature baking at 250 to 300 ° C. is necessary, and there is a problem that it cannot be applied to the process of producing display elements. Although attempts have been made to apply siloxane polymers to microlenses, no industrially successful examples have been known so far.

JP 2001-354822 A JP 2001-343743 A JP-A-2005-320542 JP 2003-255546 A JP-A-6-18702 JP-A-6-136239 JP 2006-178436 A

  The present invention has been made based on the above situation. Therefore, the object of the present invention is high heat resistance, high solvent resistance, high transmittance, low dielectric constant, high voltage holding when used for forming an interlayer insulating film under baking conditions of less than 250 ° C. Another object of the present invention is to provide a radiation-sensitive resin composition capable of forming an interlayer insulating film having a high rate and capable of forming a microlens having a high transmittance and a good melt shape when used for forming a microlens.

  Another object of the present invention is a patterned thin film having high radiation sensitivity, having a development margin capable of forming a good pattern shape even when the optimum development time is exceeded in the development process, and having excellent adhesion. It is in providing the radiation sensitive composition which can form easily.

  Still another object of the present invention is to provide a method for forming an interlayer insulating film and a microlens using the radiation sensitive resin composition.

  Still another object of the present invention is to provide an interlayer insulating film and a microlens formed by the method of the present invention.

  Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are as follows.
[A] (a1) a polysiloxane that is a hydrolysis condensate of a silane compound represented by the following formula (1) and (a2) a silane compound represented by the following formula (2),
[B] 1,2-quinonediazide compound,
It achieves by the radiation sensitive resin composition characterized by containing.

(In formula (1), X ¹ represents a vinyl group, an allyl group, a (meth) acryloyloxy group, a styryl group or a vinylbenzyloxy group, and Y ¹ represents a single bond, a methylene group or an alkylene group having 2 to 6 carbon atoms. R ¹ represents an alkoxy group having 1 to 6 carbon atoms or an acyloxy group having 2 to 6 carbon atoms, R ² represents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl having 6 to 12 carbon atoms And a and b each represent an integer of 1 to 3, c represents an integer of 0 to 2, and a + b + c = 4.)

(In Formula (2), R ⁵ represents a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms, or an acyloxy group having 2 to 6 carbon atoms, R ⁶ represents a substituted or unsubstituted alkyl group having 1 to ⁶ carbon atoms or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, g represents an integer of 1 to 4, and h represents an integer of 0 to 3 And g + h = 4.)

The above objects and advantages of the present invention are secondly,
This is achieved by a method for forming an interlayer insulating film or microlens including the following steps in the order described below.
(1) A step of forming a film of the radiation sensitive resin composition on a substrate,
(2) a step of irradiating at least a part of the coating;
(3) A step of developing the coating after irradiation, and (4) a step of heating the coating after development.

Further, the above object and advantage of the present invention are as follows.
This is achieved by the interlayer insulating film or microlens formed by the above method.

According to the radiation-sensitive resin composition of the present invention, it has sufficient hardness even under firing conditions of less than 250 ° C., is excellent in solvent resistance and heat resistance, and further has high transmittance, low dielectric constant, and high voltage holding. An interlayer insulating film having a high rate can be formed.
In addition, the radiation-sensitive resin composition of the present invention has high radiation sensitivity, has a development margin that can form a good pattern shape even when the optimum development time is exceeded in the development process, and has good adhesion. An excellent patterned thin film can be easily formed.
Further, the microlens of the present invention formed from the above composition has good adhesion to the substrate, is excellent in solvent resistance and heat resistance, and has a high transmittance and a good melt shape, It can be suitably used as a microlens for a solid-state image sensor.

It is a schematic diagram of the cross-sectional shape of a micro lens.

  Hereinafter, the radiation sensitive resin composition of this invention is explained in full detail.

[A] Component The [A] component used in the present invention is a polysiloxane having a polymerizable unsaturated bond, for example, a silane compound having a polymerizable unsaturated bond and a hydrolyzable group (hereinafter referred to as “compound ( a1) "))) and a hydrolysis condensate (hereinafter sometimes referred to as" polysiloxane [A] ").
The compound (a1) is preferably the following formula (1)

(In formula (1), X ¹ represents a vinyl group, an allyl group, a (meth) acryloyloxy group, a styryl group or a vinylbenzyloxy group, and Y ¹ represents a single bond, a methylene group or an alkylene group having 2 to 6 carbon atoms. R ¹ represents an alkoxy group having 1 to 6 carbon atoms or an acyloxy group having 2 to 6 carbon atoms, R ² represents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl having 6 to 12 carbon atoms And a and b each represent an integer of 1 to 3, c represents an integer of 0 to 2, and a + b + c = 4.)
It is a silane compound represented by these.

Y ¹ in the above formula (1) is preferably a methylene group or an alkylene group having 2 or 3 carbon atoms. Examples of the alkylene group having 2 or 3 carbon atoms include an ethylene group and a trimethylene group.
As the ^{R 1} in the formula (1), preferably an acyloxy group having an alkoxy group or a C2-4 1 to 3 carbon atoms, such as methoxy, ethoxy, n- propoxy, i- propoxy group, An acetoxy group etc. can be mentioned.
Moreover, as R < ² > in said Formula (1), a C1-C4 alkyl group or a C6-C8 aryl group is preferable, for example, a methyl group, an ethyl group, a phenyl group etc. can be mentioned. Examples of the substituent of the substituted aryl group represented by R ² include a halogen atom, a cyano group, a nitro group, or an alkyl group having 1 to 6 carbon atoms.

Specific examples of the compound (a1) include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-i-propoxysilane, vinyltriacetoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxy. Silane, vinylmethyldi-n-propoxysilane, vinylmethyldi-i-propoxysilane, vinylmethyldiacetoxysilane, vinylethyldimethoxysilane, vinylethyldiethoxysilane, vinylethyldi-n-propoxysilane, vinylethyldi-i-propoxysilane, vinylethyldi Acetoxysilane, vinylphenyldimethoxysilane, vinylphenyldiethoxysilane, vinylphenyldi-n-propoxysilane, vinylphenyldi-i-propoxy Vinylphenyldiacetoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltri-n-propoxysilane, allyltri-i-propoxysilane, allyltriacetoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldi- n-propoxysilane, allylmethyldi-i-propoxysilane, allylmethyldiacetoxysilane, allylethyldimethoxysilane, allylethyldiethoxysilane, allylethyldi-n-propoxysilane, allylethyldi-i-propoxysilane, allylethyldiacetoxysilane, allyl Phenyldimethoxysilane, allylphenyldiethoxysilane, allylphenyldi-n-propoxysilane, allylphenyldi-i-propoxysilane Allyl phenyl diacetoxy silane,
(Meth) acryloxymethyltrimethoxysilane, (meth) acryloxymethyltriethoxysilane, (meth) acryloxymethyltri-n-propoxysilane, (meth) acryloxymethyltriacetoxysilane, (meth) acryloxymethylmethyl Dimethoxysilane, (meth) acryloxymethylmethyldiethoxysilane, (meth) acryloxymethylmethyldi-n-propoxysilane, (meth) acryloxymethylmethyldiacetoxysilane, (meth) acryloxymethylethyldimethoxysilane, ( (Meth) acryloxymethylethyldiethoxysilane, (meth) acryloxymethylethyldi-n-propoxysilane, (meth) acryloxymethylethyldiacetoxysilane, (meth) acryloxymethylphenyldimethoxysilane, (Meth) acryloxymethylphenyldiethoxysilane, (meth) acryloxymethylphenyldi-n-propoxysilane, (meth) acryloxymethylphenyldiacetoxysilane, 2- (meth) acryloxyethyltrimethoxysilane, 2- ( (Meth) acryloxyethyltriethoxysilane, 2- (meth) acryloxyethyltri-n-propoxysilane, 2- (meth) acryloxyethyltriacetoxysilane, 2- (meth) acryloxyethylmethyldimethoxysilane, 2- (Meth) acryloxyethylmethyldiethoxysilane, 2- (meth) acryloxyethylmethyldi-n-propoxysilane, 2- (meth) acryloxyethylmethyldiacetoxysilane, 2- (meth) acryloxyethylethyldimethoxy Silane, 2- (meta Acryloxyethylethyldiethoxysilane, 2- (meth) acryloxyethylethyldi-n-propoxysilane, 2- (meth) acryloxyethylethyldiacetoxysilane, 2- (meth) acryloxyethylphenyldimethoxysilane, 2 -(Meth) acryloxyethylphenyldiethoxysilane, 2- (meth) acryloxyethylphenyldi-n-propoxysilane, 2- (meth) acryloxyethylphenyldiacetoxysilane, 3- (meth) acryloxypropyltri Methoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n-propoxysilane, 3- (meth) acryloxypropyltriacetoxysilane, 3- (meth) acryloxypropyl Methyldimethoxysilane 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropylmethyldi-n-propoxysilane, 3- (meth) acryloxypropylmethyldiacetoxysilane, 3- (meth) acryloxy Propylethyldimethoxysilane, 3- (meth) acryloxypropylethyldiethoxysilane, 3- (meth) acryloxypropylethyldi-n-propoxysilane, 3- (meth) acryloxypropylethyldiacetoxysilane, 3- ( (Meth) acryloxypropylphenyldimethoxysilane, 3- (meth) acryloxypropylphenyldiethoxysilane, 3- (meth) acryloxypropylphenyldi-n-propoxysilane, 3- (meth) acryloxypropylphenyldiacetoxysilane ,
p-styryltrimethoxysilane, p-styryltriethoxysilane, p-styryltri-n-propoxysilane, p-styryltriacetoxysilane, p-styrylmethyldimethoxysilane, p-styrylmethyldiethoxysilane, p-styrylmethyldi -N-propoxysilane, p-styrylmethyldiacetoxysilane, p-styrylethyldimethoxysilane, p-styrylethyldiethoxysilane, p-styrylethyldi-n-propoxysilane, p-styrylethyldiacetoxysilane, p- Styrylphenyldimethoxysilane, p-styrylphenyldiethoxysilane, p-styrylphenyldi-n-propoxysilane, p-styrylphenyldiacetoxysilane, m-styryltrimethoxysilane, m-styryltriethoxysilane M-styryltri-n-propoxysilane, m-styryltriacetoxysilane, m-styrylmethyldimethoxysilane, m-styrylmethyldiethoxysilane, m-styrylmethyldi-n-propoxysilane, m-styrylmethyldiacetoxy Silane, m-styrylethyldimethoxysilane, m-styrylethyldiethoxysilane, m-styrylethyldi-n-propoxysilane, m-styrylethyldiacetoxysilane, m-styrylphenyldimethoxysilane, m-styrylphenyldiethoxysilane M-styrylphenyl di-n-propoxysilane, m-styrylphenyldiacetoxysilane, and the like;
p-vinylbenzyloxytrimethoxysilane, p-vinylbenzyloxytriethoxysilane, p-vinylbenzyloxytri-n-propoxysilane, p-vinylbenzyloxytriacetoxysilane, p-vinylbenzyloxymethyldimethoxysilane, p- Vinyl benzyloxymethyldiethoxysilane, p-vinylbenzyloxymethyldi-n-propoxysilane, p-vinylbenzyloxymethyldiacetoxysilane, p-vinylbenzyloxyethyldimethoxysilane, p-vinylbenzyloxyethyldiethoxysilane, p-vinylbenzyloxyethyldi-n-propoxysilane, p-vinylbenzyloxyethyldiacetoxysilane, p-vinylbenzyloxyphenyldimethoxysilane, p-vinylbenzyloxyphenyldiethoxysilane, p- Nylbenzyloxyphenyldi-n-propoxysilane, p-vinylbenzyloxyphenyldiacetoxysilane, m-vinylbenzyloxytrimethoxysilane, m-vinylbenzyloxytriethoxysilane, m-vinylbenzyloxytri-n-propoxysilane , M-vinylbenzyloxytriacetoxysilane, m-vinylbenzyloxymethyldimethoxysilane, m-vinylbenzyloxymethyldiethoxysilane, m-vinylbenzyloxymethyldi-n-propoxysilane, m-vinylbenzyloxymethyldiacetoxy Silane, m-vinylbenzyloxyethyldimethoxysilane, m-vinylbenzyloxyethyldiethoxysilane, m-vinylbenzyloxyethyldi-n-propoxysilane, m-vinylbenzyloxyethyldiacetoxysilane m- vinyl benzyloxycarbonyl phenyl dimethoxysilane, m- vinyl benzyloxycarbonyl phenyl diethoxy silane, m- vinyl benzyloxycarbonyl phenyl di -n- propoxysilane, m- vinyl benzyloxycarbonyl, phenyl diacetoxy silane;
Among these, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, p-styryltrimethoxysilane, p -Styryltriethoxysilane is preferably used from the viewpoint of increasing the sensitivity of the radiation-sensitive resin composition, widening the development margin, and improving heat resistance. These compounds (a1) may be used alone or in combination of two or more.

