KR20090089802A - Radiation-sensitive resin composition, interlayer insulation film, microlens and process for producing them - Google Patents

Abstract

A radiation-sensitive composition is provided to have developing margin for forming better profile and easily form pattern phase thin film by having high radiation sensitivity. A radiation-sensitive composition comprises a silane compound of the chemical formula 1 : (X^1-Y^1)_a-SiR^1_bR^2_c, polysiloxane which is hydrolysate of silane compound of the chemical formula 2 : SiR^5_gR^6_h and 1,2-quinonediazide compound. A method for forming an interlayer insulation or microlense comprises: a step of forming a film of the radiation-sensitive resin composition on a substrate; a step of irradiating to a part of the film; a step of developing the film; and a step of heating the film.

Description

Radiation-sensitive resin composition, interlayer insulating film, microlens and a method of forming the same {RADIATION-SENSITIVE RESIN COMPOSITION, INTERLAYER INSULATION FILM, MICROLENS AND PROCESS FOR PRODUCING THEM}

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

Thin film transistors (hereinafter referred to as "TFT") type liquid crystal display elements, organic EL display elements, magnetic head elements, integrated circuit elements, and in general, in order to insulate between wirings arranged in layers in electronic components such as solid-state imaging elements. An interlayer insulating film is provided. As a material which forms an interlayer insulation film, since the number of processes for obtaining the required pattern shape is small, and it is preferable that it has sufficient flatness, the radiation sensitive resin composition is used widely (refer patent document 1 and patent document 2 below).

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 forming a liquid crystal alignment film thereon, so that the interlayer insulating film is formed at a high temperature in the process of forming a transparent electrode film. Since they are exposed to the conditions or exposed to the stripping solution of the resist used for pattern formation of the electrode, sufficient resistance to them is required.

In recent years, TFT type liquid crystal display devices tend to have large screens, high brightness, high precision, high speed response, and thinning, and have high sensitivity as the interlayer insulating film forming composition used therein, and have a low dielectric constant in the interlayer insulating film to be formed. In high transmittance and the like, conventionally, high performance has been demanded.

As such a low dielectric constant and high transmittance interlayer insulating film, a combination of an acrylic resin and a quinone diazide (Patent Document 3) and a combination of a phenol resin and a quinone diazide (Patent Document 4) are known. However, these materials have a problem that outgassing occurs in the heating step after film formation or transparency is lowered.

Moreover, in the image development process at the time of forming an interlayer insulation film from the radiation sensitive resin composition conventionally known, peeling may arise in a pattern when it becomes excess even if developing time is less than optimal time.

The improvement of the display defect of the liquid crystal display element called "baking" is calculated | required from the viewpoint of the improvement of the production yield of a liquid crystal display element, and the reliability improvement. The "small part" is a problem in which impurities, uncured products, etc. elute from the cured film or the like inside the liquid crystal display element, cause problems in the response of the liquid crystal when voltage is applied, and afterimages occur in the liquid crystal display element. This problem is a big problem that lowers the productivity of the liquid crystal display element and impairs reliability.

As described above, in forming the interlayer insulating film from the radiation-sensitive resin composition, it is required that the composition be highly sensitive, and even if the developing time in the developing step during the forming step is more than the predetermined time, the pattern is not peeled off. Although high heat resistance, high solvent resistance, low dielectric constant, high transmittance, high voltage retention and the like are required for the interlayer insulating film formed from the interlayer insulating film formed therefrom, a radiation-sensitive resin composition that satisfies such a requirement is not known in the art. .

On the other hand, a microlens having a lens diameter of about 3 to 100 µm as an imaging system of an on-chip color filter such as a facsimile, an electron copier, a solid-state imaging device, or an optical system of an optical fiber connector, or a microlens array in which these microlenses are regularly arranged Is being 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 dry etching using a melt-flowed lens pattern as a mask. The method of transferring a shape is known. The radiation sensitive resin composition is widely used for formation of the said lens pattern (refer 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 coated with a planarizing film and an etching resist film in order to remove various insulating films on the bonding pads, which are wiring forming portions, and is exposed using a desired mask. It develops and removes the etching resist of a bonding pad part, and then removes a planarization film and various insulating films by etching, and exposes a bonding pad part. Therefore, the microlens or the microlens array requires solvent resistance and heat resistance in the coating film forming step and the etching step of the planarization film and the etching resist.

The radiation sensitive resin composition used for forming such a microlens is highly sensitive, and the microlens formed therefrom has a desired radius of curvature, and is required to have high heat resistance and high transmittance.

In addition, the microlenses obtained from conventionally known radiation-sensitive resin compositions have excessive development even when the developing time is less than the optimum time in the developing step when forming them, and when the developing solution penetrates between the pattern and the substrate, peeling occurs. Since it became easy to produce, it was necessary to strictly control developing time, and there existed a problem from the point of product yield.

As described above, in forming the microlenses from the radiation-sensitive resin composition, a high sensitivity is required as the composition, and even if the developing time is excessively greater than the predetermined time in the developing step during the forming step, no peeling of the pattern occurs. A good melt shape, that is, a good melt shape as a microlens, that is, a melt shape of a desired radius of curvature, high heat resistance, high solvent resistance, and high transmittance are required, but the radiation-sensitive resin composition satisfying such a requirement Not known.

In addition, 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 below). However, in order to sufficiently crosslink the siloxane, a high temperature baking of 250 to 300 ° C. or higher is required. Thus, there is a problem that it is impossible to apply to a process for producing a display element. In addition, attempts have been made to apply siloxane polymers to microlenses, but industrially successful examples are not known until now.

<Patent Document 1> Japanese Patent Application Laid-Open No. 2001-354822

<Patent Document 2> Japanese Patent Application Laid-Open No. 2001-343743

<Patent Document 3> Japanese Unexamined Patent Publication No. 2005-320542

<Patent Document 4> Japanese Patent Application Laid-Open No. 2003-255546

<Patent Document 5> Japanese Unexamined Patent Publication No. 6-18702

<Patent Document 6> Japanese Unexamined Patent Publication No. 6-136239

Patent Document 7: Japanese Unexamined Patent Publication No. 2006-178436

This invention is made | formed based on the above circumstances. Therefore, it is an object of the present invention to form an interlayer insulating film having high heat resistance, high solvent resistance, high transmittance, low dielectric constant, and high voltage retention when used for formation of an interlayer insulating film under baking conditions of less than 250 ° C. When using for formation of a lens, it is providing the radiation sensitive resin composition which can form the micro lens which has a high transmittance | permeability and a favorable melt shape.

Another object of the present invention is to develop a patterned thin film having a high radiation sensitivity, having a developing margin capable of forming a better pattern shape even when the optimum developing time is exceeded in the developing process, and having excellent adhesion. It is to provide a radiation sensitive composition.

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

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 first,

[A] a polysiloxane which is a hydrolytic condensate of (a1) a silane compound represented by the following formula (1) and a silane compound represented by the following formula (2),

[B] 1,2-quinonediazide compound

It is achieved by the radiation sensitive resin composition characterized by including the following.

In Formula 1, X ¹ represents a vinyl group, an allyl group, a (meth) acryloyloxy group, a styryl group or a vinylbenzyloxy group, 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 group having 6 to 12 carbon atoms, and a and b each represent 1 An integer of 3 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, and R ⁶ represents 1 to 6 carbon atoms A substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, g represents an integer of 1 to 4, h represents an integer of 0 to 3, and g + h = 4)

The above object and advantages of the present invention are second,

The following steps are achieved by a method for forming an interlayer insulating film or microlens including the following steps in the order described below.

(1) process of forming the film of said radiation sensitive resin composition on a board | substrate,

(2) irradiating at least a part of said film with radiation,

(3) developing the film after irradiation; and

(4) The process of heating the film after image development.

In addition, the above object and advantage of the present invention is a third,

It is achieved by an interlayer insulating film or microlens formed by the above method.

According to the radiation-sensitive resin composition of the present invention, it is possible to form an interlayer insulating film having sufficient hardness even under baking conditions of less than 250 ° C, excellent in solvent resistance and heat resistance, and having high transmittance, low dielectric constant, and high voltage retention.

In addition, the radiation-sensitive resin composition of the present invention has a high radiation sensitivity, has a developing margin capable of forming a better pattern shape even when the optimum development time is exceeded in the developing step, and facilitates a patterned thin film excellent in adhesion. Can be formed.

In addition, the microlens of the present invention formed from the composition has good adhesion to a substrate, excellent solvent resistance and heat resistance, and has high transmittance and good melt shape, and can be suitably used as a microlens of a solid-state imaging device. have.

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

[A] component

[A] component used by this invention is polysiloxane which has a polymerizable unsaturated bond, For example, of the silane compound (Hereinafter, it may be called "compound (a1)") which has a polymerizable unsaturated bond and a hydrolysable group. And hydrolysis-condensed products (hereinafter sometimes referred to as "polysiloxane [A]").

The compound (a1) is preferably a silane compound represented by the following general formula (1).

<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, 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 group having 6 to 12 carbon atoms, and a and b each represent 1 An integer of 3 to 3, c represents an integer of 0 to 2, and a + b + c = 4)

As Y ¹ in the formula 1 is preferably an alkylene group of a methylene group or a carbon number of 2 or 3; As a C2 or C3 alkylene group, an ethylene group, trimethylene group, etc. are mentioned, for example.

Further, as the R ¹ in said general formula (1), and an acyloxy group having 1 to 3 carbon atoms in the alkoxy group or 2 to 4 carbon atoms preferably, such as methoxy, ethoxy, n- propoxy, i- propoxy And an acetoxy group.

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. are mentioned. As a substituent of the substituted aryl group of R <^2> , a halogen atom, a cyano group, a nitro group, or a C1-C6 alkyl group etc. are mentioned, for example.

