JP2009075326A - Radiation-sensitive resin composition, interlayer insulation film and microlens, and method for producing those - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition capable of forming an interlayer dielectric excellent in adhesion and various resistances under a baking condition of ≤200°C when used to form the interlayer dielectric, and capable of forming microlenses having a good melt shape when used to form microlenses. <P>SOLUTION: The radiation-sensitive resin composition comprises (A) a polysiloxane having at least one group selected from the group consisting of an oxiranyl group and an oxetanyl group, and a functional group capable of addition reaction to an oxiranyl group or an oxetanyl group, (B) a 1,2-quinonediazide compound, and (C) a specific onium-fluorinated alkylfluorophosphate. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

In an electronic component such as a thin film transistor (hereinafter referred to as “TFT”) type liquid crystal display element, magnetic head element, integrated circuit element, solid-state imaging element, etc., an interlayer insulation is generally used to insulate between wirings arranged in layers. A membrane is provided. As a material for forming an interlayer insulating film, a material having a small number of steps for obtaining a required pattern shape and having sufficient flatness is preferable, and therefore, a radiation-sensitive resin composition is widely used (patent) Reference 1 and Patent Document 2).
Among the electronic components, for example, a TFT type liquid crystal display element is manufactured through a process of forming a transparent electrode film on the interlayer insulating film and further forming a liquid crystal alignment film on the interlayer insulating film. Since the film is exposed to high temperature conditions in the transparent electrode film forming step or exposed to a resist stripping solution used for electrode pattern formation, sufficient resistance to these is required.
In recent years, TFT-type liquid crystal display devices have been trended toward larger screens, higher brightness, higher definition, faster response, thinner thickness, etc., and the composition for forming an interlayer insulating film used therefor has high sensitivity. In addition, the interlayer insulating film to be formed is required to have higher performance than ever in terms of low dielectric constant and high transmittance.
It is also known to use a siloxane polymer as an interlayer insulating film as a material having high heat resistance, high transparency, and low dielectric constant (see Patent Document 3 and Patent Document 4). There is a problem that high-temperature baking at 300 ° C. or higher is necessary, and it cannot be applied to the process of producing display elements.

On the other hand, a microlens having a lens diameter of about 3 to 100 μm or an optical system material for an on-chip color filter such as a facsimile, an electronic copying machine, a solid-state image sensor, or the like is defined as an optical system material. An array of microlenses is used.
To form a microlens or microlens array, a resist pattern corresponding to the lens is formed and then melt-flowed by heat treatment and used as it is as a lens, or by using the melt-flowed lens pattern as a mask and drying. A method of transferring a lens shape to a base by etching is known. For the formation of the lens pattern, a radiation-sensitive resin composition is widely used (see Patent Document 5 and Patent Document 6).
By the way, the element in which the microlens or the microlens array as described above is formed is then applied with a planarizing film and an etching resist film in order to remove various insulating films on the bonding pad which is a wiring forming portion. Exposure and development are performed using a desired mask to remove the etching resist in the bonding pad portion, and then the step is performed to remove the planarizing film and various insulating films by etching to expose the bonding pad portion. Therefore, the microlens or the microlens array requires solvent resistance and heat resistance in the flattening film and etching resist coating film forming process and the etching process.
The radiation-sensitive resin composition used to form such a microlens has high sensitivity, and the microlens formed therefrom has a desired radius of curvature, and has high heat resistance and high transmittance. It is required to be a rate.

By the way, the final pattern is formed on the interlayer insulating film and the microlens through a heat baking process (hereinafter referred to as “post-bake”) for 60 minutes or more, usually at a temperature of 200 ° C. or higher performed after development. However, in recent years, from the viewpoint of reducing manufacturing costs and dealing with substrates with limited heat resistance, such as plastic substrates, lowering or shortening of the thermal baking process has been studied. There is a strong demand for a radiation-sensitive resin composition that has the same performance as that of the conventional process.

JP 2001-354822 A JP 2001-343743 A JP 2006-178436 A JP 2007-276598 A JP-A-6-18702 JP-A-6-136239

The present invention has been made based on the above situation. Therefore, an object of the present invention is to provide an interlayer insulation having high radiation sensitivity and excellent adhesion and various resistance even at a post-bake temperature of 200 ° C. or lower when used for forming an interlayer insulating film. The object is to provide a radiation-sensitive resin composition capable of easily forming a film.
Another object of the present invention is to form a microlens having a high radiation sensitivity and having a good lens shape even at a post-baking temperature of 200 ° C. or lower when used for forming a microlens. It is providing the radiation sensitive resin composition.