  In the present invention, the polysiloxane [A] is a hydrolysis condensate of the compound (a1) and a compound represented by the following formula (2) (hereinafter sometimes referred to as “compound (a2)”). preferable.

(In Formula (2), R ⁵ represents a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms, or an acyloxy group having 2 to 6 carbon atoms, R ⁶ represents a substituted or unsubstituted alkyl group having 1 to ⁶ carbon atoms or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, g represents an integer of 1 to 4, and h represents an integer of 0 to 3 And g + h = 4.)
R ⁵ in the above formula (2) is preferably an alkoxy group having 1 to 4 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, or an acyloxy group having 2 to 4 carbon atoms. For example, methoxy group, ethoxy group, n- A propoxy group, i-propoxy group, phenoxy group, naphthyloxy group, acetoxy group, etc. can be mentioned. Examples of the substituent for the alkoxy group having 1 to 6 carbon atoms in R ⁵ include a methoxy group and an ethoxy group. Examples of the substituent for the aryloxy group having 6 to 18 carbon atoms in R ⁵ include halogen atoms. Examples thereof include an atom, a cyano group, a nitro group, and an alkyl group having 1 to 6 carbon atoms. A 4-chlorophenoxy group, a 4-cyanophenoxy group, a 4-nitrophenoxy group, a 4-toluyloxy group, and the like can be given.

As the ^{R 6} in the formula (2), preferably an alkyl group or an aryl group having a carbon number of 6-8 having from 1 to 5 carbon atoms, such as methyl group, ethyl group, n- propyl group, i- propyl group, A pentyl group, a phenyl group, etc. can be mentioned. Examples of the substituent of the substituted alkyl group having 1 to 6 carbon atoms include oxiranyl group, glycidyl group, glycidoxy group, 3,4-epoxycyclohexyl group, 3-oxetanyl group, hydroxyl group, hydroxyphenylcarbonyloxy group, mercapto group, Formula (2-1)
^HO-Y 2 -S- (2-1)
(In Formula (2-1), Y ² represents a methylene group, an alkylene group having 2 to 6 carbon atoms, or an arylene group having 6 to 12 carbon atoms.)
The group etc. which are represented by these can be mentioned. The 3-position carbon of the 3-oxetanyl group may be substituted with an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, or an n-propyl group. Examples of the substituent of the substituted aryl group having 6 to 18 carbon atoms include a halogen atom, a hydroxyl group, a cyano group, a nitro group, a mercapto group, and an alkyl group having 1 to 6 carbon atoms.

Specific examples of the compound (a2) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane; methyltrimethoxysilane, methyltri Monoalkyltrialkoxysilanes such as ethoxysilane, methyltri-n-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, cyclohexyltriethoxysilane;
Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, naphthyltriethoxysilane, 4-chlorophenyltriethoxysilane, 4-cyanophenyltriethoxysilane, 4-nitrophenyltriethoxysilane, 4-methylphenyltriethoxysilane Monoaryltrialkoxysilanes such as
Monoaryloxy such as phenoxytriethoxysilane, naphthyloxytriethoxysilane, 4-chlorophenyloxytriethoxysilane, 4-cyanophenyltrioxyethoxysilane, 4-nitrophenyloxytriethoxysilane, 4-methylphenyloxytriethoxysilane Trialkoxysilane;
Dialkyl dialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, methyl (ethyl) diethoxysilane, methyl (cyclohexyl) diethoxysilane;
Monoalkylmonoaryl dialkoxysilanes such as methyl (phenyl) diethoxysilane; diaryl dialkoxysilanes such as diphenyldiethoxysilane;
Diaryloxy dialkoxysilanes such as diphenoxydiethoxysilane;
Monoalkyl monoaryloxy dialkoxysilanes such as methyl (phenoxy) diethoxysilane;
Monoaryl monoaryloxy dialkoxysilanes such as phenyl (phenoxy) diethoxysilane;
Trialkyl monoalkoxysilanes such as trimethylmethoxysilane, trimethylethoxysilane, trimethyl-n-propoxysilane, dimethyl (ethyl) ethoxysilane, dimethyl (cyclohexyl) ethoxysilane;
Dialkyl monoaryl monoalkoxysilanes such as dimethyl (phenyl) ethoxysilane;
Monoalkyldiarylmonoalkoxysilanes such as methyl (diphenyl) ethoxysilane;
Triaryloxymonoalkoxysilanes such as triphenoxyethoxysilane;
Monoalkyldiaryloxymonoalkoxysilanes such as methyl (diphenoxy) ethoxysilane; monoaryldiaryloxymonoalkoxysilanes such as phenyl (diphenoxy) ethoxysilane;
Dialkylmonoaryloxymonoalkoxysilanes such as dimethyl (phenoxy) ethoxysilane;
Diarylmonoaryloxymonoalkoxysilanes such as diphenyl (phenoxy) ethoxysilane;
Monoalkylmonoarylmonoaryloxymonoalkoxysilanes such as methyl (phenyl) (phenoxy) ethoxysilane;
Glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, glycidoxymethyltri-n-propoxysilane, glycidoxymethyltri-i-propoxysilane, glycidoxymethyltriacetoxysilane, glycidoxymethyl Methyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, glycidoxymethylmethyldi-n-propoxysilane, glycidoxymethylmethyldi-i-propoxysilane, glycidoxymethylmethyldiacetoxysilane, glycidoxymethyl Ethyldimethoxysilane, glycidoxymethylethyldiethoxysilane, glycidoxymethylethyldi-n-propoxysilane, glycidoxymethylethyldi-i-propoxysilane, glycidoxymethylethyldiacetoxysilane, group Sidoxymethylphenyldimethoxysilane, glycidoxymethylphenyldiethoxysilane, glycidoxymethylphenyldi-n-propoxysilane, glycidoxymethylphenyldi-i-propoxysilane, glycidoxymethylphenyldiacetoxysilane, 2 -Glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 2-glycidoxyethyltri-n-propoxysilane, 2-glycidoxyethyltri-i-propoxysilane, 2-glycidoxy Ethyltriacetoxysilane, 2-glycidoxyethylmethyldimethoxysilane, 2-glycidoxyethylmethyldiethoxysilane, 2-glycidoxyethylmethyldi-n-propoxysilane, 2-glycidoxyethylmethyldi-i -Propoxysilane, 2 Glycidoxyethylmethyldiacetoxysilane, 2-glycidoxyethylethyldimethoxysilane, 2-glycidoxyethylethyldiethoxysilane, 2-glycidoxyethylethyldi-n-propoxysilane, 2-glycidoxyethyl Ethyldi-i-propoxysilane, 2-glycidoxyethylethylacetoxysilane, 2-glycidoxyethylphenyldimethoxysilane, 2-glycidoxyethylphenyldiethoxysilane, 2-glycidoxyethylphenyldi-n -Propoxysilane, 2-glycidoxyethylphenyldi-i-propoxysilane, 2-glycidoxyethylphenyldiacetoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3 -Glycidoxypropyltri -N-propoxysilane, 3-glycidoxypropyltri-i-propoxysilane, 3-glycidoxypropyltriacetoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldi-n-propoxysilane, 3-glycidoxypropylmethyldi-i-propoxysilane, 3-glycidoxypropylmethyldiacetoxysilane, 3-glycidoxypropylethyldimethoxysilane, 3 -Glycidoxypropylethyldiethoxysilane, 3-glycidoxypropylethyldi-n-propoxysilane, 3-glycidoxypropylethyldi-i-propoxysilane, 3-glycidoxypropylethyldiacetoxysilane, 3 -Glycidoxypropyl fe Rudimethoxysilane, 3-glycidoxypropylphenyldiethoxysilane, 3-glycidoxypropylphenyldi-n-propoxysilane, 3-glycidoxypropylphenyldi-i-propoxysilane, 3-glycidoxypropylphenyl Diacetoxysilane and the like;
(3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, (3,4-epoxycyclohexyl) methyltri-n-propoxysilane, (3,4-epoxycyclohexyl) methyl Triacetoxysilane, (3,4-epoxycyclohexyl) methylmethyldimethoxysilane, (3,4-epoxycyclohexyl) methylmethyldiethoxysilane, (3,4-epoxycyclohexyl) methylmethyldi-n-propoxysilane, (3,4 -Epoxycyclohexyl) methylmethyldiacetoxysilane, (3,4-epoxycyclohexyl) methylethyldimethoxysilane, (3,4-epoxycyclohexyl) methylethyldiethoxysilane, (3,4-epoxysilane) (Hexyl) methylethyldi-n-propoxysilane, (3,4-epoxycyclohexyl) methylethyldiacetoxysilane, (3,4-epoxycyclohexyl) methylphenyldimethoxysilane, (3,4-epoxycyclohexyl) methylphenyldiethoxysilane, (3,4-epoxycyclohexyl) methylphenyldi-n-propoxysilane, (3,4-epoxycyclohexyl) methylphenyldiacetoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethyltriethoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethyltri-n-propoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethyltriacetoxysilane , 2- ( 3 ′, 4′-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethylmethyldiethoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethylmethyldi-n-propoxysilane 2- (3 ′, 4′-epoxycyclohexyl) ethylmethyldiacetoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethylethyldimethoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethylethyl Diethoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethylethyldi-n-propoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethylethyldiacetoxysilane, 2- (3 ′, 4′- Epoxycyclohexyl) ethylphenyldimethoxysilane, 2- (3 ′, 4′-epoxysilane) Rohexyl) ethylphenyldiethoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethylphenyldi-n-propoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethylphenyldiacetoxysilane, 3- ( 3 ', 4'-epoxycyclohexyl) propyltrimethoxysilane, 3- (3', 4'-epoxycyclohexyl) propyltriethoxysilane, 3- (3 ', 4'-epoxycyclohexyl) propyltri-n-propoxysilane 3- (3 ′, 4′-epoxycyclohexyl) propyltriacetoxysilane, 3- (3,4-epoxycyclohexyl) propylmethyldimethoxysilane, 3- (3 ′, 4′-epoxycyclohexyl) propylmethyldiethoxysilane , 3- (3 ′, 4′-epoxycyclohexyl) propyl Tildi-n-propoxysilane, 3- (3 ′, 4′-epoxycyclohexyl) propylmethyldiacetoxysilane, 3- (3 ′, 4′-epoxycyclohexyl) propylethyldimethoxysilane, 3- (3 ′, 4 ′ -Epoxycyclohexyl) propylethyldiethoxysilane, 3- (3 ', 4'-epoxycyclohexyl) propylethyldi-n-propoxysilane, 3- (3', 4'-epoxycyclohexyl) propylethyldiacetoxysilane, 3 -(3 ', 4'-epoxycyclohexyl) propylphenyldimethoxysilane, 3- (3', 4'-epoxycyclohexyl) propylphenyldiethoxysilane, 3- (3 ', 4'-epoxycyclohexyl) propylphenyldi- n-propoxysilane, 3- (3 ′, 4′-epoxycyclohexyl) Propylphenyldiacetoxysilane and the like;