As a specific example of such a compound (a1), vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tri-n-propoxy silane, vinyl tri-i-propoxy silane, vinyl triacetoxy silane, vinyl methyl, for example. Dimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldi-n-propoxysilane, vinylmethyldi-i-propoxysilane, vinylmethyldiacetoxysilane, vinylethyldimethoxysilane, vinylethyldiethoxysilane, vinyl Ethyldi-n-propoxysilane, vinylethyldi-i-propoxysilane, vinylethyldiacetoxysilane, vinylphenyldimethoxysilane, vinylphenyldiethoxysilane, vinylphenyldi-n-propoxysilane, vinylphenyl Di-i-propoxysilane, vinylphenyldiacetoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltri-n-propoxysilane, allyltri-i-propoxysilane, allyltriacetoxysilane , Allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldi-n-propoxy Silane, allylmethyldi-i-propoxysilane, allylmethyldiacetoxysilane, allylethyldimethoxysilane, allylethyldiethoxysilane, allylethyldi-n-propoxysilane, allylethyldi-i-propoxysilane Allyl ethyl diacetoxy silane, allyl phenyl dimethoxy silane, allyl phenyl diethoxy silane, allyl phenyl di-n-propoxy silane, allyl phenyl di-i-propoxy silane, allyl phenyl di-ethoxy silane,

(Meth) acryloxymethyltrimethoxysilane, (meth) acryloxymethyltriethoxysilane, (meth) acryloxymethyltri-n-propoxysilane, (meth) acryloxymethyltriacetoxysilane, (meth) Acryloxymethylmethyldimethoxysilane, (meth) acryloxymethylmethyldiethoxysilane, (meth) acryloxymethylmethyldi-n-propoxysilane, (meth) acryloxymethylmethyldiacetoxysilane, (meth) Acryloxymethylethyldimethoxysilane, (meth) acryloxymethylethyldiethoxysilane, (meth) acryloxymethylethyldi-n-propoxysilane, (meth) acryloxymethylethyldiacetoxysilane, (meth) acrylic Oxymethylphenyl dimethoxysilane, (meth) acryloxymethylphenyl diethoxysilane, (meth) acryloxymethylphenyl di-n-propoxysilane, (meth) acryloxymethylphenyl diacetoxysilane, 2- (meth) acryloxyethyl tree Methoxysilane, 2- (meth) acryloxyethyltrie Cysilane, 2- (meth) acryloxyethyl tri-n-propoxysilane, 2- (meth) acryloxyethyltriacetoxysilane, 2- (meth) acryloxyethylmethyldimethoxysilane, 2- (meth) acryl Oxyethylmethyldiethoxysilane, 2- (meth) acryloxyethylmethyldi-n-propoxysilane, 2- (meth) acryloxyethylmethyldiacetoxysilane, 2- (meth) acryloxyethylethyldimethoxysilane , 2- (meth) acryloxyethylethyldiethoxysilane, 2- (meth) acryloxyethylethyldi-n-propoxysilane, 2- (meth) acryloxyethylethyldiacetoxysilane, 2- (meth) Acryloxyethylphenyldimethoxysilane, 2- (meth) acryloxyethylphenyldiethoxysilane, 2- (meth) acryloxyethylphenyldi-n-propoxysilane, 2- (meth) acryloxyethylphenyldiacetoxy Silane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n- Lopoxysilane, 3- (meth) acryloxypropyltriacetoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxy Propylmethyldi-n-propoxysilane, 3- (meth) acryloxypropylmethyldiacetoxysilane, 3- (meth) acryloxypropylethyldimethoxysilane, 3- (meth) acryloxypropylethyldiethoxysilane, 3- (meth) acryloxypropylethyldi-n-propoxy silane, 3- (meth) acryloxypropylethyldiacetoxysilane, 3- (meth) acryloxypropylphenyldimethoxysilane, 3- (meth) acrylic Oxypropylphenyldiethoxysilane, 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-propoxy Silane, p-styrylphenyldiacetoxysilane, m-styryltrimethoxysilane, m-styryltriethoxysilane, m-styryltri-n-propoxysilane, m-styryltriacetoxysilane , m-styrylmethyldimethoxysilane, m-styrylmethyldiethoxysilane, m-styrylmethyldi-n-propoxysilane, m-styrylmethyldiacetoxysilane, m-styrylethyldimethoxysilane , m-styrylethyldiethoxysilane, m-sty Rylethyldi-n-propoxysilane, m-styrylethyldiacetoxysilane, m-styrylphenyldimethoxysilane, m-styrylphenyldiethoxysilane, m-styrylphenyldi-n-propoxysilane , m-styrylphenyldiacetoxysilane and the like;

p-vinylbenzyloxytrimethoxysilane, p-vinylbenzyloxytriethoxysilane, p-vinylbenzyloxytri-n-propoxysilane, p-vinylbenzyloxytriacetoxysilane, p-vinylbenzyloxymethyldimeth Methoxysilane, p-vinylbenzyloxymethyldiethoxysilane, p-vinylbenzyloxymethyldi-n-propoxysilane, p-vinylbenzyloxymethyldiacetoxysilane, p-vinylbenzyloxyethyldimethoxysilane, p- Vinylbenzyloxyethyldiethoxysilane, p-vinylbenzyloxyethyldi-n-propoxysilane, p-vinylbenzyloxy ethyldiacetoxysilane, p-vinylbenzyloxyphenyldimethoxysilane, p-vinylbenzyloxyphenyldie Oxysilane, p-vinylbenzyloxyphenyldi-n-propoxysilane, p-vinylbenzyloxyphenyldiacetoxysilane, m-vinylbenzyloxytrimethoxysilane, m-vinylbenzyloxytriethoxysilane, m- Vinylbenzyloxytri-n-propoxysilane, m-vinylbenzyloxytriacetoxysilane, m-vinylbenzyloxymethyldimethoxysilane, m-vinylbene Oxymethyldiethoxysilane, m-vinylbenzyloxymethyldi-n-propoxysilane, m-vinylbenzyloxymethyldiacetoxysilane, m-vinylbenzyloxyethyldimethoxysilane, m-vinylbenzyloxyethyldiethoxysilane , m-vinylbenzyloxyethyldi-n-propoxysilane, m-vinylbenzyloxyethyldiacetoxysilane, m-vinylbenzyloxyphenyldimethoxysilane, m-vinylbenzyloxyphenyl diethoxysilane, m-vinylbenzyl Oxyphenyldi-n-propoxysilane, m-vinylbenzyloxyphenyldiacetoxysilane and the like;

Among them, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, p -Styryl trimethoxysilane and p-styryl triethoxysilane are used preferably at the point which raises the sensitivity of a radiation sensitive resin composition, widens image development margin, and improves heat resistance. These compounds (a1) are used individually or in combination of 2 or more types.

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

<Formula 2>

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, and R ⁶ represents 1 to 6 carbon atoms A substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, g represents an integer of 1 to 4, h represents an integer of 0 to 3, and g + h = 4)

As R <^5> in said Formula (2), a C1-C4 alkoxy group, a C6-C12 aryloxy group, or a C2-C4 acyloxy group is preferable, For example, a methoxy group, an ethoxy group, n-propoxy A time period, i-propoxy group, a phenoxy group, a naphthyloxy group, an acetoxy group, etc. are mentioned. As a substituent of the C1-C6 alkoxy group in R <^5> , a methoxy group, an ethoxy group, etc. are mentioned, for example, As a substituent of a C6-C18 aryloxy group in R <^5> , for example And halogen atoms, cyano groups, nitro groups, or alkyl groups having 1 to 6 carbon atoms. 4-chlorophenoxy group, 4-cyanophenoxy group, 4-nitrophenoxy group, 4-toluyloxy group, etc. are mentioned.

Moreover, as R <^6> in said Formula (2), a C1-C5 alkyl group or a C6-C8 aryl group is preferable, For example, a methyl group, an ethyl group, n-propyl group, i-propyl group, a pentyl group, a phenyl group etc. Can be mentioned. As a substituent of a C1-C6 substituted alkyl group, for example, an oxiranyl group, glycidyl group, glycidoxy group, 3, 4- epoxycyclohexyl group, 3-oxetanyl group, a hydroxyl group, a hydroxyphenylcarbonyloxy group , A mercapto group, a group represented by the following formula (2a), and the like.

HO-Y ² -S-

(In the formula 2a, Y ² represents an arylene group of a methylene group, having 2 to 6 carbon atoms or an alkylene group having 6 to 12)

An alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, and an n-propyl group, may be substituted with the third position carbon of the 3-oxetanyl group. As a substituent of a C6-C18 substituted aryl group, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a mercapto group, a C1-C6 alkyl group, etc. are mentioned, for example.

Specific examples of the compound (a2) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane and tetra-n-butoxysilane; Methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, cyclo Monoalkyltrialkoxysilanes such as hexyltriethoxysilane;

Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, naphthyltriethoxysilane, 4-chlorophenyltriethoxysilane, 4-cyanophenyltriethoxysilane, 4-nitrophenyltrier Monoaryltrialkoxysilanes such as oxysilane and 4-methylphenyltriethoxysilane;

Phenoxycitriethoxysilane, naphthyloxytriethoxysilane, 4-chlorophenyloxytriethoxysilane, 4-cyanophenyltrioxyethoxysilane, 4-nitrophenyloxytriethoxysilane, 4-methylphenyloxytri Monoaryloxytrialkoxysilanes such as ethoxysilane;

Dialkyl dialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, methyl (ethyl) diethoxysilane, methyl (cyclohexyl) diethoxysilane;

Monoalkylmonoaryldialkoxysilanes such as methyl (phenyl) diethoxysilane; Diaryldialkoxysilanes, such as diphenyldiethoxysilane;

Diaryloxydialkoxysilanes such as diphenoxydiethoxysilane;

Monoalkylmonoaryloxydialkoxysilanes such as methyl (phenoxy) diethoxysilane;

Monoaryl monoaryloxy dialkoxysilanes such as phenyl (phenoxy) diethoxysilane;

Trialkylmonoalkoxysilanes such as trimethylmethoxysilane, trimethylethoxysilane, trimethyl-n-propoxysilane, dimethyl (ethyl) ethoxysilane and dimethyl (cyclohexyl) ethoxysilane;

Dialkylmonoarylmonoalkoxysilanes such as dimethyl (phenyl) ethoxysilane;

Monoalkyldiaryl monoalkoxysilanes 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;

Diaryl monoaryloxy monoalkoxysilanes such as diphenyl (phenoxy) ethoxysilane;

Monoalkylmonoarylmonoaryloxymonoalkoxysilanes such as methyl (phenyl) (phenoxy) ethoxysilane;

Glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, glycidoxymethyltri-n-propoxysilane, glycidoxymethyltri-i-propoxysilane, glycidoxymethyltriacetoxysilane , Glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, glycidoxymethylmethyldi-n-propoxysilane, glycidoxymethylmethyldi-i-propoxysilane, glycidoxymethylmethyl Diacetoxysilane, glycidoxymethylethyldimethoxysilane, glycidoxymethylethyldiethoxysilane, glycidoxymethylethyldi-n-propoxysilane, glycidoxymethylethyldi-i-propoxysilane, glyc Cydoxymethylethyldiacetoxysilane, glycidoxymethylphenyldimethoxysilane, glycidoxymethylphenyldiethoxysilane, glycidoxymethylphenyldi-n-propoxysilane, glycidoxymethylphenyldi-i-propoxysilane, glyc Cidoxymethylphenyldiacetoxysilane, 2-glycidoxy Ethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 2-glycidoxyethyltri-n-propoxysilane, 2-glycidoxyethyltri-i-propoxysilane, 2-glycidoxy Ethyltriacetoxysilane, 2-glycidoxyethylmethyldimethoxysilane, 2-glycidoxyethylmethyldiethoxysilane, 2-glycidoxyethylmethyldi-n-propoxysilane, 2-glycidoxyethylmethyl Di-i-propoxysilane, 2-glycidoxyethylmethyldiacetoxysilane, 2-glycidoxyethylethyldimethoxysilane, 2-glycidoxyethylethyldiethoxysilane, 2-glycidoxyethylethyldi -n-propoxysilane, 2-glycidoxyethylethyldi-i-propoxysilane, 2-glycidoxyethylethyldiacetoxysilane, 2-glycidoxyethylphenyldimethoxysilane, 2-glycidoxy Ethylphenyl diethoxysilane, 2-glycidoxy, phenylphenyl di-n-propoxysilane, 2-glycidoxyethylphenyldi-i-propoxysilane, 2-glycidoxyethylphenyldiacetox Cysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltri-n-propoxysilane, 3-glycidoxypropyltri-i-propoxy Silane, 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-glycidoxypropylphenyldimethoxy Silane, 3-glycidoxypropylphenyldiethoxysilane, 3-glycidoxypropylphenyldi-n-propoxysilane, 3-glycidoxy Propylphenyldi-i-propoxysilane, 3-glycidoxypropylphenyldiacetoxysilane, and the like;