According to the present invention, the above objects and advantages of the present invention are as follows.
[A] a polysiloxane having at least one group selected from the group consisting of an oxiranyl group and an oxetanyl group and a functional group capable of undergoing an addition reaction with the oxiranyl group or the oxetanyl group,
[B] containing at least one compound selected from the group consisting of 1,2-quinonediazide compounds, and [C] a compound represented by general formula (1) and a compound represented by general formula (4) It is achieved by the radiation sensitive resin composition characterized by the above.

[In the formula (1), A represents an element having a valence m of VIA group to VIIA group (CAS notation), and m is 1 or 2. n represents the number of repeating units of the structure in parentheses and is an integer of 0 to 3. R is an organic group bonded to A, and is an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or Represents an alkynyl group having 2 to 30 carbon atoms, and R represents alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy , Alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups, and at least one selected from the group consisting of halogen may be substituted. The number of R is m + n (m−1) +1, and each R may be the same as or different from each other. In addition, two or more R's are each directly or —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR′—, —CO—, —COO—, —CONH—, carbon number A ring structure containing element A may be formed by bonding via 1 to 3 alkylene groups or phenylene groups. Here, R ′ is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.
D is a structure represented by the following general formula (2),

式（２）中、Ｅは炭素数１〜８のアルキレン基、炭素数６〜２０のアリーレン基または炭素数８〜２０の複素環化合物の２価の基を表し、更にＥは炭素数１〜８のアルキル、炭素数１〜８のアルコキシ、炭素数６〜１０のアリール、ヒドロキシ、シアノ、ニトロの各基およびハロゲンからなる群より選ばれる少なくとも１種で置換されていてもよい。Ｇは−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＮＨ−、−ＮＲ’−、−ＣＯ−、−ＣＯＯ−、−ＣＯＮＨ−、炭素数１〜３のアルキレン基またはフェニレン基を表す。ａは０〜５の整数である。ａ＋１個のＥおよびａ個のＧはそれぞれ同一であっても異なっていてもよい。ここでＲ’は前記のものと同じ。
Ｘ⁻はオニウムの対イオンである。その個数は１分子当りｎ＋１であり、そのうち少なくとも1個は一般式（３）で表されるフッ素化アルキルフルオロリン酸アニオンであって、

In the formula (2), E represents a divalent group of an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a heterocyclic compound having 8 to 20 carbon atoms, and E represents 1 to 1 carbon atoms. It may be substituted with at least one selected from the group consisting of 8 alkyls, C 1-8 alkoxys, C 6-10 aryls, hydroxy, cyano, nitro groups and halogens. G represents —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR′—, —CO—, —COO—, —CONH—, an alkylene group having 1 to 3 carbon atoms, or phenylene. Represents a group. a is an integer of 0-5. a + 1 E and a G may be the same or different. Here, R ′ is the same as described above.
X ⁻ is a counter ion of onium. The number thereof is n + 1 per molecule, at least one of which is a fluorinated alkyl fluorophosphate anion represented by the general formula (3),

The rest may be other anions. In the general formula (3), Rf represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms. b shows the number and is an integer of 1-5. The b Rf's may be the same or different. ]

[In Formula (4), M is one type of transition metal element selected from Group VIB to Group VIII (CAS notation), and L1 and L2 are ligands of transition metal element M. L1 is an aromatic compound having 6 to 24 carbon atoms or a heterocyclic compound having 4 to 20 carbon atoms, L2 is an indene, fluorene or cyclopentagen anion, and these L1 and L2 are further alkyl, alkoxy, alkylthio, arylthio , Alkylcarbonyl, alkoxycarbonyl, phenyl, benzoyl, cyano, nitro, and at least one selected from the group consisting of halogen. c and d represent the numbers of L1 and L2, respectively, both are integers of 0 to 2, and the total number (c + d) is 2. When both of the two ligands are L1 or both, they may be the same as or different from each other. The total charge e of the charges of the ligands L1 and L2 and the charge of the transition metal element M is positive and is 1 or 2. X ^- X in formula (1) ^- which is synonymous. ]

The above objects and advantages of the present invention are secondly,
This is achieved by a method for forming an interlayer insulating film or microlens comprising the following steps in the order described below.
(1) The process of forming the coating film of said radiation sensitive resin composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) Development step, and (4) Heating step.
Further, the above object and advantage of the present invention are as follows.
This is achieved by the interlayer insulating film or microlens formed by the above method.