(Oxetane-3-yl) methyltrimethoxysilane, (oxetane-3-yl) methyltriethoxysilane, (oxetane-3-yl) methyltri-n-propoxysilane, (oxetane-3-yl) methyltri-i-propoxy Silane, (oxetane-3-yl) methyltriacetoxysilane, (oxetane-3-yl) methylmethyldimethoxysilane, (oxetane-3-yl) methylmethyldiethoxysilane, (oxetane-3-yl) methylmethyldi-n- Propoxysilane, (oxetane-3-yl) methylmethyldi-i-propoxysilane, (oxetane-3-yl) methylmethyldiacetoxysilane, (oxetane-3-yl) methylethyldimethoxysilane, (oxetane-3-yl) methyl Ethyldiethoxysilane, ( Xetane-3-yl) methylethyldi-n-propoxysilane, (oxetane-3-yl) methylethyldi-i-propoxysilane, (oxetane-3-yl) methylethyldiacetoxysilane, (oxetane-3-yl) methylphenyldimethoxy Silane, (oxetane-3-yl) methylphenyldiethoxysilane, (oxetane-3-yl) methylphenyldi-n-propoxysilane, (oxetane-3-yl) methylphenyldi-i-propoxysilane, (oxetane- 3-yl) methylphenyldiacetoxysilane, 2- (oxetane-3′-yl) ethyltrimethoxysilane, 2- (oxetane-3′-yl) ethyltriethoxysilane, (oxetane-3-yl) ethyltri-n -Propoxysilane, 2- (oxetane-3'- L) Ethyltri-i-propoxysilane, 2- (oxetane-3'-yl) ethyltriacetoxysilane, 2- (oxetane-3'-yl) ethylmethyldimethoxysilane, 2- (oxetane-3'-yl) ethyl Methyldiethoxysilane, 2- (oxetane-3′-yl) ethylmethyldi-n-propoxysilane, 2- (oxetane-3′-yl) ethylmethyldi-i-propoxysilane, 2- (oxetane-3′-yl) ethyl Methyldiacetoxysilane, 2- (oxetane-3′-yl) ethylethyldimethoxysilane, 2- (oxetane-3′-yl) ethylethyldiethoxysilane, 2- (oxetane-3′-yl) ethylethyldi-n- Propoxysilane, 2- (oxetane-3′-yl) ethylethyldi-i-propoxysilane, 2- (o Cetane-3′-yl) ethylethyldiacetoxysilane, 2- (oxetane-3′-yl) ethylphenyldimethoxysilane, 2- (oxetane-3′-yl) ethylphenyldiethoxysilane, 2- (oxetane-3 '-Yl) ethylphenyldi-n-propoxysilane, 2- (oxetane-3'-yl) ethylphenyldi-i-propoxysilane, 2- (oxetane-3'-yl) ethylphenyldiacetoxysilane, 3- (Oxetane-3′-yl) propyltrimethoxysilane, 3- (oxetane-3′-yl) propyltriethoxysilane, 3- (oxetane-3′-yl) propyltri-n-propoxysilane, 3- (oxetane -3'-yl) propyltri-i-propoxysilane, 3- (oxetane-3'-yl) propyltriacetoxy Lan, 3- (oxetane-3′-yl) propylmethyldimethoxysilane, 3- (oxetane-3′-yl) propylmethyldiethoxysilane, 3- (oxetane-3′-yl) propylmethyldi-n-propoxy Silane, 3- (oxetane-3′-yl) propylmethyldi-i-propoxysilane, 3- (oxetane-3′-yl) propylmethyldiacetoxysilane, 3- (oxetane-3′-yl) propylethyldimethoxy Silane, 3- (oxetane-3′-yl) propylethyldiethoxysilane, 3- (oxetane-3′-yl) propylethyldi-n-propoxysilane, 3- (oxetane-3′-yl) propylethyldi -I-propoxysilane, 3- (oxetane-3'-yl) propylethyldiacetoxysilane, 3- (oxetane 3'-yl) propylphenyldimethoxysilane, 3- (oxetane-3'-yl) propylphenyldiethoxysilane, 3- (oxetane-3'-yl) propylphenyldi-n-propoxysilane, 3- (oxetane- 3′-yl) propylphenyldi-i-propoxysilane, 3- (oxetane-3′-yl) propylphenyldiacetoxysilane, (3-methyloxetane-3-yl) methyltrimethoxysilane, (3-methyloxetane -3-yl) methyltriethoxysilane, (3-methyloxetane-3-yl) methyltri-n-propoxysilane, (3-methyloxetane-3-yl) methyltri-i-propoxysilane, (3-methyloxetane- 3-yl) methyltriacetoxysilane, (3-methyloxetane-3-yl) Methylmethyldimethoxysilane, (3-methyloxetane-3-yl) methylmethyldiethoxysilane, (3-methyloxetane-3-yl) methylmethyldi-n-propoxysilane, (3-methyloxetane-3-yl) methylmethyldi- i-propoxysilane, (3-methyloxetane-3-yl) methylmethyldiacetoxysilane, (3-methyloxetane-3-yl) methylethyldimethoxysilane, (3-methyloxetane-3-yl) methylethyldiethoxy Silane, (3-methyloxetane-3-yl) methylethyldi-n-propoxysilane, (3-methyloxetane-3-yl) methylethyldi-i-propoxysilane, (3-methyloxetane-3-yl) methylethyldiacetoxy Silane, (3-methyloxetane- -Yl) methylphenyldimethoxysilane, (3-methyloxetane-3-yl) methylphenyldiethoxysilane, (3-methyloxetane-3-yl) methylphenyldi-n-propoxysilane, (3-methyloxetane-3 -Yl) methylphenyldi-i-propoxysilane, (3-methyloxetane-3-yl) methylphenyldiacetoxysilane, 2- (3'-methyloxetane-3'-yl) ethyltrimethoxysilane, 2- ( 3'-methyloxetane-3'-yl) ethyltriethoxysilane, 2- (3'-methyloxetane-3'-yl) ethyltri-n-propoxysilane, 2- (3'-methyloxetane-3'-yl) ) Ethyltri-i-propoxysilane, 2- (3′-methyloxetane-3′-yl) ethyltriacetoxysilane 2- (3′-methyloxetane-3′-yl) ethylmethyldimethoxysilane, 2- (3′-methyloxetane-3′-yl) ethylmethyldiethoxysilane, 2- (3′-methyloxetane-3 ′) -Yl) ethylmethyldi-n-propoxysilane, 2- (3'-methyloxetane-3'-yl) ethylmethyldi-i-propoxysilane, 2- (3'-methyloxetane-3'-yl) ethylmethyldiacetoxysilane 2- (3′-methyloxetane-3′-yl) ethylethyldimethoxysilane, 2- (3′-methyloxetane-3′-yl) ethylethyldiethoxysilane, 2- (3′-methyloxetane-3) '-Yl) ethylethyldi-n-propoxysilane, 2- (3'-methyloxetane-3'-yl) ethylethyldi-i-propoxysilane, 2- ( '-Methyloxetane-3'-yl) ethylethyldiacetoxysilane, 2- (3'-methyloxetane-3'-yl) ethylphenyldimethoxysilane, 2- (3'-methyloxetane-3'-yl) ethyl Phenyldiethoxysilane, 2- (3′-methyloxetane-3′-yl) ethylphenyldi-n-propoxysilane, 2- (3′-methyloxetane-3′-yl) ethylphenyldi-i-propoxysilane 2- (3′-methyloxetane-3′-yl) ethylphenyldiacetoxysilane, 3- (3′-methyloxetane-3′-yl) propyltrimethoxysilane, 3- (3′-methyloxetane-3) '-Yl) propyltriethoxysilane, 3- (3'-methyloxetane-3'-yl) propyltri-n-propoxysilane, 3- (3'-methyl) Xetane-3′-yl) propyltri-i-propoxysilane, 3- (3′-methyloxetane-3′-yl) propyltriacetoxysilane, 3- (3′-methyloxetane-3′-yl) propylmethyl Dimethoxysilane, 3- (3′-methyloxetane-3′-yl) propylmethyldiethoxysilane, 3- (3′-methyloxetane-3′-yl) propylmethyldi-n-propoxysilane, 3- (3 '-Methyloxetane-3'-yl) propylmethyldi-i-propoxysilane, 3- (3'-methyloxetane-3'-yl) propylmethyldiacetoxysilane, 3- (3'-methyloxetane-3' -Yl) propylethyldimethoxysilane, 3- (3'-methyloxetane-3'-yl) propylethyldiethoxysilane, 3- (3'-methyloxe) Tan-3′-yl) propylethyldi-n-propoxysilane, 3- (3′-methyloxetane-3′-yl) propylethyldi-i-propoxysilane, 3- (3′-methyloxetane-3 ′) -Yl) propylethyldiacetoxysilane, 3- (3'-methyloxetane-3'-yl) propylphenyldimethoxysilane, 3- (3'-methyloxetane-3'-yl) propylphenyldiethoxysilane, 3- (3′-methyloxetane-3′-yl) propylphenyldi-n-propoxysilane, 3- (3′-methyloxetane-3′-yl) propylphenyldi-i-propoxysilane, 3- (3′- Methyloxetane-3′-yl) propylphenyldiacetoxysilane, (3′-ethyloxetane-3′-yl) methyltrimethoxysilane, (3-ethy Oxetane-3-yl) methyltriethoxysilane, (3-ethyloxetane-3-yl) methyltri-n-propoxysilane, (3-ethyloxetane-3-yl) methyltri-i-propoxysilane, (3-ethyloxetane -3-yl) methyltriacetoxysilane, (3-ethyloxetane-3-yl) methylmethyldimethoxysilane, (3-ethyloxetane-3-yl) methylmethyldiethoxysilane, (3-ethyloxetane-3-yl) ) Methylmethyldi-n-propoxysilane, (3-ethyloxetane-3-yl) methylmethyldi-i-propoxysilane, (3-ethyloxetane-3-yl) methylmethyldiacetoxysilane, (3-ethyloxetane-3-yl) ) Methylethyldimethoxysilane, (3-ethyloxe Tan-3-yl) methylethyldiethoxysilane, (3-ethyloxetane-3-yl) methylethyldi-n-propoxysilane, (3-ethyloxetane-3-yl) methylethyldi-i-propoxysilane, (3-ethyl Oxetane-3-yl) methylethyldiacetoxysilane, (3-ethyloxetane-3-yl) methylphenyldimethoxysilane, (3-ethyloxetane-3-yl) methylphenyldiethoxysilane, (3-ethyloxetane-3 -Yl) methylphenyldi-n-propoxysilane, (3-ethyloxetane-3-yl) methylphenyldi-i-propoxysilane, (3-ethyloxetane-3-yl) methylphenyldiacetoxysilane, 2- ( 3'-Ethyloxetane-3'-yl) ethyltrimethoxysila 2- (3′-ethyloxetane-3′-yl) ethyltriethoxysilane, 2- (3′-ethyloxetane-3′-yl) ethyltri-n-propoxysilane, 2- (3′-ethyloxetane- 3'-yl) ethyltri-i-propoxysilane, 2- (3'-ethyloxetane-3'-yl) ethyltriacetoxysilane, 2- (3'-ethyloxetane-3'-yl) ethylmethyldimethoxysilane, 2- (3′-ethyloxetane-3′-yl) ethylmethyldiethoxysilane, 2- (3′-ethyloxetane-3′-yl) ethylmethyldi-n-propoxysilane, 2- (3′-ethyloxetane- 3′-yl) ethylmethyldi-i-propoxysilane, 2- (3′-ethyloxetane-3′-yl) ethylmethyldiacetoxysilane, 2- (3′-ethyloxy) Cetane 3'-yl) ethyl ethyl dimethoxysilane,
2- (3′-ethyloxetane-3′-yl) ethylethyldiethoxysilane, 2- (3′-ethyloxetane-3′-yl) ethylethyldi-n-propoxysilane, 2- (3′-ethyloxetane- 3′-yl) ethylethyldi-i-propoxysilane, 2- (3′-ethyloxetane-3′-yl) ethylethyldiacetoxysilane, 2- (3′-ethyloxetane-3′-yl) ethylphenyldimethoxysilane 2- (3′-ethyloxetane-3′-yl) ethylphenyldiethoxysilane, 2- (3′-ethyloxetane-3′-yl) ethylphenyldi-n-propoxysilane, 2- (3′- Ethyloxetane-3′-yl) ethylphenyldi-i-propoxysilane, 2- (3′-ethyloxetane-3′-yl) ethylphenyldiacetoxysila 3- (3′-ethyloxetane-3′-yl) propyltrimethoxysilane, 3- (3′-ethyloxetane-3′-yl) propyltriethoxysilane, 3- (3′-ethyloxetane-3 ′) -Yl) propyltri-n-propoxysilane, 3- (3'-ethyloxetane-3'-yl) propyltri-i-propoxysilane, 3- (3'-ethyloxetane-3'-yl) propyltriacetoxy Silane, 3- (3′-ethyloxetane-3′-yl) propylmethyldimethoxysilane, 3- (3′-ethyloxetane-3′-yl) propylmethyldiethoxysilane, 3- (3′-ethyloxetane- 3′-yl) propylmethyldi-n-propoxysilane, 3- (3′-ethyloxetane-3′-yl) propylmethyldi-i-propoxysilane, 3- ( '-Ethyloxetane-3'-yl) propylmethyldiacetoxysilane, 3- (3'-ethyloxetane-3'-yl) propylethyldimethoxysilane, 3- (3'-ethyloxetane-3'-yl) propyl Ethyldiethoxysilane, 3- (3′-ethyloxetane-3′-yl) propylethyldi-n-propoxysilane, 3- (3′-ethyloxetane-3′-yl) propylethyldi-i-propoxysilane 3- (3′-ethyloxetane-3′-yl) propylethyldiacetoxysilane, 3- (3′-ethyloxetane-3′-yl) propylphenyldimethoxysilane, 3- (3′-ethyloxetane-3) '-Yl) propylphenyldiethoxysilane, 3- (3'-ethyloxetane-3'-yl) propylphenyldi-n-propoxysilane 3- (3′-ethyloxetane-3′-yl) propylphenyldi-i-propoxysilane, 3- (3′-ethyloxetane-3′-yl) propylphenyldiacetoxysilane, and the like;

Hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, hydroxymethyltri-n-propoxysilane, hydroxymethyltri-i-propoxysilane, hydroxymethyltriacetoxysilane, hydroxymethyltri (methoxyethoxy) silane, hydroxymethylmethyldimethoxysilane , Hydroxymethylmethyldiethoxysilane, hydroxymethylmethyldi-n-propoxysilane, hydroxymethylmethyldi-i-propoxysilane, hydroxymethylmethyldiacetoxysilane, hydroxymethylethyldimethoxysilane, hydroxymethylethyldiethoxysilane, hydroxymethyl Ethyldi-n-propoxysilane, hydroxymethylethyldi-i-propoxysilane, hydroxymethylethyldia Toxisilane, hydroxymethylethyldi (methoxyethoxy) silane, hydroxymethylphenyldimethoxysilane, hydroxymethylphenyldiethoxysilane, hydroxymethylphenyldi-n-propoxysilane, hydroxymethylphenyldi-i-propoxysilane, hydroxymethylphenyldiacetoxy Silane, hydroxymethylphenyldi (methoxyethoxy) silane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxyethyltri-n-propoxysilane, 2-hydroxyethyltri-i-propoxysilane, 2-hydroxyethyltriacetoxysilane, 2-hydroxyethyltri (methoxyethoxy) silane, 2-hydroxyethylmethyldimethoxysilane, 2 Hydroxyethylmethyldiethoxysilane, 2-hydroxyethylmethyldi-n-propoxysilane, 2-hydroxyethylmethyldi-i-propoxysilane, 2-hydroxyethylmethyldiacetoxysilane, 2-hydroxyethylethyldimethoxysilane, 2- Hydroxyethylethyldiethoxysilane, 2-hydroxyethylethyldi-n-propoxysilane, 2-hydroxyethylethyldi-i-propoxysilane, 2-hydroxyethylethyldiacetoxysilane, 2-hydroxyethylethyldi (methoxyethoxy) Silane, 2-hydroxyethylphenyldimethoxysilane, 2-hydroxyethylphenyldiethoxysilane, 2-hydroxyethylphenyldi-n-propoxysilane, 2-hydroxyethylphenyldi-i- Propoxysilane, 2-hydroxyethylphenyldiacetoxysilane, 2-hydroxyethylphenyldi (methoxyethoxy) silane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-hydroxypropyltri-n-propoxysilane 3-hydroxypropyltri-i-propoxysilane, 3-hydroxypropyltriacetoxysilane, 3-hydroxypropyltri (methoxyethoxy) silane, 3-hydroxypropylmethyldimethoxysilane, 3-hydroxypropylmethyldiethoxysilane, 3- Hydroxypropylmethyldi-n-propoxysilane, 3-hydroxypropylmethyldi-i-propoxysilane, 3-hydroxypropylmethyldiacetoxysilane, 3-hydroxy Propylethyldimethoxysilane, 3-hydroxypropylethyldiethoxysilane, 3-hydroxypropylethyldi-n-propoxysilane, 3-hydroxypropylethyldi-i-propoxysilane, 3-hydroxypropylethyldiacetoxysilane, 3-hydroxy Propylethyldi (methoxyethoxy) silane, 3-hydroxypropylphenyldimethoxysilane, 3-hydroxypropylphenyldiethoxysilane, 3-hydroxypropylphenyldi-n-propoxysilane, 3-hydroxypropylphenyldi-i-propoxysilane, 3-hydroxypropylphenyldiacetoxysilane, 3-hydroxypropylphenyldi (methoxyethoxy) silane, 4-hydroxyphenyltrimethoxysilane, 4-hydroxy Phenyltriethoxysilane, 4-hydroxyphenyltri-n-propoxysilane, 4-hydroxyphenyltri-i-propoxysilane, 4-hydroxyphenyltriacetoxysilane, 4-hydroxyphenyltri (methoxyethoxy) silane, 4-hydroxyphenyl Methyldimethoxysilane, 4-hydroxyphenylmethyldiethoxysilane, 4-hydroxyphenylmethyldi-n-propoxysilane, 4-hydroxyphenylmethyldi-i-propoxysilane, 4-hydroxyphenylmethyldiacetoxysilane, 4-hydroxyphenyl Ethyldimethoxysilane, 4-hydroxyphenylethyldiethoxysilane, 4-hydroxyphenylethyldi-n-propoxysilane, 4-hydroxyphenylethyldi-i-propoxy Silane, 4-hydroxyphenylethyldiacetoxysilane, 4-hydroxyphenylethyldi (methoxyethoxy) silane, 4-hydroxyphenylphenyldimethoxysilane, 4-hydroxyphenylphenyldiethoxysilane, 4-hydroxyphenylphenyldi-n-propoxy Silane, 4-hydroxyphenylphenyldi-i-propoxysilane, 4-hydroxyphenylphenyldiacetoxysilane, 4-hydroxyphenylphenyldi (methoxyethoxy) silane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl Trimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltriethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyl) Xyl) pentyltri-n-propoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltri-i-propoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltriacetoxysilane, 4 -Hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltri (methoxyethoxy) silane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylmethyldimethoxysilane, 4-hydroxy-5- (p-hydroxyphenyl) Carbonyloxy) pentylmethyldiethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylmethyldi-n-propoxysilane, 4-hydroxy-5- (p-hydroxyphene) Rucarbonyloxy) pentylmethyldi-i-propoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylmethyldiacetoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylethyldimethoxy Silane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylethyldiethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylethyldi-n-propoxysilane, 4-hydroxy-5 -(P-hydroxyphenylcarbonyloxy) pentylethyldi-i-propoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylethyldiacetoxysilane, 4-hydroxy-5- ( p-hydroxyphenylcarbonyloxy) pentylethyldi (methoxyethoxy) silane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylphenyldimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl Phenyldiethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylphenyldi-n-propoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylphenyldi-i-propoxysilane 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylphenyldiacetoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylphenyldi (me Kishietokishi) silane, the following equation (2-2)
HO—Y ² —S—Y ³ —Si (OR) ₃ (2-2)
(In Formula (2-2), Y ² has the same meaning as in Formula (2-1) above, Y ³ represents a methylene group or an alkylene group having 2 to 6 carbon atoms, and R is independently from each other. Represents an alkyl group having 1 to 6 carbon atoms or an acyl group having 2 to 6 carbon atoms.)
A compound represented by:

As a silane compound containing a mercapto group, for example,
Mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyltri-n-propoxysilane, mercaptomethyltri-i-propoxysilane, mercaptomethyltriacetoxysilane, mercaptomethyltri (methoxyethoxy) silane, mercaptomethylmethyldimethoxysilane , Mercaptomethylmethyldiethoxysilane, mercaptomethylmethyldi-n-propoxysilane, mercaptomethylmethyldi-i-propoxysilane, mercaptomethylmethyldiacetoxysilane, mercaptomethylethyldimethoxysilane, mercaptomethylethyldiethoxysilane, mercaptomethyl Ethyldi-n-propoxysilane, mercaptomethylethyldi-i-propoxysilane, mercaptomethylethyldia Toxisilane, mercaptomethylethyldi (methoxyethoxy) silane, mercaptomethylphenyldimethoxysilane, mercaptomethylphenyldiethoxysilane, mercaptomethylphenyldi-n-propoxysilane, mercaptomethylphenyldi-i-propoxysilane, mercaptomethylphenyldiacetoxy Silane, mercaptomethylphenyldi (methoxyethoxy) silane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethyltri-n-propoxysilane, 2-mercaptoethyltri-i-propoxysilane, 2-mercaptoethyltriacetoxysilane, 2-mercaptoethyltri (methoxyethoxy) silane, 2-mercaptoethylmethyldimethoxysilane, 2 Mercaptoethylmethyldiethoxysilane, 2-mercaptoethylmethyldi-n-propoxysilane, 2-mercaptoethylmethyldi-i-propoxysilane, 2-mercaptoethylmethyldiacetoxysilane, 2-mercaptoethylethyldimethoxysilane, 2- Mercaptoethylethyldiethoxysilane, 2-mercaptoethylethyldi-n-propoxysilane, 2-mercaptoethylethyldi-i-propoxysilane, 2-mercaptoethylethyldiacetoxysilane, 2-mercaptoethylethyldidi (methoxyethoxy) Silane, 2-mercaptoethylphenyldimethoxysilane, 2-mercaptoethylphenyldiethoxysilane, 2-mercaptoethylphenyldi-n-propoxysilane, 2-mercaptoethylphenyldi-i- Propoxysilane, 2-mercaptoethylphenyldiacetoxysilane, 2-mercaptoethylphenyldi (methoxyethoxy) silane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane 3-mercaptopropyltri-i-propoxysilane, 3-mercaptopropyltriacetoxysilane, 3-mercaptopropyltri (methoxyethoxy) silane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3- Mercaptopropylmethyldi-n-propoxysilane, 3-mercaptopropylmethyldi-i-propoxysilane, 3-mercaptopropylmethyldiacetoxysilane, 3-mercap Propylethyldimethoxysilane, 3-mercaptopropylethyldiethoxysilane, 3-mercaptopropylethyldi-n-propoxysilane, 3-mercaptopropylethyldi-i-propoxysilane, 3-mercaptopropylethyldiacetoxysilane, 3-mercapto Propylethyldi (methoxyethoxy) silane, 3-mercaptopropylphenyldimethoxysilane, 3-mercaptopropylphenyldiethoxysilane, 3-mercaptopropylphenyldi-n-propoxysilane, 3-mercaptopropylphenyldi-i-propoxysilane, 3-mercaptopropylphenyldiacetoxysilane, 3-mercaptopropylphenyldi (methoxyethoxy) silane, etc .;

  Of these compounds (a2), tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyl Diethoxysilane and 3-mercaptopropyltrimethoxysilane can be suitably used in terms of reactivity and the heat resistance, transparency, and stripping solution resistance of the resulting interlayer insulating film or microlens.