(3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, (3,4-epoxycyclohexyl) methyltri-n-propoxysilane, (3 , 4-epoxycyclohexyl) methyltriacetoxysilane, (3,4-epoxycyclohexyl) methylmethyldimethoxysilane, (3,4-epoxycyclohexyl) methylmethyldiethoxysilane, (3,4-epoxycyclo Hexyl) methylmethyldi-n-propoxysilane, (3,4-epoxycyclohexyl) methylmethyldiacetoxysilane, (3,4-epoxycyclohexyl) methylethyldimethoxysilane, (3,4-epoxycyclo Hexyl) methylethyldiethoxysilane, (3,4-epoxycyclohexyl) methylethyldi-n-propoxysilane, (3,4-epoxycyclohexyl) methylethyldiacetoxysilane, (3,4-epoxycyclo Hexyl) methylphenyldimethoxysilane, (3,4-epoxycyclohexyl) methylphenyldiethoxysilane, (3,4-epoxycyclohexyl) methylphenyldi-n-propoxysilane, (3,4-epoxycyclohexyl) methylphenyl Dia Cetoxysilane, 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) ethylmethyldimethoxy Silane, 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) ethylethyldiethoxy Silane, 2- (3 ', 4'-epoxycyclohexyl) ethylethyldi-n-propoxysilane, 2- (3', 4'-epoxycyclohexyl) ethylethyldiacetoxysilane, 2- (3 ' , 4'-epoxycyclohexyl) ethylphenyldimethoxysilane, 2- (3 ', 4'-epoxycyclohexyl) ethylphenyldiethoxysilane, 2- (3', 4'-epoxycyclohexyl) ethylfe Di-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) propylmethyldi-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) propylethyldiacetoxisilane, 3- (3', 4'-epoxycyclohexyl) propylphenyldimethok Silane, 3- (3 ', 4'-epoxycyclohexyl) propylphenyldiethoxysilane, 3- (3', 4'-epoxycyclohexyl) propylphenyldi-n-propoxysilane, 3- (3 ', 4'-epoxycyclohexyl) phthalic phenyl diacetoxysilane, etc .;

(Oxetan-3-yl) methyltrimethoxysilane, (oxetan-3-yl) methyltriethoxysilane, (oxetan-3-yl) methyltri-n-propoxysilane, (oxetane-3 -Yl) methyltri-i-propoxysilane, (oxetan-3-yl) methyltriacetoxysilane, (oxetan-3-yl) methylmethyldimethoxysilane, (oxetan-3-yl) methylmethyl Diethoxysilane, (oxetan-3-yl) methylmethyldi-n-propoxysilane, (oxetan-3-yl) methylmethyldi-i-propoxysilane, (oxetan-3-yl) methylmethyl Diacetoxysilane, (oxetan-3-yl) methylethyldimethoxysilane, (oxetan-3-yl) methylethyldiethoxysilane, (oxetan-3-yl) methylethyldi-n-propoxysilane , (Oxetan-3-yl) methylethyldi-i-propoxysilane, (oxetan-3-yl) methylethyldiacetoxysilane, (oxetan-3-yl) methylphenyldimethoxysilane, (oxetane -3-yl) methylphenyldiethoxysilane, (oxetan-3-yl) methylphenyldi-n-propoxysilane, (oxetan-3-yl) methylphenyldi-i-propoxysilane, (oxetane-3- (1) Methylpe Diacetoxysilane, 2- (oxetane-3'-yl) ethyltrimethoxysilane, 2- (oxetane-3'-yl) ethyltriethoxysilane, (oxetan-3-yl) ethyltri- n-propoxysilane, 2- (oxetane-3'-yl) ethyltri-i-propoxysilane, 2- (oxetane-3'-yl) ethyltriacetoxysilane, 2- (oxetane-3 '-Yl) ethylmethyldimethoxysilane, 2- (oxetane-3'-yl) ethylmethyldiethoxysilane, 2- (oxetane-3'-yl) ethylmethyldi-n-propoxysilane, 2- (Oxetane-3'-yl) ethylmethyldi-i-propoxysilane, 2- (oxetane-3'-yl) ethylmethyldiacetoxysilane, 2- (oxetane-3'-yl) ethylethyl Dimethoxysilane, 2- (oxetane-3'-yl) ethylethyldiethoxysilane, 2- (oxetane-3'-yl) ethylethyldi-n-propoxysilane, 2- (oxetane-3 ' -Yl) ethylethyldi-i-propoxysilane, 2- (oxetane-3'-yl) ethylethyldiacetoxysilane, 2- (oxetane-3'-yl) ethylphenyldimethoxysilane, 2- (Oxetane-3'-yl) ethylphenyldiethoxysilane, 2- (oxetane-3'-yl) ethylphenyldi-n-propoxysilane, 2- ( Cetane-3'-yl) ethylphenyldi-i-propoxysilane, 2- (oxetane-3'-yl) ethylphenyldiacetoxysilane, 3- (oxetane-3'-yl) propyltrimethoxy Silane, 3- (oxetane-3'-yl) propyltriethoxysilane, 3- (oxetane-3'-yl) propyltri-n-propoxysilane, 3- (oxetane-3'-yl) Propyltri-i-propoxysilane, 3- (oxetane-3'-yl) propyltriacetoxysilane, 3- (oxetane-3'-yl) propylmethyldimethoxysilane, 3- (oxetane-3 '-Yl) propylmethyldiethoxysilane, 3- (oxetane-3'-yl) propylmethyldi-n-propoxysilane, 3- (oxetane-3'-yl) propylmethyldi-i-propoxy Silane, 3- (oxetane-3'-yl) propylmethyldiacetoxysilane, 3- (oxetane-3'-yl) propylethyldimethoxysilane, 3- (oxetane-3'-yl) propylethyl Diethoxysilane, 3- (oxetane-3'-yl) propylethyldi-n-propoxysilane, 3- (oxetane-3'-yl) propylethyldi-i-propoxysilane, 3- (jade Cetane-3'-yl) propylethyldiacetoxysilane, 3- (oxetane-3'-yl) propylphenyl Methoxysilane, 3- (oxetane-3'-yl) propylphenyldiieri cysilane, 3- (oxetane-3'-yl) propylphenyldi-n-propoxysilane, 3- (oxetane-3 ' -Yl) propylphenyldi-i-propoxysilane, 3- (oxetane-3'-yl) propylphenyldiacetoxysilane, (3-methyloxetan-3-yl) methyltrimethoxysilane, (3 -Methyloxetan-3-yl) methyltriethoxysilane, (3-methyloxetan-3-yl) methyltri-n-propoxysilane, (3-methyloxetan-3-yl) methyltri-i -Propoxysilane, (3-methyloxetan-3-yl) methyltriacetoxysilane, (3-methyloxetan-3-yl) methylmethyldimethoxysilane, (3-methyloxetan-3-yl) Methylmethyldiethoxysilane, (3-methyloxetan-3-yl) methylmethyldi-n-propoxysilane, (3-methyloxetan-3-yl) methylmethyldi-i-propoxysilane, (3 -Methyloxetan-3-yl) methylmethyldiacetoxysilane, (3-methyloxetan-3-yl) methylethyldimethoxysilane, (3-methyloxetan-3-yl) methylethyldiethoxysilane , (3-methyloxetan-3-yl) methylethyldi-n-prop Foxysilane, (3-methyloxetan-3-yl) methylethyldi-i-propoxysilane, (3-methyloxetan-3-yl) methylethyldiacetoxysilane, (3-methyloxetane-3 -Yl) methylphenyldimethoxysilane, (3-methyloxetan-3-yl) methylphenyldiethoxysilane, (3-methyloxetan-3-yl) methylphenyldi-n-propoxysilane, (3-methyloxetane 3-yl) methylphenyldi-i-propoxysilane, (3-methyloxetan-3-yl) methylphenyldiacetoxysilane, 2- (3'-methyloxetane-3'-yl) ethyltrimethoxy Silane, 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'-methyljade Cetane-3'-yl) ethylmethyldimethoxysilane, 2- (3'-methyloxetane-3'-yl) ethylmethyldiethoxysilane, 2- (3'-methyloxetane-3'-yl) ethyl Methyldi-n-propoxysilane, 2- (3'-methyloxetane-3'-yl) ethylmethyldi-i-propoxysilane, 2- (3'-methyloxetane-3'-yl) ethylmethyldiacetoxysilane, 2- (3'-methyloxetane-3'-yl) ethylethyldimethoxysilane, 2- (3'-methyl Oxetane-3'-yl) ethylethyldiethoxysilane, 2- (3'-methyloxetane-3'-yl) ethylethyldi-n-propoxysilane, 2- (3'-methyloxetane-3 '-Yl) ethylethyldi-i-propoxysilane, 2- (3'-methyloxetane-3'-yl) ethylethyldiacetoxysilane, 2- (3'-methyloxetane-3'-yl ) Ethylphenyldimethoxysilane, 2- (3'-methyloxetane-3'-yl) ethylphenyldiethoxysilane, 2- (3'-methyloxetane-3'-yl) ethylphenyldi-n-pro Foxysilane, 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'-methyljade Cetane-3'-yl) propyltri-n-propoxysilane, 3- (3'-methyloxetane-3'-yl) propyltri-i-propoxy silane, 3- (3'-methyloxetane- 3'-day) profile Riacetoxysilane, 3- (3'-methyloxetane-3'-yl) propylmethyldimethoxysilane, 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'-methyloxetane-3'-yl) propylethyldi-n-propoxysilane, 3- (3'-methyloxetane-3'-yl ) Propylethyldi-i-propoxysilane, 3- (3'-methyloxetane-3'-yl) propylethyldiacetoxysilane, 3- (3'-methyloxetane-3'-yl) propylphenyl Dimethoxysilane, 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) prop Phenyldiacetoxysilane, (3'-ethyloxetane-3'-yl) methyltrimethoxysilane, (3-ethyloxetan-3-yl) methyltriethoxysilane, (3-ethyloxetane-3 -Yl) methyltri-n-propoxysilane, (3-ethyloxetan-3-yl) methyltri-i-propoxysilane, (3-ethyloxetan-3-yl) methyltriacetoxysilane, ( 3-ethyloxetan-3-yl) methylmethyldimethoxysilane, (3-ethyloxetan-3-yl) methylmethyldiethoxysilane, (3-ethyloxetan-3-yl) methylmethyldi-n- Propoxysilane, (3-ethyloxetan-3-yl) methylmethyldi-i-propoxysilane, (3-ethyloxetan-3-yl) methylmethyldiacetoxysilane, (3-ethyloxetane- 3-yl) methylethyldimethoxysilane, (3-ethyloxetan-3-yl) methylethyldiethoxysilane, (3-ethyloxetan-3-yl) methylethyldi-n-propoxysilane, (3 -Ethyl oxetan-3-yl) methylethyldi-i-propoxysilane, (3-ethyloxetan-3-yl) methylethyldiacetoxysilane, (3-ethyloxetan-3-yl) methylphenyldimeth Oxysilane, (3-ethyloxetan-3-yl) Tylphenyldiethoxysilane, (3-ethyl oxetan-3-yl) methylphenyldi-n-propoxysilane, (3-ethyloxetan-3-yl) methylphenyldi-i-propoxysilane, (3-ethyl Oxetane-3-yl) methylphenyldiacetoxysilane, 2- (3'-ethyloxetane-3'-yl) ethyltrimethoxysilane, 2- (3'-ethyloxetane-3'-yl) ethyl Triethoxysilane, 2- (3'-ethyloxetane-3'-yl) ethyltri-n-propoxysilane, 2- (3'-ethyloxetane-3'-yl) ethyltri-i-prop Foxysilane, 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'-ethyloxetane-3 ' -Yl) ethylethyldimethoxysilane, 2- (3'-ethyloxetane-3'-yl) ethylethyldiethoxysilane, 2- (3'-ethyloxetane-3'-yl) ethyl Ethyldi-n-propoxysilane, 2- (3'-ethyloxetane-3'-yl) ethylethyldi-i-propoxysilane, 2- (3'-ethyloxetane-3'-yl) ethyl Ethyldiacetoxysilane, 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) ethylphenyldiacetoxysilane, 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) propyltriacetoxysilane, 3- (3'-ethyloxetane-3'-yl) propylmethyldimethoxy Silane, 3- (3'-ethyloxetane-3'-yl) propylmethyldiethoxysilane, 3- (3'-ethyloxetane-3'-yl) propylmethyldi-n-propoxysilane, 3- (3'-ethyloxetane-3'-yl) propylmethyldi-i-propoxysilane, 3- (3'-ethyloxetane-3'-yl) propylmethyldiacetoxysilane, 3- (3'-ethyloxetane-3'-yl) propylethyldimethoxysilane, 3- (3'-ethyloxetane-3'-yl) propylethyldiethoxysilane, 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) propylphenyl Diethoxysilane, 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, hydroxy Methylmethyldiacetoxysilane, hydroxymethylethyldimethoxysilane, hydroxymethylethyldiethoxysilane, hydroxymethylethyldi-n-propoxysilane, hydroxymethylethyldi-i-propoxysilane, hydroxymethyl Ethyldiacetoxysilane, hydroxymethylethyldi (methoxyethoxy) silane, hydroxymethylphenyldimethoxysilane, hydroxymethylphenyldiethoxysilane, hydroxymethylphenyldi-n-propoxysilane, hydroxymethylphenyldi-i Propoxysilane, hydroxymeth Butylphenyl diacetoxysilane, hydroxymethylphenyldi (methoxyethoxy) silane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxyethyltri-n-propoxy Silane, 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-hydroxy Ethylethyldiacetoxysilane, 2-hydroxyethylethyldi (methoxyethoxy) silane, 2-hydroxyethylphenyldimethoxysilane, 2-hydroxyethylphenyldiethoxy Cysilane, 2-hydroxyethylphenyldi-n-propoxysilane, 2-hydroxyethylphenyldi-i-propoxysilane, 2-hydroxyethylphenyldiacetoxysilane, 2-hydroxyethylphenyldi (meth Methoxyethoxy) silane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-hydroxypropyltri-n-propoxysilane, 3-hydroxypropyltri-i-propoxy Silane, 3-hydroxypropyltriacetoxysilane, 3-hydroxypropyltri (methoxyethoxy) silane, 3-hydroxypropylmethyldimethoxysilane, 3-hydroxypropylmethyldiethoxysilane, 3-hydroxy Propylmethyldi-n-propoxysilane, 3-hydroxypropylmethyldi-i-propoxysilane, 3-hydroxypropylmethyldiacetoxysilane, 3-hydroxypropylethyldimethoxysilane, 3-hydroxypropyl Ethyldiethoxysilane, 3-hydroxypropylethyldi-n-propoxysilane, 3-hydroxypropylethyldi-i-propoxysilane, 3-hydroxy Cipropylethyldiacetoxysilane, 3-hydroxypropylethyldi (methoxyethoxy) silane, 3-hydroxypropylphenyldimethoxysilane, 3-hydroxypropylphenyldiethoxysilane, 3-hydroxypropylphenyldi -n-propoxysilane, 3-hydroxypropylphenyldi-i-propoxysilane, 3-hydroxypropylphenyldiacetoxysilane, 3-hydroxypropylphenyldi (methoxyethoxy) silane, 4-hydroxy Hydroxyphenyltrimethoxysilane, 4-hydroxyphenyltriethoxysilane, 4-hydroxyphenyltri-n-propoxysilane, 4-hydroxyphenyltri-i-propoxysilane, 4-hydroxyphenyltriace Methoxysilane, 4-hydroxyphenyltri (methoxyethoxy) silane, 4-hydroxyphenylmethyldimethoxysilane, 4-hydroxyphenylmethyldiethoxysilane, 4-hydroxyphenylmethyldi-n-propoxysilane 4-hydroxyphenylmethyldi-i-propoxysilane, 4-hydroxyphenylmethyldiacetoxysilane, 4-hydroxyphenylethyldimethoxysilane, 4 -Hydroxyphenylethyldiethoxysilane, 4-hydroxyphenylethyldi-n-propoxysilane, 4-hydroxyphenylethyldi-i-propoxysilane, 4-hydroxyphenylethyldiacetoxysilane, 4- Hydroxyphenylethyldi (methoxyethoxy) silane, 4-hydroxyphenylphenyldimethoxysilane, 4-hydroxyphenylphenyldiethoxysilane, 4-hydroxyphenylphenyldi-n-propoxysilane, 4-hydroxy Hydroxyphenylphenyldi-i-propoxysilane, 4-hydroxyphenylphenyldiacetoxysilane, 4-hydroxyphenylphenyldi (methoxyethoxy) silane, 4-hydroxy-5- (p-hydroxyphenyl Carbonyloxy) pentyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltriethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) Pentyltri-n-propoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltri-i-propoxysilane, 4-hydroxy-5- (p-hydroxyphenyl Carbonyloxy) pentyltriacetoxysilane , 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltri (methoxyethoxy) silane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylmethyldimethoxy Silane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylmethyldiethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylmethyldi-n-propoxy Silane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylmethyldi-i-propoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylmethyldiacene Methoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylethyldimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylethyldiethoxysilane, 4 -Hydroxy-5- (p-hydroxy phenylcarbonyloxy) pentylethyldi-n-propoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylethyldi-i-prop Foxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylethyldi Acetoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylethyldi (methoxyethoxy) silane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl Phenyldimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylphenyldiethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylphenyldi-n -Propoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylphenyldi-i-propoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl Phenyl diacetoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylphenyldi (methoxyethoxy) silane, the compound represented by the following general formula (2b), and the like;