  The radiation-sensitive resin composition of the present invention has high radiation sensitivity and can easily form an interlayer insulating film excellent in adhesion and various resistances even at a post-bake temperature of 200 ° C. or lower. Also, a microlens having a good lens shape can be easily formed even at a post-bake temperature of 200 ° C. or lower.

Hereinafter, the radiation sensitive resin composition of this invention is explained in full detail.
[A] component The [A] component used in the present invention comprises at least one group selected from the group consisting of an oxiranyl group and an oxetanyl group, and a functional group capable of undergoing an addition reaction with the oxiranyl group or the oxetanyl group. Polysiloxane having
Examples of the functional group capable of undergoing addition reaction with the oxiranyl group or oxetanyl group include a hydroxyl group, a mercapto group, and an amino group.
As the component [A] used in the present invention,
(A1) a silane compound having at least one group selected from the group consisting of an oxiranyl group and an oxetanyl group and a hydrolyzable group (hereinafter also referred to as “compound (a1)”);
(A2) a silane compound having a functional group capable of addition reaction to oxiranyl group or oxetanyl group and a hydrolyzable group (hereinafter also referred to as “compound (a2)”), and (a3) (a1), (a2) Other hydrolyzable silane compounds (hereinafter also referred to as “compound (a3)”)
It is preferable that it is a hydrolysis-condensation product (henceforth polysiloxane [A]).
The polysiloxane [A] preferably used in the present invention is preferably a structural unit derived from the compound (a1) based on the total of repeating units derived from the compounds (a1), (a2) and (a3). 5 to 70% by weight, particularly preferably 10 to 60% by weight. When a copolymer having a structural unit of less than 5% by weight is used, the heat resistance, surface hardness, and stripping solution resistance of the interlayer insulating film and microlens obtained under baking conditions of less than 250 ° C. tend to be reduced. On the other hand, a copolymer exceeding 70% by weight tends to deteriorate the storage stability.

The compound (a1) is preferably the following formula (5)











(X ¹ Y ¹ ) _a SiR ¹ _b R ² _c (5)

(In the formula (5), ^{X 1} is oxiranyl group, a glycidyl group, glycidoxy group, 3,4-epoxy cyclohexyl group or a 3-oxetanyl group, provided that the 3-position carbon of the 3-oxetanyl group having 1 to 6 carbon atoms Y ¹ is a single bond, a methylene group or an alkylene group having 2 to 6 carbon atoms, and R ¹ is an alkoxyl group having 1 to 6 carbon atoms or an acyloxy group having 2 to 6 carbon atoms. R ² is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, a and b are each independently an integer of 1 to 3, and c is an integer of 0 to 2. Yes, but a + b + c = 4)
It is a silane compound represented by these.
As the alkyl group having 1 to 6 carbon atoms that may be substituted on the 3-position carbon of the 3-oxetanyl group of X ¹ in the above formula (5), an alkyl group having 1 to 3 carbon atoms is preferable, for example, a methyl group, Examples thereof include an ethyl group and an n-propyl group. Y ¹ is preferably a methylene group or an alkylene group having 2 or 3 carbon atoms. Examples of the alkylene group having 2 or 3 carbon atoms of Y ¹ include an ethylene group and a trimethylene group. R ¹ is preferably an alkoxyl group having 1 to 3 carbon atoms or an acyloxy group having 2 to 4 carbon atoms, and examples thereof include a methoxyl group, an ethoxyl group, an n-propyloxy group, an i-propyloxy group, and an acetyl group. it can. R ² is preferably an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a phenyl group.