  Specific examples of polysiloxane [A] preferably used in the present invention include, for example, vinyltrimethoxysilane / phenyltrimethoxysilane cocondensate, vinyltrimethoxysilane / methyltrimethoxysilane / phenyltrimethoxysilane cocondensate, vinyl Trimethoxysilane / phenyltrimethoxysilane / 3-mercaptopropyltrimethoxysilane cocondensate, allyltrimethoxysilane / phenyltrimethoxysilane cocondensate, 3-methacryloxypropyltrimethoxysilane / phenyltrimethoxysilane cocondensate, 3-methacryloxypropyltrimethoxysilane / 3-mercaptopropyltrimethoxysilane / phenyltrimethoxysilane cocondensate and p-styryltrimethoxysilane / phenyltrimethoxysilane cocondensate It can gel.

  In the present invention, the content of the structural unit derived from the compound (a1) is preferably 5 to 70% by weight, particularly preferably based on the total of repeating units derived from the compounds (a1) and (a2). 10 to 60% by weight. When the content of the structural unit derived from the compound (a1) is less than 5% by weight, the heat resistance, surface hardness, and stripping solution resistance of the interlayer insulating film and microlens obtained under firing conditions of less than 250 ° C. are reduced. On the other hand, the storage stability of polysiloxane [A] exceeding 70% by weight tends to deteriorate.

Further, the content of the structural unit derived from the compound (a2) is preferably 30 to 95% by weight, particularly preferably 40 to 40% based on the total of repeating units derived from the compounds (a1) and (a2). 90% by weight. When the structural unit derived from the compound (a2) is less than 30% by weight, the storage stability of the resulting radiation-sensitive resin composition tends to be reduced, whereas when it exceeds 95% by weight, the resulting interlayer insulation is obtained. There is a risk that the heat resistance, surface hardness, and stripping solution resistance of the film or microlens may be insufficient.
The polysiloxane [A] preferably used in the present invention can be synthesized by hydrolyzing and condensing the compounds (a1) and (a2) as described above, preferably in a solvent, preferably in the presence of a catalyst. it can.

  Solvents that can be used for the synthesis of polysiloxane [A] include, for example, alcohol, ether, glycol ether, ethylene glycol monoalkyl ether acetate, diethylene glycol, diethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether, propylene glycol alkyl ether. Acetates, propylene glycol alkyl ether propionates, aromatic hydrocarbons, ketones, esters and the like can be mentioned.

Specific examples thereof include alcohols such as methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, and 3-phenyl-1-propanol;
Tetrahydrofuran as ether;
Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Examples of ethylene glycol monoalkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
Examples of diethylene glycol include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether;
Examples of diethylene glycol monoalkyl ether acetate include diethylene glycol monoethyl ether acetate;
Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
As propylene glycol monoalkyl ether propionate, for example, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate, etc .;
Examples of the propylene glycol monoalkyl ether acetate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;
Aromatic hydrocarbons such as toluene, xylene, etc .;
Examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone;
Examples of esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxy Ethyl acetate, hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy -3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, propoxy Methyl acetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid Propyl, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate Propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropyl Butyl pionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropionate Examples thereof include propyl acid, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, and the like.

  Of these solvents, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether or propylene glycol alkyl ether acetate are preferred, and in particular, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol methyl. Ether acetate or methyl 3-methoxypropionate is preferred. The amount of the solvent used is preferably such that the total amount of the compounds (a1) and (a2) in the reaction solution is 10 to 300% by weight, more preferably 100 to 200% by weight. .

  The hydrolysis and condensation reaction for synthesizing polysiloxane [A] is preferably an acid catalyst (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion Exchange resins, various Lewis acids, etc.) or base catalysts (eg, nitrogen-containing aromatic compounds such as ammonia, primary amines, secondary amines, tertiary amines, pyridine; basic ion exchange resins; sodium hydroxide, etc. Hydroxides; carbonates such as potassium carbonate; carboxylates such as sodium acetate; various Lewis bases). The amount of the catalyst used is preferably 0.2 mol or less, more preferably 0.00001 to 0.1 mol, relative to 1 mol of the monomer.

The amount of water used, the reaction temperature and the reaction time are appropriately set. For example, the following conditions can be adopted.
The amount of water used is preferably 0.1 to 3 mol, more preferably 0.3 to 2 with respect to 1 mol of the total amount of the group R ¹ in the compound (a1) and the group R ^{5 in} the compound (a2). Mol, more preferably 0.5 to 1.5 mol.
The reaction temperature is preferably 40 to 200 ° C, more preferably 50 to 150 ° C.
The reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours.
The compound (a1), (a2) and water and catalyst may be added at once to carry out the hydrolysis and condensation reaction in one step, or the compounds (a1) and (a2), water and catalyst may be added stepwise. By adding, hydrolysis and condensation reaction may be performed in multiple stages.

The weight average molecular weight (hereinafter referred to as “Mw”) of the [A] component used in the present invention is preferably 5 × 10 ^{2 to} 5 × 10 ⁴ , more preferably 1 × 10 ^{3 to} 3 × 10 ⁴ . is there. If the Mw is less than 5 × 10 ² , the development margin may not be sufficient, and the remaining film ratio of the obtained film may decrease, or the pattern shape of the obtained interlayer insulating film or microlens, heat resistance, etc. On the other hand, if it exceeds 5 × 10 ⁴ , the sensitivity may be lowered or the pattern shape may be inferior. The radiation-sensitive resin composition containing the [A] component as described above can easily form a predetermined pattern shape without causing a development residue during development.

[B] Component The [B] component used in the present invention is a 1,2-quinonediazide compound that generates a carboxylic acid upon irradiation with radiation, and is a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus having a hydroxyl group”). Or a condensate of a mother nucleus having an amino group and 1,2-naphthoquinonediazide sulfonic acid halide.
Examples of the mother nucleus having a hydroxyl group include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nucleus having a hydroxyl group.

Specific examples thereof include trihydroxybenzophenone such as 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone;
As tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3,4 2,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, etc .;
Examples of pentahydroxybenzophenone include 2,3,4,2 ′, 6′-pentahydroxybenzophenone;
Examples of hexahydroxybenzophenone include 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone and the like;
Examples of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, and 1,1,1-tri (p-hydroxyphenyl). ) Ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-4) -Hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl- 4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5 6,7,5 ′, 6 ′, 7′-hexanol, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan and the like;
Examples of other mother nucleus having a hydroxyl group include 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 2- [bis {(5-isopropyl-4 -Hydroxy-2-methyl) phenyl} methyl], 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl]- 3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis {1- (4- And hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene.

Examples of the mother nucleus having an amino group include compounds in which the hydroxyl group of the mother nucleus having the hydroxyl group is substituted with an amino group.
Among these mother nuclei, 2,3,4,4′-tetrahydroxybenzophenone, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] Bisphenol is preferred.
As the 1,2-naphthoquinonediazidesulfonic acid halide, 1,2-naphthoquinonediazidesulfonic acid chloride is preferable, and specific examples thereof include 1,2-naphthoquinonediazide-4-sulfonic acid chloride and 1,2-naphthoquinonediazide- 5-sulfonic acid chloride can be mentioned, and among these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferably used.
In the condensation reaction, 1 corresponds to preferably 30 to 85 mol%, more preferably 50 to 70 mol%, based on the number of hydroxyl groups in the phenolic compound or alcoholic compound or the number of amino groups in the mother nucleus having an amino group. , 2-Naphthoquinonediazide sulfonic acid halide can be used.
The condensation reaction can be carried out by a known method.
These [B] components can be used individually or in combination of 2 or more types.

[B] The usage-amount of a component becomes like this. Preferably it is 1-25 weight part with respect to 100 weight part of [A] component, More preferably, it is 5-20 weight part.
If this proportion is less than 1 part by weight, the difference in solubility between the irradiated portion and the unirradiated portion in the alkaline aqueous solution that is the developer may be small, and patterning may be difficult. Alternatively, the heat resistance and solvent resistance of the microlens may be insufficient. On the other hand, when this ratio exceeds 25 parts by weight, the solubility in the alkaline aqueous solution may be insufficient in the radiation-irradiated portion, and development may be difficult.

Other Components The radiation-sensitive resin composition of the present invention contains the above-mentioned [A] component and [B] component as essential components, and further, unsaturated bonds and reactivity contained in the polysiloxane as necessary. [C] a compound having at least one functional group consisting of a group consisting of a polymerizable unsaturated bond, a hydrosilyl group and a mercapto group in the molecule (excluding the component [A]) , [D] a heat-sensitive radical generator, [E] a surfactant, and [F] an adhesion assistant.
Compound having at least two functional groups selected from the group consisting of the above-mentioned [C] polymerizable unsaturated bond, hydrosilyl group and mercapto group in the molecule (except for the component [A]. ] Is a compound having reactivity with the polymerizable unsaturated bond of polysiloxane [A], and is obtained by crosslinking polysiloxane [A]. Alternatively, it can be used to improve the heat resistance and hardness of the microlens.

[C] Among the crosslinkable compounds, examples of the compound having two or more polymerizable unsaturated bonds in the molecule include divinylbenzene, 1,2,4-trivinylcyclohexane, divinyl adipate, and 1,3-divinyl. Compounds having two or more vinyl groups in the molecule, such as tetramethyldisiloxane and divinyldimethylsilane;
Diallylbenzene, 1,5-hexadiene, 1,7-octadiene, diallyl adipate, 1,3-diallyltetramethyldisiloxane, diallylamine, triallylamine, triallylphosphine, diallyldimethylsilane, tetraallylsilane, diallyl phthalate, malein Compounds having two or more allyl groups in the molecule, such as diallyl acid,
Ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol Compounds having two (meth) acryloxy groups in the molecule, such as full orange acrylate and bisphenoxyethanol full orange acrylate,
Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Compounds having 3 or more (meth) acryloxy groups in the molecule, such as hexa (meth) acrylate,
A compound having a vinyl group such as (meth) vinyl acrylate and a (meth) acryloxy group in the molecule;
Examples include compounds having an allyl group such as allyl (meth) acrylate and a (meth) acryloxy group in the molecule.