HO-Y ² -SY ³ -Si (OR) ₃

In Formula 2b, Y ² has the same meaning as in Formula 2a, Y ³ represents a methylene group or an alkylene group having 2 to 6 carbon atoms, and R independently of each other is an alkyl group having 1 to 6 carbon atoms or 2 to 6 carbon atoms. Acyl)

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, mercapto Methylmethyldiacetoxysilane, mercaptomethylethyldimethoxysilane, mercaptomethylethyldiethoxysilane, mercaptomethylethyldi-n-propoxysilane, mercaptomethylethyldi-i-propoxysilane, mercaptomethyl Ethyldiacetoxysilane, mercaptomethylethyldi (methoxyethoxy) silane, mercaptomethylphenyldimethoxysilane, mercaptomethylphenyldiethoxysilane, mercaptomethylphenyldi-n-propoxysilane, mercaptomethylphenyldi-i Propoxysilane, mercaptomethylphenyldiacetoxysilane, mercaptomethylphenyldi (methok Ethoxy) silane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethyltri-n-propoxysilane, 2-mercaptoethyltri-i-propoxysilane , 2-mercaptoethyltriacetoxysilane, 2-mercaptoethyltri (methoxyethoxy) silane, 2-mercaptoethylmethyldimethoxysilane, 2-mercaptoethylmethyldiethoxysilane, 2-mercaptoethyl Methyldi-n-propoxysilane, 2-mercaptoethylmethyldi-i-propoxysilane, 2-mercaptoethylmethyldiacetoxysilane, 2-mercaptoethylethyldimethoxysilane, 2-mercaptoethylethyl Diethoxysilane, 2-mercaptoethylethyldi-n-propoxysilane, 2-mercaptoethylethyldi-i-propoxysilane, 2-mercaptoethylethyldiacetoxysilane, 2-mercaptoethylethyldi (Methoxyethoxy) silane, 2-mercaptoethylphenyldimethoxysilane, 2-mercaptoethylphenyldiethoxysilane, 2-mercaptoethylphenyldi-n-propoxysilane, 2-mercaptoethylphenyldi- i-propoxysilane, 2-mercaptoethyl Phenyldiacetoxysilane, 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- mercaptopropylethyldimethoxysilane, 3-mercaptopropylethyldiethoxysilane, 3-mercaptopropylethyldi-n-propoxysilane, 3-mercaptopropylethyldi-i-propoxysilane, 3- Mercaptopropylethyldiacetoxysilane, 3-mercaptopropylethyldi (methoxyethoxy) silane, 3-mercaptopropylphenyldimethoxysilane, 3-mercaptopropylphenyldiethoxy Column, 3-mercaptopropylphenyldi-n-propoxysilane, 3-mercaptopropylphenyldi-i-propoxysilane, 3-mercaptopropylphenyldiacetoxysilane, 3-mercaptopropylphenyldi (meth Methoxyethoxy) silane and the like;

Among these compounds (a2), tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane , Diphenyldimethoxysilane, diphenyldiethoxysilane and 3-mercaptopropyltrimethoxysilane can be preferably used in view of reactivity and heat resistance, transparency and peeling liquid resistance of the interlayer insulating film or microlens obtained.

As a specific example of polysiloxane [A] used preferably by this invention, a vinyl trimethoxysilane / phenyl trimethoxysilane cocondensate, a vinyl trimethoxysilane / methyl trimethoxysilane / phenyl trimethoxysilane, for example. Co-condensates, vinyltrimethoxysilane / phenyltrimethoxysilane / 3-mercaptopropyltrimethoxysilane co-condensates, allyltrimethoxysilane / phenyltrimethoxysilane co-condensates, 3-methacryloxypropyl Trimethoxysilane / phenyltrimethoxysilane cocondensate, 3-methacryloxypropyltrimethoxysilane / 3-mercaptopropyltrimethoxysilane / phenyltrimethoxysilane cocondensate, and p-styryltree And methoxysilane / phenyltrimethoxysilane cocondensates.

In the present invention, the content of the structural unit derived from the compound (a1) is preferably 5 to 70% by weight, in particular preferably based on the sum of the repeating units derived from the compound (a1) and (a2). 10 to 60% by weight. If the content of the structural unit derived from the compound (a1) is less than 5% by weight, the heat resistance, surface hardness, and peeling liquid resistance of the interlayer insulating film or microlens obtained under the firing conditions of less than 250 ° C tend to be lowered, while 70% by weight. There exists a tendency for the storage stability of polysiloxane [A] exceeding% to deteriorate.