  Specific examples of the compound (a1) include oxiranyl group-containing silane compounds such as glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, glycidoxymethyltri-n-propyloxysilane, Sidoxymethyltri-i-propyloxysilane, glycidoxymethyltriacetoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, glycidoxymethylmethyldi-n-propyloxysilane, glycidoxymethyl Cidoxymethylmethyldi-i-propyloxysilane, glycidoxymethylmethyldiacetoxysilane, glycidoxymethylethyldimethoxysilane, glycidoxymethylethyldiethoxysilane, glycidoxymethylethyldi-n-propyloxy Sisilane, glycidoxymethylethyl di-i-propyloxysilane, glycidoxymethylethyldiacetoxysilane, glycidoxymethylphenyldimethoxysilane, glycidoxymethylphenyldiethoxysilane, glycidoxymethylphenyldi-n- Propyloxysilane, glycidoxymethylphenyl di-i-propyloxysilane, glycidoxymethylphenyldiacetoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 2-glycid Xylethyltri-n-propyloxysilane, 2-glycidoxyethyltri-i-propyloxysilane, 2-glycidoxyethyltriacetoxysilane, 2-glycidoxyethylmethyldimethoxysilane, 2-glycidoxyethyl Methyl Ethoxysilane, 2-glycidoxyethyl methyldi-n-propyloxysilane, 2-glycidoxyethylmethyldi-i-propyloxysilane, 2-glycidoxyethylmethyldiacetoxysilane, 2-glycidoxyethyl Ethyldimethoxysilane, 2-glycidoxyethylethyldiethoxysilane, 2-glycidoxyethylethyldi-n-propyloxysilane, 2-glycidoxyethylethyldi-i-propyloxysilane, 2-glycidoxy Ethylethyldiacetoxysilane, 2-glycidoxyethylphenyldimethoxysilane, 2-glycidoxyethylphenyldiethoxysilane, 2-glycidoxyethylphenyldi-n-propyloxysilane, 2-glycidoxyethylphenyldi -I-propyloxysilane, 2-glycidoxy Siethylphenyldiacetoxysilane,

3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltri-n-propyloxysilane, 3-glycidoxypropyltri-i-propyloxysilane, 3- Glycidoxypropyltriacetoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldi-n-propyloxysilane, 3-glycidoxypropyl Methyldi-i-propyloxysilane, 3-glycidoxypropylmethyldiacetoxysilane, 3-glycidoxypropylethyldimethoxysilane, 3-glycidoxypropylethyldiethoxysilane, 3-glycidoxypropylethyldi- n-propyloxysilane 3-glycidoxypropylethyldi-i-propyloxysilane, 3-glycidoxypropylethyldiacetoxysilane, 3-glycidoxypropylphenyldimethoxysilane, 3-glycidoxypropylphenyldiethoxysilane, 3-glycidoxysilane Sidoxypropylphenyldi-n-propyloxysilane, 3-glycidoxypropylphenyldi-i-propyloxysilane, 3-glycidoxypropylphenyldiacetoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane (3,4-epoxycyclohexyl) methyltriethoxysilane, (3,4-epoxycyclohexyl) methyltri-n-propyloxysilane, (3,4-epoxycyclohexyl) methyltriacetoxysilane, (3,4-epoxycyclohexane) Xyl) methylmethyldimethoxysilane, (3,4-epoxycyclohexyl) methylmethyldiethoxysilane, (3,4-epoxycyclohexyl) methylmethyldi-n-propyloxysilane, (3,4-epoxycyclohexyl) methylmethyldiacetoxysilane (3,4-epoxycyclohexyl) methylethyldimethoxysilane, (3,4-epoxycyclohexyl) methylethyldiethoxysilane, (3,4-epoxycyclohexyl) methylethyldi-n-propyloxysilane, (3,4-epoxy (Cyclohexyl) methylethyldiacetoxysilane, (3,4-epoxycyclohexyl) methylphenyldimethoxysilane, (3,4-epoxycyclohexyl) methylphenyldiethoxysilane, (3,4-epoxysilane) Chloroyl) methylphenyldi-n-propyloxysilane, (3,4-epoxycyclohexyl) methylphenyldiacetoxysilane,