  Examples of the compound having two or more mercapto groups in the molecule among the above [C] crosslinkable compounds include thioglycolic acid, 3-mercaptopropionic acid, 3-mercaptobutanoic acid, and 3-mercaptopentanoic acid. Mercaptocarboxylic acids, ethylene glycol, tetraethylene glycol, butanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,3,5-tris (2-hydroxyethyl) cyanurate, sorbitol, etc. An esterified product with a monohydric alcohol can be mentioned.

  Among the [C] crosslinkable compounds, compounds having two or more hydrosilyl groups in the molecule include diphenylsilane, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetra Phenyldisiloxane, hydride-terminated polydimethylsiloxane such as DMS-H03, DMS-H11, DMS-H21, DMS-H25, DMS-H31, and DMS-H41 among the compounds manufactured by Gelest, DMS-H031, DMS- Polymethylhydrosiloxanes such as H071, DMS-H082, DMS-H151, DMS-H301, DMS-H501, DMS-H271, polymethylhydrosiloxanes such as HMS-991, HMS-992, and HMS-993, HMS-991, etc. Polyethylhydrosiloxane, such as HDP-111 Phenyldimethylhydrosiloxysilane, methylhydrosiloxane / phenylmethylsiloxane copolymer such as HPM-502, methylhydrosilane / octylmethylsiloxane copolymer such as HAM-301 and HAM-3012, HQM-105, HQM-107, etc. Can be mentioned.

  Of these [C] crosslinkable compounds, compounds having 3 or more (meth) acryloxy groups in the molecule and compounds having 2 or more mercapto groups in the molecule are preferred, and 3 (meth) acryloxy groups in the molecule are preferred. Examples of the compound having two or more compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and compounds having two or more mercapto groups in the molecule. Tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), penta Lithritol tetrakis (thioglycolate), 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5, -tris (3-mercaptobutyloxy) Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is particularly preferred.

Examples of commercially available compounds having three or more (meth) acryloxy groups in the molecule include Aronix M-309, M-400, M-405, M-450, M-7100, and M-8030. , M-8060, M-8100 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (above, Japan) Kayaku Co., Ltd.), Biscoat 295, 300, 360, GPT, 3PA, 400 (above, Osaka Organic Chemical Industries, Ltd.), and the like.
The said [C] crosslinkable compound can be used individually or in mixture of 2 or more types.
[C] The use ratio of the crosslinkable compound is preferably 50 parts by weight or less, more preferably 30 parts by weight or less with respect to 100 parts by weight of the component (A).
By containing the component [C] at such a ratio, the heat resistance and surface hardness of the interlayer insulating film or microlens obtained from the radiation-sensitive resin composition of the present invention can be improved. When the amount used exceeds 50 parts by weight, film roughening may occur in the step of forming a film of the radiation sensitive resin composition on the substrate.

  In the radiation-sensitive resin composition of the present invention, the above-mentioned [D] heat-sensitive radical generator can be used to further improve the crosslinkability of the polysiloxane [A]. [D] As the heat-sensitive radical generator, those generally known as radical polymerization initiators can be used. Examples of such a heat-sensitive radical generator include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2 , 2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1- Azo compounds such as cyano-1-methylethyl) azo] formamide; organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane; and Hydrogen peroxide etc. can be mentioned. When a peroxide is used as the heat-sensitive radical generator, the peroxide may be used together with a reducing agent to form a redox initiator.

  [D] The heat-sensitive radical generator preferably has a decomposition half-life at 60 ° C of 100 minutes or more and a decomposition half-life at 200 ° C of 30 minutes or less. In this case, if the decomposition half-life at 60 ° C. is 100 minutes or less, the crosslinking reaction due to the generation of radicals proceeds during pre-baking, which may deteriorate the sensitivity and resolution, and the decomposition half-life at 200 ° C. If it is 30 minutes or longer, radical generation in the heating step after development is insufficient, and the crosslinking reaction does not proceed, so that sufficient solvent resistance and hardness may not be obtained. Specific examples of preferable [D] heat-sensitive radical generators include, for example, 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1 Examples include '-azobis (cyclohexane-1-carbonitrile) and 1-[(1-cyano-1-methylethyl) azo] formamide.

In the present invention, the ratio of the [D] heat-sensitive radical generator used is preferably 10 parts by weight or less, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the component [A].
By including the component [D] at such a ratio, the chemical resistance, heat resistance and surface hardness of the interlayer insulating film or microlens obtained from the radiation-sensitive resin composition of the present invention can be improved.
[E] Surfactant can be used for the radiation sensitive resin composition of this invention in order to improve applicability | paintability further. As the [E] surfactant that can be used here, for example, fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants can be suitably used.

  Specific examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether. , Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1 , 2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2,3 , 3,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc., and fluoroalkyl Sodium Nzensuruhon acid; fluoroalkyl polyoxyethylene ethers; fluoroalkyl ammonium iodide, fluoroalkyl polyoxyethylene ethers, perfluoroalkyl polyoxyethylene ethanol; perfluoroalkyl alkoxylate; fluorine-based alkyl ester, and the like.

  These commercial products include BM-1000, BM-1100 (manufactured by BM Chemie), MegaFuck F142D, F172, F173, F183, F178, F191, F191 (and above, Dainippon Ink). Chemical Industries, Ltd.), Fluorad FC-170C, FC-171, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.) ), Ftop EF301, 303, and 352 (manufactured by Shin-Akita Kasei Co., Ltd.).

Examples of the silicone surfactant include DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032 (above, Toray Dow Corning)・ Silicon Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above, GE Toshiba Silicone Co., Ltd.) are commercially available. You can list what you have.
Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, and the like. Polyoxyethylene aryl ether of polyoxyethylene dilaurate, polyoxyethylene dialkyl ester such as polyoxyethylene distearate, etc .; (meth) acrylic acid copolymer polyflow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.) Etc. can be used.

These surfactants can be used alone or in combination of two or more.
These [E] surfactants are preferably used in an amount of 5 parts by weight or less, more preferably 2 parts by weight or less based on 100 parts by weight of the component [A]. [E] When the amount of the surfactant used exceeds 5 parts by weight, the coating film may be easily formed when the coating film is formed on the substrate.
In the radiation sensitive resin composition of the present invention, [F] an adhesion assistant can be further used in order to improve the adhesion to the substrate.

  As such [F] adhesion assistant, a functional silane coupling agent is preferably used, and examples thereof include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. . Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like. Such an [F] adhesion assistant is preferably used in an amount of 20 parts by weight or less, more preferably 10 parts by weight or less, relative to 100 parts by weight of the component [A]. In the case where the amount of the adhesion assistant exceeds 20 parts by weight, there may be a case where development residue is likely to occur in the development process.

Radiation-sensitive resin composition The radiation-sensitive resin composition of the present invention is prepared by uniformly mixing the above-mentioned [A] component and [B] component and other components optionally added as described above. . The radiation-sensitive resin composition of the present invention is preferably used in a solution state after being dissolved in an appropriate solvent. For example, the radiation sensitive resin composition in a solution state can be prepared by mixing the [A] component and the [B] component and other components optionally added at a predetermined ratio.
As a solvent used for the preparation of the radiation sensitive resin composition of the present invention, the [A] component and the [B] component and other components optionally blended are uniformly dissolved and reacted with each component. What is not used is used.
As such a solvent, the thing similar to what was illustrated above as a solvent for synthesize | combining polysiloxane [A] preferably used as a [A] component can be mentioned.

  Among such solvents, alcohol, glycol ether, ethylene glycol alkyl ether acetate, ester and diethylene glycol are preferably used from the viewpoints of solubility of each component, reactivity with each component, ease of film formation, and the like. . Among these, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, Purpylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and ethyl 2-ethoxypropionate can be particularly preferably used.

  Furthermore, in order to improve the in-plane uniformity of the film thickness together with the solvent, a high boiling point solvent can be used in combination. Examples of the high boiling point solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether. , Dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl Examples include cellosolve acetate. Of these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.

When a high boiling point solvent is used in combination as the solvent of the radiation sensitive resin composition of the present invention, the amount used is preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 30%, based on the total amount of the solvent. It can be made into weight% or less. If the amount of the high-boiling solvent used exceeds this amount, the coating film thickness uniformity, sensitivity, and residual film rate may decrease.
When preparing the radiation-sensitive resin composition of the present invention in a solution state, components other than the solvent in the solution (that is, the total amount of the [A] component and the [B] component and other components optionally added) The ratio (solid content concentration) can be arbitrarily set according to the purpose of use and the value of the desired film thickness, but is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and still more preferably Is 15 to 35% by weight.
The composition solution thus prepared may be used after being filtered using a Millipore filter having a pore size of about 0.2 μm.

Formation of Interlayer Insulating Film and Microlens Next, a method for forming the interlayer insulating film or microlens of the present invention using the radiation sensitive resin composition of the present invention will be described. The method for forming an interlayer insulating film or microlens of the present invention includes the following steps in the order described below.
(1) forming a film of the radiation sensitive resin composition of the present invention on a substrate;
(2) a step of irradiating at least a part of the coating;
(3) A step of developing the coating after irradiation, and (4) a step of heating the coating after development.

  Hereafter, each process of the formation method of the interlayer insulation film or microlens of this invention is demonstrated in detail.

(1) In the process step (1) of forming a film of the radiation-sensitive resin composition of the present invention on a substrate, the solvent is removed by applying the composition solution of the present invention to the substrate surface and preferably performing pre-baking. It removes and forms the film of a radiation sensitive resin composition.
Examples of the substrate that can be used include a glass substrate, a silicon substrate, and a substrate on which various metals are formed.
The method of applying the composition solution is not particularly limited, and an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet method, or the like is employed. In particular, a spin coating method or a slit die coating method is preferable. Prebaking conditions vary depending on the type of each component, the proportion of use, and the like. For example, it can be set at 60 to 110 ° C. for about 30 seconds to 15 minutes.
The film thickness to be formed is preferably 3 to 6 μm, for example, when the interlayer insulating film is formed, and 0.5 to 3 μm, for example, when the microlens is formed, as the value after pre-baking. .

(2) In the step (2) of irradiating at least part of the coating, radiation is applied to at least part of the coating formed as described above. In order to irradiate a part of the film with radiation, for example, a method of irradiating radiation through a mask having a predetermined pattern can be used.
Thereafter, patterning is performed by developing with a developer to remove the irradiated portion. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
Examples of the ultraviolet rays include radiation including g-line (wavelength 436 nm), i-line (wavelength 365 nm), and the like. Examples of the far ultraviolet light include KrF excimer laser. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include an electron beam.
Among these, ultraviolet rays are preferable, and radiation containing g-line and / or i-line is particularly preferable.
The dose of radiation as (exposure amount), 50~1,500J / ^{m 2} In the case of forming an interlayer insulating film, in the case of forming the microlenses and 50~2,000J / ^{m 2} It is preferable to do.

(3) Step of developing the film after irradiation The developer used in the development step (3) is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine , N-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8- An aqueous solution of an alkali (basic compound) such as diazabicyclo [5.4.0] -7-undecene or 1,5-diazabicyclo [4.3.0] -5-nonane can be used. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous alkali solution described above, or various organic solvents that dissolve the composition of the present invention can be used as a developing solution.
As a developing method, for example, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time at this time varies depending on the composition of the composition, but can be, for example, 30 to 120 seconds.
In addition, conventionally known radiation-sensitive resin compositions need to strictly control the development time because peeling occurs in the formed pattern when the development time exceeds about 20 to 25 seconds from the optimum value. In the case of the radiation sensitive resin composition of the invention, good pattern formation is possible even when the excess time from the optimum development time is 30 seconds or more, and there is an advantage in product yield.