Moreover, the content rate of the structural unit derived from compound (a2) is based on the sum total of the repeating unit derived from compound (a1) and (a2), Preferably it is 30 to 95 weight%, Especially preferably, it is 40 to 90 weight %to be. When the structural unit derived from a compound (a2) is less than 30 weight%, the storage stability of the radiation sensitive resin composition obtained tends to fall, and when it exceeds 95 weight%, the heat resistance of the interlayer insulation film and microlenses obtained, and the surface will be reduced. There exists a possibility that hardness and peeling liquid resistance may run short.

Polysiloxane [A] preferably used in the present invention can be synthesized by hydrolyzing and condensing the compounds (a1) and (a2) as described above in a solvent, preferably in the presence of a catalyst.

As a solvent which can be used for the synthesis | combination of polysiloxane [A], 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 acetate, a propylene glycol alkyl ether propionate, an aromatic hydrocarbon, a ketone, ester, etc. are mentioned.

As these specific examples, As alcohol, For example, methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl- 1-propanol etc .;

Tetrahydrofuran and the like as ether;

As glycol ether, For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc .;

As ethylene glycol monoalkyl ether acetate, For example, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc .;

As diethylene glycol, For example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .;

As diethylene glycol monoalkyl ether acetate, For example, diethylene glycol monoethyl ether acetate etc .;

As propylene glycol monoalkyl ether, For example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc .;

Examples of the propylene glycol monoalkyl ether propionate include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate and the like;

As propylene glycol monoalkyl ether acetate, For example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, a propylene glycol monopropyl ether acetate, a propylene glycol monobutyl ether acetate, etc .;

As an aromatic hydrocarbon, For example, toluene, xylene, etc .;

As the ketone, for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and the like;

Examples of the esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate and hydroxyacetic acid. Methyl, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate, 3-hydroxypropionic acid propyl, 3-hydroxypropionic acid Butyl, 2-hydroxy-3-methyl butyrate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid propyl, butyl acetate, ethoxyacetic acid, ethyl ethoxyacetate, ethoxyacetic acid propyl Butyl oxyacetate, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate Ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 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, 3-methoxy methyl propionate, 3-methoxy ethylpropionate, 3-methoxy propylpropionate, 3-methoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3 Butyl ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, 3-butoxypropionic acid Butyl, and 3-butoxy-propyl propionate, butyl propionate, 3-butoxy respectively.

Among these solvents, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether or propylene glycol alkyl ether acetate are preferable, and in particular, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, and propylene glycol Ethyl ether, propylene glycol methyl ether acetate or methyl 3-methoxypropionate is preferred. As the usage-amount of a solvent, it is preferable to set it as the quantity used as the total amount of a compound (a1) and (a2) 10-300 weight% in a reaction solution, and it is more preferable to set it as the amount which becomes 100-200 weight%.

The hydrolysis and condensation reactions for synthesizing polysiloxane [A] are preferably acid catalysts (e.g. hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic). Nitrogen-containing aromatic compounds such as ion exchange resins, various Lewis acids and the like or base catalysts (e.g., ammonia, primary amines, secondary amines, tertiary amines, pyridine); basic ion exchange resins; hydroxides such as sodium hydroxide; Carbonates such as potassium, carboxylates such as sodium acetate, various Lewis bases, and the like. The amount of the catalyst to be used is preferably 0.2 mol or less, more preferably 0.00001 to 0.1 mol with respect 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 may be adopted.

The amount of water to be used is preferably 0.1 to 3 moles, more preferably 0.3 to 2 moles, and even more preferably 0.5 to 1 moles of the total amount of the group R ¹ in the compound (a1) and the total amount of the group R ^{5 in} the compound (a2). Amount of 1.5 moles.

Reaction temperature becomes like this. Preferably it is 40-200 degreeC, More preferably, it is 50-150 degreeC.

The reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours.

The hydrolysis and condensation reaction may be performed in one step by adding the compound (a1), (a2) and water and the catalyst at one time, or by hydrolyzing the compound (a1), (a2) and the water and the catalyst in steps. And condensation reaction may be carried out in multiple stages.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") of the component [A] used in the present invention is preferably 5 × 10 ² to 5 × 10 ⁴ , and more preferably 1 × 10 ³ to 3 × 10 ⁴ . When Mw is less than 5x10 <^2> , developing margin may not become enough, the residual film rate etc. of a film obtained may fall, the pattern shape, heat resistance, etc. of an interlayer insulation film or microlens obtained may fall, and 5 When it exceeds * 10 < ⁴ >, a sensitivity may fall or a pattern shape may fall. As above-mentioned, the radiation sensitive resin composition containing the component [A] can easily form a predetermined pattern shape without generating developing residue when developing.

[B] component

[B] component used by this invention is a 1, 2- quinonediazide compound which generate | occur | produces a carboxylic acid by irradiation of a radiation, and is a phenolic compound or an alcoholic compound (henceforth "mother nucleus which has a hydroxyl group"), or Condensates of a mother nucleus having an amino group and 1,2-naphthoquinone diazide sulfonic acid halide can be used.

Examples of the mother nucleus having the hydroxyl group include a trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, a (polyhydroxyphenyl) alkane, and a mother nucleus having other hydroxyl groups. Can be.

As these specific examples, it is trihydroxy benzophenone, For example, 2,3, 4- trihydroxy benzophenone, 2,4, 6- trihydroxy benzophenone, etc .;

As tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxy Benzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone and the like;

As pentahydroxy benzophenone, For example, 2,3,4,2 ', 6'- pentahydroxy benzophenone etc .;

As hexahydroxybenzophenone, for example, 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone, 3,4,5,3 ', 4', 5'-hexahydroxybenzo Phenone and the like;

As (polyhydroxyphenyl) alkanes, for example, bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, 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;

As a mother nucleus which has another hydroxyl group, for example, 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-di Hydroxyphenyl) -1-methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl ) Benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene, etc. are mentioned, respectively.

As a mother nucleus which has the said amino group, the compound etc. which substituted the hydroxyl group of the mother nucleus which has the said hydroxyl group with an amino group are mentioned.

Of these mother cores, 2,3,4,4'-tetrahydroxybenzophenone, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene Bisphenol is preferable.

As said 1, 2- naphthoquinone diazide sulfonic-acid halide, 1, 2- naphthoquinone diazide sulfonic-acid chloride is preferable, As a specific example, 1, 2- naphthoquinone diazide- 4-sulfonic acid chloride and 1,2- Naphthoquinone diazide-5-sulfonic acid chloride is mentioned, Among these, it is preferable to use 1,2-naphthoquinone diazide-5-sulfonic acid chloride.

In the condensation reaction, 1,2-naph corresponding to 30 to 85 mol%, more preferably 50 to 70 mol%, with respect to the number of hydroxyl groups in the phenolic compound or the alcoholic compound or the number of amino groups in the mother core having an amino group. Toquinone diazide 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.

The use ratio of the component [B] is preferably 1 to 25 parts by weight, more preferably 5 to 20 parts by weight based on 100 parts by weight of the component [A].

When this ratio is less than 1 part by weight, the difference in solubility between the irradiated portion and the unirradiated portion of the alkaline aqueous solution serving as the developing solution may be small, and patterning may be difficult, and the heat resistance and contents of the resulting interlayer insulating film or microlens may be difficult. Inability to perform may become inadequate. On the other hand, when this ratio exceeds 25 weight part, the solubility to the said aqueous alkali solution in a radiation part may become inadequate and it may become difficult to develop.

Other ingredients

Although the radiation sensitive resin composition of this invention contains the above-mentioned [A] component and [B] component as an essential component, it also has a [C] polymerizable unsaturated bond which has reactivity with the unsaturated bond contained in polysiloxane as needed. Compounds containing two or more in the molecule, one or more functional groups including groups consisting of groups, hydrosilyl groups and mercapto groups (except component [A]), [D] thermosensitive radical generators, [E ] Surfactant, [F] adhesion | attachment adjuvant, etc. can be contained.

Compounds having at least two functional groups selected from the group consisting of the above-mentioned [C] polymerizable unsaturated bonds, hydrosilyl groups and mercapto groups in a molecule (except component [A]. Crosslinkable compound ”may be a compound having reactivity with a polymerizable unsaturated bond possessed by polysiloxane [A], and in order to improve heat resistance and hardness of the interlayer insulating film or microlens obtained by crosslinking polysiloxane [A]. Can be used.

[C] As a compound which has 2 or more of polymerizable unsaturated bonds in a molecule | numerator in a crosslinkable compound, it is divinylbenzene, 1,2, 4- trivinyl cyclohexane, divinic adipic acid, 1, 3-di, for example. A compound having two or more vinyl groups in a molecule such as vinyltetramethyldisiloxane and divinyldimethylsilane;

Diallylbenzene, 1,5-hexadiene, 1,7-octadiene, adipicdiallyl, 1,3-diallyltetramethyldisiloxane, diallylamine, triallylamine, triallylphosphine, diallyldimethyl Compounds having two or more allyl groups in the molecule such as silane, tetraallylsilane, diallyl phthalate, diallyl maleate,

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 Compound which has two (meth) acryloxy groups, such as an acrylate, bisphenoxy ethanol fluorene diacrylate, and a bisphenoxy ethanol fluorene diacrylate, in a molecule | numerator,

Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth Compound which has 3 or more (meth) acryloxy groups, such as an acrylate and dipentaerythritol hexa (meth) acrylate in a molecule | numerator,

Compound which has vinyl groups, such as vinyl (meth) acrylate, and a (meth) acryloxy group in a molecule | numerator,

The compound etc. which have allyl groups, such as allyl (meth) acrylate, and a (meth) acryloxy group in a molecule | numerator are mentioned.

Moreover, as a compound which has two or more mercapto groups in a molecule | numerator among the said [C] crosslinkable compounds, mermers, such as thioglycolic acid, 3-mercaptopropionic acid, 3-mercaptobutanoic acid, and 3-mercaptopentanoic acid, are mentioned, for example. Captocarboxylic acid, ethylene glycol, tetraethylene glycol, butanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,3,5-tris (2-hydroxyethyl) cyanurate, And esterified products with polyhydric alcohols such as sorbitol.

Moreover, as a compound which has two or more hydrosilyl groups in a molecule | numerator among [C] crosslinkable compounds, it is diphenylsilane, 1,1,3,3- tetramethyldisiloxane, 1,1,3,3- tetraphenyldisiloxane. Among the compounds manufactured by Guerest Co., Ltd., hydride-terminated polydimethylsiloxanes such as DMS-H03, DMS-H11, DMS-H21, DMS-H25, DMS-H31, and DMS-H41, DMS-H031, DMS-H071, Polymethylhydrosiloxanes such as DMS-H082, DMS-H151, DMS-H301, DMS-H501, and DMS-H271, polymethylhydrosiloxanes such as HMS-991, HMS-992, HMS-993, poly such as HMS-991 Copolymers of methylhydrosiloxane / phenylmethylsiloxane, such as polyphenyldimethylhydrosiloxysilane, such as ethylhydrosiloxane and HDP-111, HPM-502, and methylhydrosilane / octylmethylsiloxane, such as HAM-301 and HAM-3012. Water, HQM-105, HQM-107 and the like.