2- (3 ′, 4′-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethyltriethoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethyltri-n- Propyloxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethyltriacetoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) Ethylmethyldiethoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethylmethyldi-n-propyloxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethylmethyldiacetoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethylethyldimethoxysilane, 2- ( ', 4'-epoxycyclohexyl) ethylethyldiethoxysilane, 2- (3', 4'-epoxycyclohexyl) ethylethyldi-n-propyloxysilane, 2- (3 ', 4'-epoxycyclohexyl) ethylethyldiacetoxy Silane, 2- (3 ′, 4′-epoxycyclohexyl) ethylphenyldimethoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethylphenyldiethoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethyl Phenyldi-n-propyloxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethylphenyldiacetoxysilane, 3- (3 ′, 4′-epoxycyclohexyl) propyltrimethoxysilane, 3- (3 ′, 4'-epoxycyclohexyl) propyltriethoxy Lan, 3- (3 ′, 4′-epoxycyclohexyl) propyltri-n-propyloxysilane, 3- (3 ′, 4′-epoxycyclohexyl) propyltriacetoxysilane, 3- (3,4-epoxycyclohexyl) Propylmethyldimethoxysilane, 3- (3 ′, 4′-epoxycyclohexyl) propylmethyldiethoxysilane, 3- (3 ′, 4′-epoxycyclohexyl) propylmethyldi-n-propyloxysilane, 3- (3 ′ , 4′-epoxycyclohexyl) propylmethyldiacetoxysilane, 3- (3 ′, 4′-epoxycyclohexyl) propylethyldimethoxysilane, 3- (3 ′, 4′-epoxycyclohexyl) propylethyldiethoxysilane, 3- (3 ′, 4′-epoxycyclohexyl) propyl ester Tildi-n-propyloxysilane, 3- (3 ′, 4′-epoxycyclohexyl) propylethyldiacetoxysilane, 3- (3 ′, 4′-epoxycyclohexyl) propylphenyldimethoxysilane, 3- (3 ′, 4 '-Epoxycyclohexyl) propylphenyldiethoxysilane, 3- (3', 4'-epoxycyclohexyl) propylphenyldi-n-propyloxysilane, 3- (3 ', 4'-epoxycyclohexyl) propylphenyldiacetoxysilane Such;

Examples of silane compounds containing oxetanyl groups include (oxetane-3-yl) methyltrimethoxysilane, (oxetane-3-yl) methyltriethoxysilane, (oxetane-3-yl) methyltri-n-propyloxysilane, ( Oxetane-3-yl) methyltri-i-propyloxysilane, (oxetane-3-yl) methyltriacetoxysilane, (oxetane-3-yl) methylmethyldimethoxysilane, (oxetane-3-yl) methylmethyldiethoxysilane (Oxetane-3-yl) methylmethyldi-n-propyloxysilane, (oxetane-3-yl) methylmethyldi-i-propyloxysilane, (oxetane-3-yl) methylmethyldiacetoxysilane, (oxetane-3-yl) ) Methyl ethyl dimethyl Silane, (oxetane-3-yl) methylethyldiethoxysilane, (oxetane-3-yl) methylethyldi-n-propyloxysilane, (oxetane-3-yl) methylethyldi-i-propyloxysilane, (oxetane-3- Yl) methylethyldiacetoxysilane, (oxetane-3-yl) methylphenyldimethoxysilane, (oxetane-3-yl) methylphenyldiethoxysilane, (oxetane-3-yl) methylphenyldi-n-propyloxysilane, (Oxetane-3-yl) methylphenyldi-i-propyloxysilane, (oxetane-3-yl) methylphenyldiacetoxysilane, 2- (oxetane-3′-yl) ethyltrimethoxysilane, 2- (oxetane- 3'-yl) ethyltriethoxysila , (Oxetane-3-yl) ethyltri -n- propyl silane,