(4) Step of heating the film after development After the development step of the step (3) carried out as described above, the patterned thin film is preferably subjected to, for example, rinsing treatment with running water, and more preferably high pressure The entire surface is irradiated with radiation from a mercury lamp (post-exposure) to decompose the 1,2-quinonediazide compound remaining in the thin film, and then the thin film is heated by a heating device such as a hot plate or oven. By performing the treatment (post-bake treatment), the thin film is cured. The exposure amount in the post-exposure step is preferably 2,000 to 5,000 J / m ² . Moreover, the baking temperature in this hardening process is 120 or more and less than 250 degreeC, for example. Although heating time changes with kinds of heating apparatus, for example, when performing heat processing on a hotplate, it can be set to 30 to 90 minutes when performing heat processing in oven, for example. At this time, a step baking method or the like in which a heating process is performed twice or more may be used. In addition, when forming the coating of the photosensitive material which consists of polysiloxane conventionally known as a high heat resistant material on a board | substrate, the high temperature process of 250 degreeC or more was required, but the radiation sensitive resin composition of this invention In the case of a product, since this treatment temperature can be set to less than 250 ° C., further 240 ° C. or less, and further 230 ° C. or less, there is an advantage that it can be suitably applied to a process for forming a display element.
In this manner, a patterned thin film corresponding to the target interlayer insulating film or microlens can be formed on the surface of the substrate.

Interlayer Insulating Film The interlayer insulating film of the present invention formed as described above has good adhesion to the substrate, excellent solvent resistance and heat resistance, as will be clarified from the examples described later. It has a high transmittance and a low dielectric constant, and can be suitably used as an interlayer insulating film for electronic parts.

The microlens of the present invention formed as described above has good adhesion to the substrate, excellent solvent resistance and heat resistance, and high, as will be apparent from the examples described later. It has a transmittance and a good melt shape, and can be suitably used as a microlens for a solid-state imaging device.
The shape of the microlens of the present invention is a semi-convex lens shape as shown in FIG.

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

Synthesis Example of Component [A] Synthesis Example 1 [A-1]
In a 500 mL three-necked flask, 19.3 g of vinyltrimethoxysilane, 53.1 g of methyltrimethoxysilane, and 154.7 g of phenyltrimethoxysilane were added, and 113.5 g of diethylene glycol methyl ethyl ether was added and dissolved. The resulting solution was heated to 60 ° C. over 30 minutes while stirring with a magnetic stirrer. 70.3 g of ion exchange water containing 5.9 g of oxalic acid was continuously added thereto over 30 minutes, and then reacted at 60 ° C. for 3 hours. Methanol and water were distilled off from the reaction solution under reduced pressure, and diethylene glycol methyl ethyl ether was added so that the solid content concentration was 35% by weight to obtain a solution containing polysiloxane [A-1]. . Polysiloxane [A-1] had a weight average molecular weight Mw in terms of polystyrene of 2,600.

Synthesis Example 2 [A-2]
In a 500 mL three-necked flask, take 71.1 g of vinyltrimethoxysilane and 142.8 g of phenyltrimethoxysilane, add 107.0 g of diethylene glycol methyl ethyl ether to dissolve, and stir the resulting solution with a magnetic stirrer. The temperature was raised to 60 ° C. over 30 minutes. To this was continuously added 64.9 g of ion exchange water containing 5.4 g of oxalic acid over 30 minutes, and then reacted at 60 ° C. for 3 hours. Methanol and water were distilled off from the reaction solution under reduced pressure, and diethylene glycol methyl ethyl ether was added so that the solid content concentration was 35% by weight to obtain a solution containing polysiloxane [A-2]. . Polysiloxane [A-2] had a polystyrene-equivalent weight average molecular weight Mw of 2,200.

Synthesis Example 3 [A-3]
In a 500 mL three-necked flask, 39.3 g of 3-mercaptopropyltrimethoxysilane, 32.0 g of 3-methacryloxypropyltrimethoxysilane, and 119.0 g of phenyltrimethoxysilane were taken, and 93.9 g of diethylene glycol methyl ethyl ether was added thereto. The resulting solution was heated to 60 ° C. over 30 minutes while stirring with a magnetic stirrer. To this, 54.1 g of ion-exchanged water containing 4.5 g of oxalic acid was continuously added over 30 minutes, and then reacted at 60 ° C. for 3 hours. Methanol and water were distilled off from the reaction solution under reduced pressure, and diethylene glycol methyl ethyl ether was added so that the solid content concentration was 35% by weight to obtain a solution containing polysiloxane [A-3]. . Polysiloxane [A-3] had a weight average molecular weight Mw in terms of polystyrene of 2,500.

Synthesis Example 4 [A-4]
In a 500 mL three-necked flask, take 16.2 g of allyltrimethoxysilane, 40.9 g of methyltrimethoxysilane, and 119.0 g of phenyltrimethoxysilane, and add 88.0 g of diethylene glycol methyl ethyl ether to dissolve it. The solution was heated to 60 ° C. while stirring with a magnetic stirrer. To this, 54.1 g of ion exchange water in which 4.5 g of oxalic acid was dissolved was continuously added over 1 hour. And after reacting at 60 degreeC for 3 hours, the obtained reaction liquid is cooled to 40 degreeC, Then, alcohol and water are distilled off under reduced pressure, Diethylene glycol so that solid content concentration may be 35 weight%. By adding methyl ethyl ether, a solution containing polysiloxane [A-4] was obtained. Polysiloxane [A-4] had a polystyrene equivalent weight average molecular weight Mw of 2,400.

Synthesis Example 5 [A-5]
In a 500 mL three-necked flask, 32.0 g of 3-methacryloxypropyltrimethoxysilane, 53.1 g of methyltrimethoxysilane, and 154.7 g of phenyltrimethoxysilane are added, and 119.9 g of diethylene glycol methyl ethyl ether is added and dissolved. The resulting solution was heated to 60 ° C. while stirring with a magnetic stirrer. To this, 59.5 g of ion exchange water in which 5.0 g of oxalic acid was dissolved was continuously added over 1 hour. And after reacting at 60 degreeC for 3 hours, the obtained reaction liquid was cooled to 40 degreeC. The pressure was reduced to 10 Torr at 40 ° C. over 1 minute, and the by-product methanol was distilled off. To this, 39.6 g of ion exchange water and 39.6 g of diethylene glycol methyl ethyl ether were continuously added over 30 minutes, followed by stirring at 40 ° C. for 2 hours. Thereafter, the alcohol and water were distilled off under reduced pressure. Then, a solution containing polysiloxane [A-5] was obtained by adding diethylene glycol methyl ethyl ether so that the solid content concentration was 35% by weight. Polysiloxane [A-5] had a polystyrene-equivalent weight average molecular weight Mw of 2,700.

Comparative Synthesis Example 1 [a-1]
In a 500 mL three-necked flask, 49.0 g of methyltrimethoxysilane and 166.6 g of phenyltrimethoxysilane are added and dissolved by adding 107.8 g of diethylene glycol methyl ethyl ether. The resulting solution is stirred with a magnetic stirrer. The temperature was raised to 60 ° C. To this, 64.9 g of ion exchanged water in which 5.4 g of oxalic acid was dissolved was continuously added over 1 hour. And after reacting at 60 degreeC for 3 hours, the obtained reaction liquid is cooled to 40 degreeC, Then, alcohol and water are distilled off under reduced pressure, Diethylene glycol so that solid content concentration may be 35 weight%. By adding methyl ethyl ether, a solution containing polysiloxane [a-1] was obtained. Polysiloxane [a-1] had a weight average molecular weight Mw in terms of polystyrene of 2,800.

Comparative Synthesis Example 2 [a-2]
A flask equipped with a condenser and a stirrer was charged with 8 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 20 parts by weight of styrene, 20 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 20 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged and the atmosphere was gradually replaced with nitrogen. Stirring started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer [a-2].
The copolymer [a-2] had a polystyrene equivalent weight average molecular weight Mw of 7,500 and a molecular weight distribution (Mw / Mn) of 2.5. The solid content concentration of the polymer solution obtained here was 31.6% by weight.

<Preparation of radiation-sensitive resin composition>
Example 1
The solution containing the polysiloxane [A-1] synthesized in Synthesis Example 1 was added in an amount corresponding to 100 parts by weight (solid content) of the polysiloxane [A-1] and 4,4′- as the component [B]. [1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) ) Condensate (B-1) 10 parts by weight, and after adding diethylene glycol ethyl methyl ether to a solid content concentration of 33% by weight and dissolving uniformly, it is filtered through a membrane filter having a diameter of 0.2 μm. By doing this, the solution (S-1) of the radiation sensitive resin composition was prepared.

Examples 2-11, Comparative Examples 1-2
In Example 1, it carried out like Example 1 except having used the kind and quantity as described in Table 1 as [A] component and [B] component, and the solution of a radiation sensitive resin composition (S-2) to (S-11) and (s-1) to (s-2) were prepared.
In Examples 3, 4, 8, 10, and 11, component [C] was added. In Examples 2 to 11, the component [D] was further added.

Example 12
In Example 10, it was dissolved in diethylene glycol ethyl methyl ether / propylene glycol monomethyl ether acetate = 6/4 (weight ratio) so that the solid content concentration was 20% by weight, and a surfactant SH as a component [E]. A radiation-sensitive resin composition solution (S-12) was prepared in the same manner as in Example 10 except that -28PA (Toray Dow Corning Silicone Co., Ltd.) was added.

  In Table 1, the abbreviation of each component has the following meaning.

[B-1]: 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide Condensate of -5-sulfonic acid chloride (3.0 mol) [C-1]: Dipentaerythritol hexaacrylate (trade name KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)
[C-2]: Dipentaerythritol hexakis (3-mercaptopropionate)
[D-1]: 1,1′-azobis (cyclohexane-1-carbonitrile)
[E-1]: Silicone surfactant (trade name SH-28PA, manufactured by Toray Dow Corning Silicone Co., Ltd.)

<Performance evaluation as interlayer insulation film>
Examples 13-24, Comparative Examples 3-4
Using the radiation-sensitive resin composition prepared as described above, various characteristics as an interlayer insulating film were evaluated as follows.

[Evaluation of sensitivity]
For Examples 13 to 23 and Comparative Examples 3 to 4 on a silicon substrate, the composition described in Table 2 was applied using a spinner and then prebaked on a hot plate at 100 ° C. for 2 minutes. A coating film having a thickness of 4.0 μm was formed. For Example 24, coating was performed with a slit die coater, the pressure was reduced to 0.5 Torr over 15 seconds at room temperature, the solvent was removed, and then prebaked on a hot plate at 100 ° C. for 2 minutes to obtain a film thickness of 4. A 0 μm coating film was formed.
The obtained coating film was exposed using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. through a mask having a pattern of 3.0 μm line and space (10 to 1). After exposure with varying time, development was performed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 80 seconds by a puddle method. Next, the substrate was washed with ultrapure water for 1 minute and dried to form a pattern on the silicon substrate. At this time, the minimum exposure amount necessary for the space line width to be 0.3 μm was examined. This minimum exposure amount is shown in Table 2 as sensitivity.