Among these [C] crosslinkable compounds, the compound which has three or more (meth) acryloxy groups in a molecule, and the compound which has two or more mercapto groups in a molecule are preferable, and the compound which has three or more (meth) acryloxy groups in a molecule | numerator As a compound which has 2 or more of a trimethylol propane tri (meth) acrylate, a pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a mercapto group in a molecule | numerator, it is a trimethylol propane tris (3- Mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) ), Pentaerythritol tetrakis (thioglycolate), 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5, -tris (3-mercap Butyl-oxy-ethyl) -1,3,5-triazine -2,4,6 (1H, 3H, 5H) - one tree is particularly preferred.

As a commercial item of the compound which has three or more (meth) acryloxy groups in a molecule | numerator, For example, Aronix M-309, Copper M-400, Copper M-405, Copper M-450, Copper M-7100, Copper M-8030 , East M-8060, East M-8100 (above, Toa Kosei Co., Ltd.), KAYARAD TMPTA, East DPHA, East DPCA-20, East DPCA-30, East DPCA-60, East DPCA-120 (above, Nippon Kayaku Co., Ltd.), Biscot 295, East 300, East 360, East GPT, East 3PA, East 400 (above, Osaka Yuki Kagaku Kogyo Co., Ltd.), etc. are mentioned.

Said [C] crosslinkable compound can be used individually or in mixture of 2 or more types.

The use ratio of the [C] crosslinkable compound is preferably 50 parts by weight or less, and more preferably 30 parts by weight or less based on 100 parts by weight of the [A] component.

By containing [C] component in such a ratio, the heat resistance, surface hardness, etc. of the interlayer insulation film or microlens obtained from the radiation sensitive resin composition of this invention can be improved. When this usage amount exceeds 50 weight part, film roughness may arise at the process of forming the film of a radiation sensitive resin composition on a board | substrate.

In the radiation sensitive resin composition of the present invention, in order to further improve crosslinkability of polysiloxane [A], the above-mentioned [D] thermosensitive radical generator can be used.

[D] As the thermosensitive radical generator, those generally known as radical polymerization initiators can be used. As such a thermosensitive radical generator, 2,2'- azobis (4-methoxy-2, 4- dimethylvaleronitrile) and 2,2'- azobis (2, 4- dimethylvaleronitrile, for example ), 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile) Azo compounds such as 1-[(1-cyano-1-methylethyl) azo] formamide; Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivalate, 1,1'-bis- (t-butylperoxy) cyclohexane; And hydrogen peroxide. When using a peroxide as a thermosensitive radical generator, a peroxide can be used simultaneously with a reducing agent, and it can also be set as a redox type initiator.

It is preferable that the said thermosensitive radical generating agent has a decomposition half life at 60 degreeC 100 minutes or more, and a decomposition half life at 200 degreeC is 30 minutes or less. In this case, if the decomposition half-life at 60 ° C. is 100 minutes or less, the sensitivity and resolution may deteriorate for the crosslinking reaction due to radical generation to proceed during prebaking, and the decomposition half-life at 200 ° C. is 30 minutes or more. Radical generation in the heating step after the backside development is insufficient, and the crosslinking reaction does not proceed, and there is a fear that sufficient solvent resistance and hardness may not be obtained. As a specific example of a preferable [D] thermosensitive radical generator, 2,2'- azobis (2-methyl propionitrile), 2,2'- azobis (2-methyl butyronitrile), 1, 1'- azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo] formamide, etc. are mentioned.

In the present invention, the use ratio of the [D] thermosensitive radical generator is preferably 10 parts by weight or less, and more preferably 1 to 5 parts by weight based on 100 parts by weight of the component [A].

By containing [D] component in such a ratio, the chemical-resistance, heat resistance, and surface hardness of the interlayer insulation film or microlens obtained from the radiation sensitive resin composition of this 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 [E] surfactant which can be used here, a fluorine-type surfactant, a silicone type surfactant, and a nonionic surfactant can be used preferably, for example.

Specific examples of the fluorine-based surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether and octa Ethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1 , 2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2, Sodium fluoroalkylbenzenesulfonate, in addition to 2,3,3,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane and the like; Fluoroalkyloxyethylene ethers; Fluoroalkylammonium iodide, fluoroalkylpolyoxyethylene ether, perfluoroalkylpolyoxyethanol; Perfluoroalkylalkoxylates; Fluorine-type alkyl ester etc. are mentioned.

As these commercial items, BM-1000, BM-1100 (above, BM Chemie Co., Ltd.), Megapack F142D, East F172, East F173, East F183, East F178, East F191, East F471 (above, Dai Nippon Ink Chemical Industries, Ltd. ( Co., Ltd.), fluoride FC-170C, FC-171, FC-430, FC-431 (above, Sumitomo 3M Co., Ltd.), Suplon S-112, copper S-113, copper S-131, East S-141, East S-145, East S-382, East SC-101, East SC-102, East SC-103, East SC-104, East SC-105, East SC-106 (Asahi Glass Co., Ltd.) Manufacture), F-top EF301, copper 303, copper 352 (made by Shin-Akita Kasei Co., Ltd.), etc. are mentioned.

As said silicone type surfactant, For example, DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032 (above, Toray Dow Corning Silicone ( (Manufactured by Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above, manufactured by GE Toshiba Silicone Co., Ltd.). .

As said nonionic surfactant, For example, polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; (Meth) acrylic acid copolymer polyflow No. 57, 95 (made by Kyoesha Chemical Co., Ltd.), etc. can be used.

These surfactant can be used individually or in combination of 2 or more types.

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]. When the usage-amount of [E] surfactant exceeds 5 weight part, when forming a coating film on a board | substrate, the film roughness of a coating film may arise easily.

In the radiation sensitive resin composition of this invention, in order to improve adhesiveness with a base | substrate, [F] adhesion | attachment adjuvant can be used further.

As such [F] adhesion | attachment adjuvant, a functional silane coupling agent is used preferably, For example, the silane coupling agent which has reactive substituents, such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, is mentioned. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxy Silane, (beta)-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. are mentioned. Such [F] adhesion aid is preferably used in an amount of 20 parts by weight or less, and more preferably 10 parts by weight or less, based on 100 parts by weight of the component [A]. When the amount of the adhesive aid exceeds 20 parts by weight, development residues are likely to occur in the developing step.

Radiation-sensitive resin composition

The radiation sensitive resin composition of this invention is manufactured by mixing uniformly the above-mentioned [A] component, [B] component, and the other component added arbitrarily as mentioned above. The radiation-sensitive resin composition of the present invention is preferably dissolved in a suitable solvent and used in a solution state. For example, the radiation sensitive resin composition of a solution state can be manufactured by mixing [A] component, [B] component, and the other component added arbitrarily at a predetermined ratio.

As a solvent used for manufacture of the radiation sensitive resin composition of this invention, what melt | dissolves each component of the [A] component, [B] component, and the other components arbitrarily mix | blended uniformly, and does not react with each component is used. .

As such a solvent, the same thing as what was illustrated above can be mentioned as a solvent for synthesize | combining polysiloxane [A] used preferably as a component [A].

Among these solvents, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, esters, and diethylene glycol are preferably used in view of solubility of each component, reactivity with each component, ease of coating film formation, and the like. Among them, 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, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate and ethyl 2-ethoxypropionate can be used especially preferably.

Moreover, in order to improve the in-plane uniformity of a film thickness with the said solvent, you may use a high boiling point solvent together. As a high boiling point solvent which can be used together, it is N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpi, for example. Ralidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, male Diethyl acid, gamma -butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like. Among these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.

When using a high boiling point solvent together as a solvent of the radiation sensitive resin composition of this invention, the usage-amount is preferably 50 weight% or less with respect to solvent whole quantity, More preferably, it is 40 weight% or less, More preferably, it is 30 weight It can be made% or less. When the usage-amount of a high boiling point solvent exceeds this usage-amount, the film thickness uniformity, a sensitivity, and a residual film ratio of a coating film may fall.

When manufacturing the radiation sensitive resin composition of this invention as a solution state, ratio (solid content concentration) of components other than the solvent which occupies in a solution (namely, the total amount of [A] component, [B] component, and the other components added arbitrarily) ) Can be arbitrarily set depending on the purpose of use, the value of the desired film thickness, and the like, but is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, still more preferably 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.

Interlayer insulating film, microlens formation

Next, the method of forming the interlayer insulation film or microlens of this invention using the radiation sensitive resin composition of this invention is stated. The method for forming an interlayer insulating film or microlens of the present invention includes the following steps in the order described below.

(1) process of forming the film of the radiation sensitive resin composition of this invention on a board | substrate,

(2) irradiating at least a part of said film with radiation,

(3) developing the film after irradiation; and

(4) The process of heating the film after image development.

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

(1) Process of forming film of radiation sensitive resin composition of this invention on board | substrate

In process (1), the composition solution of this invention is apply | coated to the surface of a board | substrate, Preferably a solvent is removed by prebaking, and the film of a radiation sensitive resin composition is formed.

As a kind of board | substrate which can be used, a glass substrate, a silicon substrate, and the board | substrate with which various metal was formed in these surfaces are mentioned, for example.

It does not specifically limit as a coating method of a composition solution, For example, the appropriate method, such as spraying method, the roll coating method, the spin coating method (spin coating method), the slit die coating method, the bar coating method, the inkjet method, can be employ | adopted, In particular, spin coating or slit die coating is preferable. The conditions for prebaking also vary depending on the type of each component, the use ratio, and the like. For example, it can be made into about 30 to 15 minutes at 60-110 degreeC.

As a film thickness of the film formed, it is a value after prebaking, for example, when forming an interlayer insulation film, for example, 3-6 micrometers, and forming a microlens, for example, 0.5-3 micrometers is preferable.

(2) irradiating radiation to at least a portion of the film

In step (2), radiation is irradiated to at least a portion of the film formed as described above. In order to irradiate a part of film with radiation, it can be based on the method of irradiating radiation through the mask which has a predetermined pattern, for example.

Then, patterning is performed by developing using a developing solution to remove the irradiated portion of the radiation. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like.

As said ultraviolet-ray, the radiation containing g line | wire (wavelength 436 nm), i line | wire (wavelength 365 nm), etc. are mentioned, for example. As far ultraviolet rays, KrF excimer laser etc. are mentioned, for example. As X-ray, a synchrotron radiation etc. are mentioned, for example. As a charged particle beam, an electron beam etc. are mentioned, for example.

Among these, ultraviolet rays are preferable, and among these, radiation including g-rays and / or i-rays is particularly preferable.

As an irradiation amount (exposure amount) of radiation, it is preferable to set it as 50-1,500 J / m <2> when forming an interlayer insulation film, and 50-2,000 J / m <2> when forming a microlens.

(3) Process of developing film after irradiation

As a developing solution used for the developing process of process (3), 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-diazabicyclo An aqueous solution of an alkali (basic compound) such as [5.4.0] -7-undecene and 1,5-diazabicyclo [4.3.0] -5-nonane can be used. Moreover, the aqueous solution which added water-soluble organic solvents, such as methanol and ethanol, and surfactant in an appropriate quantity to the aqueous solution of said alkali, or the various organic solvent which melt | dissolves the composition of this invention can be used as a developing solution.

As the developing method, for example, a suitable method such as a puddle method, a dipping method, a rocking dipping method or a shower method can be used. Although the developing time at this time changes with composition of a composition, it can be set as 30 to 120 second, for example.

Moreover, since the peeling will generate | occur | produce in the formed pattern, when the developing time exceeds about 20-25 second from the optimal value in the conventionally known radiation sensitive resin composition, it was necessary to strictly control developing time, but in the case of the radiation sensitive resin composition of this invention Even if the excess time from the optimum development time is 30 seconds or more, good pattern formation is possible and there is an advantage in product yield.

(4) The process of heating the film after image development

After the developing step of step (3) carried out as described above, the patterned thin film is preferably rinsed by, for example, running water washing, and preferably irradiated to the entire surface with radiation by a high pressure mercury lamp or the like. After the post-exposure, the 1,2-quinonediazide compound remaining in the thin film is subjected to decomposition treatment, and then the thin film is subjected to heat treatment (post-baking treatment) with a heating apparatus such as a hot plate or an oven. Hardening treatment is performed. The exposure amount in the post-exposure step is preferably 2,000 to 5,000 J / m 2. In addition, the baking temperature in this hardening process is 120 degreeC or more and less than 250 degreeC, for example. Although heating time changes with kinds of a heating apparatus, it can be set as 5 to 30 minutes, for example, when carrying out heat processing on a hotplate, and 30 to 90 minutes when performing heat processing in an oven. At this time, the step baking method etc. which perform two or more heating processes can also be used. In addition, when forming the film | membrane of the photosensitive material containing polysiloxane conventionally known as a high heat-resistant material on a board | substrate, high temperature processing of 250 degreeC or more is required, but in the case of the radiation sensitive resin composition of this invention, Since it can be less than 250 degreeC, 240 degrees C or less, and 230 degrees C or less, there exists an advantage which can be preferably applied also to the process of forming a display element.

In the same manner, a patterned thin film corresponding to the target interlayer insulating film or microlens can be formed on the surface of the substrate.

Interlayer insulation 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, high transmittance, and low dielectric constant, as is apparent from the following examples. It can be used preferably as an interlayer insulation film.

Microlens

The microlens of the present invention formed as described above has good adhesion to the substrate, excellent solvent resistance and heat resistance, and has high transmittance and good melt shape, as is apparent from the following examples. It can be used suitably as a micro lens of an element.

The microlens of the present invention has a semiconvex lens shape, as shown in Fig. 1A, and exhibits good light condensing characteristics.

<Example>

Although a synthesis example and an Example are shown to the following and this invention is demonstrated to it further more concretely, this invention is not limited to a following example.

Synthesis Example of Component [A]

Synthesis Example 1 [A-1]

A solution obtained by adding 19.3 g of vinyltrimethoxysilane, 53.1 g of methyltrimethoxysilane, and 154.7 g of phenyltrimethoxysilane to a 500 mL three-necked flask, adding 113.5 g of diethylene glycol methylethyl ether to this, and dissolving it. The temperature was raised to 60 ° C. over 30 minutes while stirring with a magnetic stirrer. After 70.3 g of ion-exchange water containing 5.9 g of oxalic acid was continuously added over 30 minutes to this, reaction was performed at 60 degreeC for 3 hours. Methanol and water were distilled off from the reaction liquid under reduced pressure, and the solution containing polysiloxane [A-1] was obtained by adding diethylene glycol methyl ethyl ether so that solid content concentration might be 35weight%. The polystyrene reduced weight average molecular weight Mw of polysiloxane [A-1] was 2,600.

Synthesis Example 2 [A-2]

71.1 g of vinyltrimethoxysilane and 142.8 g of phenyltrimethoxysilane were added to a 500 mL three-necked flask, and 107.0 g of diethylene glycol methylethyl ether was added thereto and dissolved, and the resulting solution was stirred with a magnetic stirrer. It heated up at 60 degreeC over minutes. After 64.9 g of ion-exchanged water containing 5.4 g of oxalic acid was continuously added over 30 minutes to this, reaction was performed at 60 degreeC for 3 hours. Methanol and water were distilled off from the reaction liquid under reduced pressure, and the solution containing polysiloxane [A-2] was obtained by adding diethylene glycol methyl ethyl ether so that solid content concentration might be 35weight%. The polystyrene reduced weight average molecular weight Mw of polysiloxane [A-2] was 2,200.

Synthesis Example 3 [A-3]

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

Synthesis Example 4 [A-4]

A solution obtained by adding 16.2 g of allyltrimethoxysilane, 40.9 g of methyltrimethoxysilane, and 119.0 g of phenyltrimethoxysilane to a 500 mL three-necked flask, adding 88.0 g of diethylene glycol methylethyl ether to this and dissolving it. The temperature was raised to 60 ° C. while stirring with a magnetic stirrer. To this, 54.1 g of ion-exchanged water in which 4.5 g of oxalic acid was dissolved was continuously added over 1 hour. After the reaction was conducted at 60 ° C. for 3 hours, the reaction solution was cooled to 40 ° C., after which alcohol and water were distilled off under reduced pressure, diethylene glycol methyl ethyl ether was added so that the solid content concentration was 35% by weight. By adding, the solution containing polysiloxane [A-4] was obtained. The polystyrene reduced weight average molecular weight Mw of polysiloxane [A-4] was 2,400.

Synthesis Example 5 [A-5]

32.0 g of 3-methacryloxypropyltrimethoxysilane, 53.1 g of methyltrimethoxysilane and 154.7 g of phenyltrimethoxysilane were added to a 500 mL three-necked flask, and 119.9 g of diethylene glycol methylethyl ether was added thereto. It melt | dissolved and heated up at 60 degreeC, stirring the obtained solution with the magnetic stirrer. To this, 59.5 g of ion-exchanged water in which 5.0 g of oxalic acid was dissolved were continuously added over 1 hour. And after performing reaction 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 methanol, a byproduct, was distilled off. To this, 39.6 g of ion-exchanged water and 39.6 g of diethylene glycol methylethyl ether were continuously added over 30 minutes, followed by stirring at 40 ° C. for 2 hours, after which the alcohol and water were distilled off under reduced pressure. The solution containing polysiloxane [A-5] was obtained by adding diethylene glycol methyl ethyl ether so that solid content concentration might be 35weight%. The polystyrene reduced weight average molecular weight Mw of polysiloxane [A-5] was 2,700.

Comparative Synthesis Example 1 [a-1]

49.0 g of methyltrimethoxysilane and 166.6 g of phenyltrimethoxysilane were added to a 500 mL three-necked flask, and 107.8 g of diethylene glycol methylethyl ether was added thereto to dissolve, and the resulting solution was stirred while stirring with a magnetic stirrer. It heated up at ° 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. After the reaction was conducted at 60 ° C. for 3 hours, the reaction solution was cooled to 40 ° C., after which alcohol and water were distilled off under reduced pressure, diethylene glycol methyl ethyl ether was added so that the solid content concentration was 35% by weight. By adding, the solution containing polysiloxane [a-1] was obtained. The polystyrene reduced weight average molecular weight Mw of polysiloxane [a-1] was 2,800.

Comparative Synthesis Example 2 [a-2]

8 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethylmethyl ether were added to a flask equipped with a cooling tube and a stirrer. 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 ] decane-8-ylmethacrylate were added and nitrogen-substituted. Stirring slowly began. The polymer solution containing copolymer [a-2] was obtained by raising the temperature of a solution to 70 degreeC and holding this temperature for 5 hours.

The polystyrene reduced weight average molecular weight Mw of the copolymer [a-2] was 7,500 and molecular weight distribution (Mw / Mn) was 2.5. In addition, the solid content concentration of the polymer solution obtained here was 31.6 weight%.

<Production of radiation sensitive resin composition>

Example 1

The solution containing polysiloxane [A-1] synthesized in Synthesis Example 1 above corresponds to 100 parts by weight (solid content) of polysiloxane [A-1], and 4,4 '-[1- [as component [B]. Condensate of 4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) with 1,2-naphthoquinone diazide-5-sulfonic acid chloride (2.0 mol) (B-1) 10 weight part is mixed, and it melt | dissolves uniformly by adding diethylene glycol ethyl methyl ether so that solid content concentration may be 33 weight%, and filter by the membrane filter of diameter 0.2micrometer, and the solution of a radiation sensitive resin composition ( S-1) was prepared.

Examples 2-11, Comparative Examples 1-2

In Example 1, it carried out similarly to Example 1 except having used the kind and quantity as Table 1 below as a component [A] and a component [B], and the solution of a radiation sensitive resin composition (S -2) to (S-11) and (s-1) to (s-2) were prepared.

In addition, in Example 3, 4, 8, 10, 11, the component [C] was added. In Examples 2-11, the [D] component was further added.

Example 12

Example 10 WHEREIN: It melt | dissolved in diethylene glycol ethyl methyl ether / propylene glycol monomethyl ether acetate = 6/4 (weight ratio) so that solid content concentration might be 20 weight%, Surfactant SH-28PA ( The solution (S-12) of the radiation sensitive resin composition was produced like Example 10 except having added Toray Dow Corning Silicone Co., Ltd. product.

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

[B-1]: 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphtho Condensate of quinonediazide-5-sulfonic acid chloride (3.0 moles)

[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 an interlayer insulation film>

Examples 13-24, Comparative Examples 3-4

The various characteristics as an interlayer insulation film were evaluated as follows using the radiation sensitive resin composition manufactured as mentioned above.

[Evaluation of sensitivity]

On the silicon substrates, for Examples 13 to 23 and Comparative Examples 3 to 4, respectively, the composition shown in Table 2 below was applied by using a spinner, and then prebaked on a hot plate at 100 ° C. for 2 minutes to achieve a film thickness of 4.0 μm. A coating film was formed. In Example 24, coating was performed with a slit die coater to reduce pressure to 0.5 Torr over 15 seconds at room temperature, remove the solvent, and then prebak on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of 4.0 μm. It was.

After exposing by varying an exposure time using the Canon-made PLA-501F exposure machine (ultra high pressure mercury lamp) through the mask which has a pattern of a line and space (10 to 1) of 3.0 micrometers, respectively, in the obtained coating film, The development by the puddle method was performed for 25 degreeC and 80 second in 2.38 weight% of tetramethylammonium hydroxide aqueous solution. Subsequently, flowing water 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 required for the space line width to be 0.3 µm was investigated. This minimum exposure amount is shown in Table 2 as the sensitivity.

[Evaluation of development margin]

On the silicon substrates, for Examples 13 to 23 and Comparative Examples 3 to 4, respectively, the composition shown in Table 2 was applied 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 4.0 μm. Formed. In Example 24, coating was performed with a slit die coater to reduce pressure to 0.5 Torr over 15 seconds at room temperature, remove the solvent, and then prebak on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of 4.0 μm. It was.

The obtained coating film was irradiated with the above-mentioned "evaluation of sensitivity" using Canon's PLA-501F exposure machine (ultra high pressure mercury lamp) through the mask which has a pattern of a line and space (10: 1) of 3.0 micrometers, respectively. After exposing at the exposure amount corresponding to the sensitivity value, it developed by the puddle method at 25 degreeC and developing time by 2.38 weight% of tetramethylammonium hydroxide aqueous solution as a variable. Subsequently, washing with water for 1 minute with ultrapure water was followed by drying to form a pattern on the silicon substrate. At this time, the developing time required for the line width to be 3 占 퐉 is shown in Table 2 as the optimum developing time. In addition, the time until the line pattern of 3.0 micrometers was peeled off when developing continued further from the optimal developing time was shown, and it shows in Table 2 as a developing margin.