[Evaluation of development margin]
For Examples 13 to 23 and Comparative Examples 3 to 4 on a silicon substrate, the composition described in Table 2 was applied using a spinner and then prebaked on a hot plate at 100 ° C. for 2 minutes. A coating film having a thickness of 4.0 μm was formed. For Example 24, coating was performed with a slit die coater, the pressure was reduced to 0.5 Torr over 15 seconds at room temperature, the solvent was removed, and then prebaked on a hot plate at 100 ° C. for 2 minutes to obtain a film thickness of 4. A 0 μm coating film was formed.
Using the PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. through a mask having a 3.0 μm line-and-space (10: 1) pattern on the obtained coating film, the above After exposure with an exposure amount corresponding to the sensitivity value examined in “[Sensitivity evaluation]”, the liquid was accumulated in a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. with the development time as a variable. Developed by the method. Next, the substrate was washed with ultrapure water for 1 minute and then dried to form a pattern on the silicon substrate. At this time, the development time necessary for the line width to be 3 μm is shown in Table 2 as the optimum development time. Further, when the development was further continued from the optimum development time, the time until the 3.0 μm line pattern was peeled off was measured and shown in Table 2 as a development margin.

[Evaluation of solvent resistance]
For Examples 13 to 23 and Comparative Examples 3 to 4 on a silicon substrate, the compositions shown in Table 2 were applied using a spinner and then prebaked on a hot plate at 100 ° C. for 2 minutes. A film was formed. For Example 24, coating was performed with a slit die coater, the pressure was reduced to 0.5 Torr at room temperature over 15 seconds, the solvent was removed, and a coating film was formed by prebaking on a hot plate at 100 ° C. for 2 minutes. did.
Each of the obtained coating films was exposed using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Co., Ltd. so that the integrated irradiation amount was 3,000 J / m ² . Was heated at 220 ° C. for 1 hour to obtain a cured film having a thickness of about 3.0 μm. The film thickness (T1) of the obtained cured film was measured. And after immersing the silicon substrate in which this cured film was formed in the dimethyl sulfoxide temperature-controlled at 70 degreeC for 20 minutes, the film thickness (t1) after immersion of the said cured film was measured, and the film thickness change rate by immersion {| T1-T1 | / T1} × 100 [%] was calculated. The results are shown in Table 2.
In addition, since the patterning was unnecessary in the solvent resistance evaluation, the development step was omitted, and only the coating film forming step, the radiation irradiation step, and the heating step were performed for evaluation.

[Evaluation of heat resistance]
A cured film was formed on a silicon substrate in the same manner as in the above “[Evaluation of solvent resistance]”, and the thickness (T2) of the obtained cured film was measured. Next, the substrate with the cured film was additionally baked in a clean oven at 240 ° C. for 1 hour, and then the film thickness (t2) after the additional baking of the cured film was measured, and the film thickness change rate {| t2- T2 | / T2} × 100 [%] was calculated. The results are shown in Table 2.

[Evaluation of transparency]
A cured film was formed on the glass substrate in the same manner as in the above “[Evaluation of solvent resistance]”, except that a glass substrate “Corning 7059” (manufactured by Corning) was used instead of the silicon substrate. The light transmittance of the glass substrate having this cured film was measured at a wavelength in the range of 400 to 800 nm using a spectrophotometer “150-20 type double beam” (manufactured by Hitachi, Ltd.). Table 2 shows the values of the minimum light transmittance at that time.

[Evaluation of relative permittivity]
On the polished SUS304 substrate, for Examples 13 to 23 and Comparative Examples 3 to 4, the compositions described in Table 2 were applied using a spinner, and then prebaked on a hot plate at 100 ° C. for 2 minutes. As a result, a coating film having a thickness of 3.0 μm was formed. For Example 24, coating was performed with a slit die coater, the pressure was reduced to 0.5 Torr at room temperature over 15 seconds, the solvent was removed, and then prebaked on a hot plate at 100 ° C. for 2 minutes to obtain a film thickness of 3.0 μm. The coating film was formed.
Each of the obtained coating films was exposed using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Co., Ltd. so that the integrated irradiation amount was 3,000 J / m ² . A cured film was formed on the substrate by heating at 220 ° C. for 1 hour. A Pt / Pd electrode pattern was formed on the cured film by vapor deposition to prepare a sample for measuring dielectric constant. About the obtained sample, the relative dielectric constant in the frequency of 10 kHz was measured by CV method using the HP16451B electrode and HP4284A precision LCR meter by Yokogawa Hewlett-Packard Co., Ltd. The results are shown in Table 2.
In addition, since the patterning was unnecessary in evaluation of a dielectric constant, the image development process was abbreviate | omitted, and only the coating-film formation process, the radiation irradiation process, and the heating process were performed for evaluation.

[Evaluation of surface hardness]
A cured film was formed on a silicon substrate in the same manner as in the above “[Evaluation of solvent resistance]”, and the obtained cured film was measured for pencil hardness by the 8.4.1 pencil scratch test of JIS K-5400-1990. It was measured. The results are shown in Table 2. When the pencil hardness is H or higher, the surface hardness is good.

[Evaluation of voltage holding ratio]
A radiation sensitive resin prepared as above using a spinner on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions is formed on the surface, and an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape The composition was applied and prebaked on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of 2.0 μm. Development was carried out with a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 80 seconds by the dipping method. Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 3,000 J / m ² without using a photomask. Further, post-baking was performed at 220 ° C. for 1 hour to form a cured film.

Next, after spraying a 5.5 μm diameter bead spacer on the substrate having the cured film, the surface is opposed to a soda glass substrate on which ITO electrodes are deposited in a predetermined shape on the surface, leaving a liquid crystal injection port and four sides. A liquid crystal cell was produced by pasting together using a sealing agent mixed with glass beads of 0.8 mm, injecting liquid crystal MLC6608 (trade name) manufactured by Merck and sealing the liquid crystal injection port.
This liquid crystal cell is put in a constant temperature layer of 60 ° C., and a liquid crystal voltage holding voltage measurement system VHR-1A type (trade name) manufactured by Toyo Technica is used to make the applied voltage a square wave of 5.5 V and a measurement frequency of 60 Hz. When the voltage holding ratio was measured, the voltage holding ratio was 97%. The results are shown in Table 1.
Here, the voltage holding ratio is a value obtained by the following formula.
Voltage holding ratio (%) = (potential difference of liquid crystal cell after 16.7 milliseconds) / (voltage applied at 0 milliseconds) × 100
The lower the value of the voltage holding ratio of the liquid crystal cell, the higher the possibility of causing a problem called “burn-in” when forming the liquid crystal panel. It can be said that the higher the voltage holding ratio, the higher the reliability of the liquid crystal panel.

<Performance evaluation as a micro lens>
Examples 25-36, Comparative Examples 5-6
Using the radiation-sensitive resin composition prepared as described above, various characteristics as a microlens were evaluated as follows. For the evaluation of solvent resistance, evaluation of heat resistance, and evaluation of transparency, refer to the results of performance evaluation as the interlayer insulating film.

[Evaluation of sensitivity]
Each composition shown in Table 3 was applied onto a silicon substrate using a spinner, and then prebaked on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of 2.0 μm. Using the NSR1755i7A reduced projection exposure machine (NA = 0.50, λ = 365 nm) manufactured by Nikon Corporation, exposure is performed with the exposure time varied through a pattern mask having a predetermined pattern on the obtained coating film. After that, the film was developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 1 minute. Next, the substrate was rinsed with ultrapure water and dried to form a pattern on the silicon substrate. The minimum exposure required for the space line width of 0.8 μm line and space pattern (1 to 1) to be 0.8 μm was examined. This minimum exposure amount is shown in Table 3 as sensitivity.

[Evaluation of development margin]
Each composition shown in Table 3 was applied onto a silicon substrate using a spinner and then pre-baked on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of 2.0 μm. Using the NSR1755i7A reduction projection exposure machine (NA = 0.50, λ = 365 nm) manufactured by Nikon Corporation through a pattern mask having a predetermined pattern on the obtained coating film, the above “[Evaluation of sensitivity]” After exposure at an exposure amount corresponding to the sensitivity value examined in this way, the film was developed with a tetramethylammonium hydroxide aqueous solution having the concentration shown in Table 3 at 25 ° C. for 1 minute. It was rinsed with water and dried to form a pattern on the silicon substrate. Table 3 shows the development time necessary for the space line width of 0.8 μm line and space pattern (one to one) to be 0.8 μm as the optimum development time. Further, the time (development margin) until the pattern having a width of 0.8 μm was peeled off when the development was further continued from the optimum development time was shown in Table 3 as the development margin.

[Formation of microlenses]
Each composition shown in Table 3 was applied onto a silicon substrate using a spinner and then pre-baked on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of 2.0 μm. Using the NSR1755i7A reduction projection exposure machine (NA = 0.50, λ = 365 nm) manufactured by Nikon Corporation through a pattern mask having 4.0 μm dots and 2.0 μm space pattern on the obtained coating film. Then, after performing exposure at an exposure amount corresponding to the value of sensitivity investigated in the above “[Evaluation of Sensitivity]”, a puddle method at 25 ° C. for 1 minute in a 2.38 wt% tetramethylammonium hydroxide aqueous solution. Developed with. Next, the substrate was rinsed with ultrapure water and dried to form a pattern on the silicon substrate. Thereafter, further exposure was performed using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. so that the integrated irradiation amount was 3,000 J / m ² . Thereafter, the pattern was heated at 160 ° C. for 10 minutes on a hot plate and further heated at 230 ° C. for 10 minutes to melt flow the pattern to form a microlens.

  Table 3 shows the size (diameter) and cross-sectional shape of the bottom (surface contacting the substrate) of the formed microlens. It can be said that the microlens bottom portion is good when it is larger than 4.0 μm and smaller than 5.0 μm. When this dimension is 5.0 μm or more, the adjacent lenses are in contact with each other, which is not preferable. Further, the cross-sectional shape is good when it is a semi-convex lens shape as shown in (a) in the schematic diagram shown in FIG. 1, and it is bad when it is on a substantially trapezoidal shape as shown in (b).

Claims (6)

[A] (a1) a polysiloxane that is a hydrolysis condensate of a silane compound represented by the following formula (1) and (a2) a silane compound represented by the following formula (2),
[B] 1,2-quinonediazide compound,
A radiation-sensitive resin composition comprising:

(In formula (1), X ¹ represents a vinyl group, an allyl group, a (meth) acryloyloxy group, a styryl group or a vinylbenzyloxy group, and Y ¹ represents a single bond, a methylene group or an alkylene group having 2 to 6 carbon atoms. R ¹ represents an alkoxy group having 1 to 6 carbon atoms or an acyloxy group having 2 to 6 carbon atoms, R ² represents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl having 6 to 12 carbon atoms And a and b each represent an integer of 1 to 3, c represents an integer of 0 to 2, and a + b + c = 4.)

(In Formula (2), R ⁵ represents a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms, or an acyloxy group having 2 to 6 carbon atoms, R ⁶ represents a substituted or unsubstituted alkyl group having 1 to ⁶ carbon atoms or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, g represents an integer of 1 to 4, and h represents an integer of 0 to 3 And g + h = 4.)   [C] A compound further containing at least two functional groups selected from the group consisting of a polymerizable unsaturated bond, a hydrosilyl group and a mercapto group in the molecule (excluding the component [A]), Item 2. The radiation-sensitive resin composition according to Item 1.   [D] The radiation sensitive resin composition according to claim 1, further comprising a heat sensitive radical generator.   The radiation-sensitive resin composition according to claim 1, which is used for forming an interlayer insulating film or for forming a microlens. A method for forming an interlayer insulating film or a microlens, comprising the following steps in the order described below.
(1) The process of forming the film of the radiation sensitive resin composition of Claim 4 on a board | substrate,
(2) a step of irradiating at least a part of the coating;
(3) A step of developing the coating after irradiation, and (4) a step of heating the coating after development.   An interlayer insulating film or a microlens formed by the method according to claim 5.

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