[Evaluation of solvent resistance]

For Examples 13 to 23 and Comparative Examples 3 to 4 on the silicon substrate, the coating compositions were formed by using a spinner, respectively, and then prebaked on a hot plate at 100 ° C. for 2 minutes. In Example 24, the coating film was formed by applying a slit die coater, depressurizing to 0.5 Torr over 15 seconds at room temperature, removing the solvent, and prebaking on a hot plate at 100 ° C for 2 minutes.

After exposing so that the accumulated irradiation amount might be 3,000 J / m <2> using the Canon-made PLA-501F exposure machine (super high pressure mercury lamp), respectively, the obtained coating film was heated at 220 degreeC for 1 hour in a clean oven, 3.0 micrometers of cured films were obtained. The film thickness (T1) of the obtained cured film was measured. After the silicon substrate on which the cured film was formed was immersed in dimethyl sulfoxide for 20 minutes at a temperature controlled at 70 ° C., the film thickness t1 after the immersion of the cured film was measured, and the film thickness change rate due to immersion {| t1-T1 / T1} × 100 [%] was calculated. The results are shown in Table 2.

In addition, since patterning is unnecessary in evaluation of solvent resistance, the image development process was abbreviate | omitted and it evaluated by performing only a coating film formation process, a radiation irradiation process, and a heating process.

[Evaluation of heat resistance]

The film thickness (T2) of the cured film obtained by forming a cured film on a silicon substrate similarly to said "evaluation of solvent resistance" was measured. Subsequently, after further baking the board | substrate which has this cured film at 240 degreeC in a clean oven for 1 hour, the film thickness (t2) after further baking of the said cured film was measured, and the film thickness change rate by further baking {| t2-T2 | / T2} x100 [%] was calculated. The results are shown in Table 2.

[Evaluation of transparency]

In the said "evaluation of solvent resistance", the cured film was formed on the glass substrate similarly except having used the glass substrate "Corning 7059" (made by Corning Corporation) instead of the silicon substrate. The light transmittance of the glass substrate which has this cured film was measured with the wavelength of the range of 400-800 nm using the spectrophotometer "150-20 type double beam" (made by Hitachi Seisakusho Co., Ltd.). The value of the minimum light transmittance at that time is shown in Table 2.

[Evaluation of relative dielectric constant]

For Examples 13 to 23 and Comparative Examples 3 to 4 on the polished SUS304 manufactured substrate, the composition shown in Table 2 was applied using a spinner, respectively, and then prebaked at 100 ° C. for 2 minutes on a hot plate to obtain a thickness of 3.0 μm. The coating film of was formed. In Example 24, coating was performed with a slit die coater to reduce the pressure to 0.5 Torr over 15 seconds at room temperature, remove the solvent, and then prebak on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. .

After exposing to the obtained coating film using the Canon Co., Ltd. product PLA-501F exposure machine (ultra high pressure mercury lamp) so that accumulated irradiation amount might be 3,000 J / m <2>, it heated in 220 degreeC for 1 hour in a clean oven, The cured film was formed in. The Pt / Pd electrode pattern was formed on this cured film by the vapor deposition method, and the sample for dielectric constant measurement was produced. About the obtained sample, the dielectric constant in the frequency of 10 kHz was measured by CV method using the Yokogawa Hewlett-Packard Co., Ltd. product HP16451B electrode and HP4284A flashzone LCR meter. The results are shown in Table 2.

In addition, in the evaluation of the dielectric constant, since patterning is unnecessary, the developing step was omitted, and only the coating film forming step, the irradiation step, and the heating step were evaluated.

[Evaluation of Surface Hardness]

In the same manner as in the above "evaluation of solvent resistance", a cured film was formed on a silicon substrate, and the pencil hardness was measured by the 8.4.1 pencil scraping test of JISK-5400-1990 about the obtained cured film. The results are shown in Table 2. When the pencil hardness is H or harder than that, it can be said that the surface hardness is good.

[Evaluation of Voltage Retention Rate]

A radiation sensitive resin composition prepared above using a spinner on a soda glass substrate on which a SiO ₂ film is formed on the surface to prevent elution of sodium ions, and an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape. Was applied and prebaked for 2 minutes on a 100 degreeC hotplate, and the coating film of 2.0 micrometers in thickness was formed. The development by the immersion method was performed for 25 degreeC and 80 second in 2.38 weight% of tetramethylammonium hydroxide aqueous solution. Subsequently, a high pressure mercury lamp was used to expose the coating film with a radiation amount of 3,000 J / m 2 at a wavelength of 365 nm, 405 nm and 436 nm, without passing through a photomask. Furthermore, postbaking was performed at 220 degreeC for 1 hour, and the cured film was formed.

Subsequently, after dispersing a 5.5 μm diameter bead spacer on the substrate having the cured film, the soda glass substrates as long as the ITO electrodes were deposited in a predetermined shape on the surface thereof were opposed to each other, leaving four liquid crystal inlets and leaving 0.8 mm of glass beads. The liquid crystal cell was manufactured by bonding using the sealing compound which mixed this, and inject | pouring liquid crystal MLC6608 (brand name) by a Merck company, and sealing a liquid crystal injection port.

The liquid crystal cell was placed in a constant temperature layer at 60 ° C., and the applied voltage was a square wave of 5.5 V, the measurement frequency was 60 Hz, and the voltage of the liquid crystal cell was measured by a Toyo Technica liquid crystal voltage retention measuring system VHR-1A (brand name). When the retention rate was measured, the voltage retention was 97%. The results are shown in Table 1.

In addition, a voltage retention is a value calculated | required by following formula (1) here.

Voltage retention (%) = (liquid crystal cell potential difference after 16.7 milliseconds) / (voltage applied at 0 milliseconds) × 100

The lower the value of the voltage retention of the liquid crystal cell, the higher the possibility of causing a problem called "baking" at the time of liquid crystal panel formation. It can be said that the higher the value of the voltage retention, the higher the reliability of the liquid crystal panel.

<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 microlenses were evaluated as follows. In addition, evaluation of solvent resistance, evaluation of heat resistance, and evaluation of transparency refer to the result in performance evaluation as the said interlayer insulation film.

[Evaluation of sensitivity]

Each of the compositions shown in Table 3 below was applied onto the silicon substrate using a spinner, followed by prebaking at 100 ° C. for 2 minutes on a hot plate to form a coating film having a thickness of 2.0 μm. 2.38% by weight of tetra, after exposure by varying the exposure time using a Nikon Corporation NSR1755i7A reduced projection exposure machine (NA = 0.50, λ = 365 nm) through a pattern mask having a predetermined pattern in the obtained coating film. The solution was developed in a methyl ammonium hydroxide aqueous solution at 25 ° C. for 1 minute using a puddle method. The pattern was then formed on the silicon substrate by rinsing with ultrapure water and drying. The minimum exposure amount required for the space line width of the 0.8 μm line and space pattern (1 to 1) to 0.8 μm was investigated. This minimum exposure amount is shown in Table 3 as the sensitivity.

[Evaluation of development margin]

After coating the composition of Table 3 using a spinner on the silicon substrate, respectively, it prebaked at 100 degreeC for 2 minutes on the hotplate, and the coating film of 2.0 micrometers in thickness was formed. It corresponds to the value of the sensitivity irradiated by said "evaluation of sensitivity" using the Nikon Corporation NSR1755i7A reduced projection exposure machine (NA = 0.50, (lambda == 365 nm) through the pattern mask which has a predetermined | prescribed pattern to the obtained coating film. After exposing at the exposure amount to which it is made, it developed by the puddle method at 25 degreeC for 1 minute in the tetramethylammonium hydroxide aqueous solution of the density | concentration shown in Table 3. Rinse with water and dry to form a pattern on the silicon substrate. The developing time required for the space line width of the 0.8 μm line and space pattern (1 to 1) to 0.8 μm is shown in Table 3 as the optimum developing time. Moreover, the time (development margin) until peeling of the pattern of 0.8 micrometers in width | variety was further measured from the optimal development time, and it shows in Table 3 as a development margin.

[Formation of Micro Lens]

After coating the composition of Table 3 using a spinner on the silicon substrate, respectively, it prebaked at 100 degreeC for 2 minutes on the hotplate, and the coating film of 2.0 micrometers in thickness was formed. Sensitivity investigated by said "[evaluation of sensitivity]" using the Nikon Corporation NSR1755i7A reduced projection exposure machine (NA = 0.50, (lambda == 365 nm) through the pattern mask which has a 4.0 micrometer dot 2.0 micrometer space pattern to the obtained coating film. After exposing at the exposure amount corresponding to the value of, it developed by the puddle method at 25 degreeC for 1 minute in 2.38 weight% of tetramethylammonium hydroxide aqueous solution. The pattern was then formed on the silicon substrate by rinsing with ultrapure water and drying. Then, exposure was further performed so that accumulated irradiation amount might be 3,000 J / m <2> using Canon PLA-501F exposure machine (super high pressure mercury lamp). Thereafter, the plate was heated at 160 ° C. for 10 minutes and further heated at 230 ° C. for 10 minutes, and the pattern was meltflowed to form a microlens.

Table 3 shows the dimensions (diameter) and the cross-sectional shape of the bottom (surface in contact with the substrate) of the formed microlenses. The dimension of the microlens bottom portion is said to be good when it exceeds 4.0 micrometers and is less than 5.0 micrometers. When this dimension becomes 5.0 micrometers or more, it is unpreferable in the state which the adjacent lenses contact. Moreover, in the schematic diagram shown in FIG. 1, a cross-sectional shape is favorable when it is a semi-convex lens shape like (a), and it is bad when it is a substantially trapezoid shape like (b).

1 is a schematic diagram of a cross-sectional shape of a microlens.

Claims (6)

[A] a polysiloxane which is a hydrolytic condensate of (a1) a silane compound represented by the following formula (1) and a silane compound represented by the following formula (2), [B] 1,2-quinonediazide compound A radiation-sensitive resin composition comprising a. <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, 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 group having 6 to 12 carbon atoms, and a and b each represent 1 An integer of 3 to 3, c represents an integer of 0 to 2, and a + b + c = 4) <Formula 2>

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, and R ⁶ represents 1 to C A substituted or unsubstituted alkyl group of 6 or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, g represents an integer of 1 to 4, h represents an integer of 0 to 3, and g + h = 4) The compound according to claim 1, wherein the compound having 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 (except for the component [A]). The radiation sensitive resin composition which contains further. The radiation sensitive resin composition of Claim 1 which further contains [D] a thermosensitive radical generator. The radiation sensitive resin composition according to claim 1, which is for forming an interlayer insulating film or for forming a microlens. A method of forming an interlayer insulating film or microlens comprising the following steps in the order described below. (1) forming a film of the radiation-sensitive resin composition according to claim 4 on a substrate; (2) irradiating at least a part of said film with radiation, (3) developing the film after irradiation; and (4) The process of heating the film after image development. An interlayer insulating film or microlens formed by the method of claim 5.

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