2- (oxetane-3′-yl) ethyltri-i-propyloxysilane, 2- (oxetane-3′-yl) ethyltriacetoxysilane, 2- (oxetane-3′-yl) ethylmethyldimethoxysilane, 2- (Oxetane-3′-yl) ethylmethyldiethoxysilane, 2- (oxetane-3′-yl) ethylmethyldi-n-propyloxysilane, 2- (oxetane-3′-yl) ethylmethyldi-i-propyloxysilane, 2- (oxetane-3′-yl) ethylmethyldiacetoxysilane, 2- (oxetane-3′-yl) ethylethyldimethoxysilane, 2- (oxetane-3′-yl) ethylethyldiethoxysilane, 2- ( Oxetane-3′-yl) ethylethyldi-n-propyloxysilane, 2- (oxetane-3 ′ Yl) ethyl ethyl di-i-propyloxysilane, 2- (oxetane-3'-yl) ethyl ethyl diacetoxy silane, 2- (oxetane-3'-yl) ethylphenyldimethoxysilane, 2- (oxetane-3'-yl ) Ethylphenyldiethoxysilane, 2- (oxetane-3′-yl) ethylphenyldi-n-propyloxysilane, 2- (oxetane-3′-yl) ethylphenyldi-i-propyloxysilane, 2- ( Oxetane-3′-yl) ethylphenyldiacetoxysilane, 3- (oxetane-3′-yl) propyltrimethoxysilane, 3- (oxetane-3′-yl) propyltriethoxysilane, 3- (oxetane-3 ′ -Yl) propyltri-n-propyloxysilane, 3- (oxetane-3'-yl) propyl Pyrtri-i-propyloxysilane, 3- (oxetane-3′-yl) propyltriacetoxysilane, 3- (oxetane-3′-yl) propylmethyldimethoxysilane, 3- (oxetane-3′-yl) propylmethyl Diethoxysilane, 3- (oxetane-3′-yl) propylmethyldi-n-propyloxysilane, 3- (oxetane-3′-yl) propylmethyldi-i-propyloxysilane, 3- (oxetane-3 '-Yl) propylmethyldiacetoxysilane, 3- (oxetane-3'-yl) propylethyldimethoxysilane, 3- (oxetane-3'-yl) propylethyldiethoxysilane, 3- (oxetane-3'-yl ) Propylethyldi-n-propyloxysilane, 3- (oxetane-3′-yl) propi Ruethyldi-i-propyloxysilane, 3- (oxetane-3′-yl) propylethyldiacetoxysilane, 3- (oxetane-3′-yl) propylphenyldimethoxysilane, 3- (oxetane-3′-yl) propyl Phenyldiethoxysilane, 3- (oxetane-3′-yl) propylphenyldi-n-propyloxysilane, 3- (oxetane-3′-yl) propylphenyldi-i-propyloxysilane, 3- (oxetane- 3'-yl) propylphenyldiacetoxysilane,

(3-methyloxetane-3-yl) methyltrimethoxysilane, (3-methyloxetane-3-yl) methyltriethoxysilane, (3-methyloxetane-3-yl) methyltri-n-propyloxysilane, (3 -Methyloxetane-3-yl) methyltri-i-propyloxysilane, (3-methyloxetane-3-yl) methyltriacetoxysilane, (3-methyloxetane-3-yl) methylmethyldimethoxysilane, (3-methyl Oxetane-3-yl) methylmethyldiethoxysilane, (3-methyloxetane-3-yl) methylmethyldi-n-propyloxysilane, (3-methyloxetane-3-yl) methylmethyldi-i-propyloxysilane, (3 -Methyloxetane-3-yl) methylmethyldiacetoxy (3-methyloxetane-3-yl) methylethyldimethoxysilane, (3-methyloxetane-3-yl) methylethyldiethoxysilane, (3-methyloxetane-3-yl) methylethyldi-n-propyloxysilane (3-methyloxetane-3-yl) methylethyldi-i-propyloxysilane, (3-methyloxetane-3-yl) methylethyldiacetoxysilane, (3-methyloxetane-3-yl) methylphenyldimethoxysilane, (3-methyloxetane-3-yl) methylphenyldiethoxysilane, (3-methyloxetane-3-yl) methylphenyldi-n-propyloxysilane, (3-methyloxetane-3-yl) methylphenyldi- i-propyloxysilane, (3-methyloxetane-3 Yl) methyl phenyl diacetoxy silane,

2- (3′-methyloxetane-3′-yl) ethyltrimethoxysilane, 2- (3′-methyloxetane-3′-yl) ethyltriethoxysilane, 2- (3′-methyloxetane-3′- Yl) ethyltri-n-propyloxysilane, 2- (3′-methyloxetane-3′-yl) ethyltri-i-propyloxysilane, 2- (3′-methyloxetane-3′-yl) ethyltriacetoxysilane 2- (3′-methyloxetane-3′-yl) ethylmethyldimethoxysilane, 2- (3′-methyloxetane-3′-yl) ethylmethyldiethoxysilane, 2- (3′-methyloxetane-3) '-Yl) ethylmethyldi-n-propyloxysilane, 2- (3'-methyloxetane-3'-yl) ethylmethyldi-i-propyloxy Sisilane, 2- (3′-methyloxetane-3′-yl) ethylmethyldiacetoxysilane, 2- (3′-methyloxetane-3′-yl) ethylethyldimethoxysilane, 2- (3′-methyloxetane- 3'-yl) ethylethyldiethoxysilane, 2- (3'-methyloxetane-3'-yl) ethylethyldi-n-propyloxysilane, 2- (3'-methyloxetane-3'-yl) ethylethyldi-i -Propyloxysilane, 2- (3'-methyloxetane-3'-yl) ethylethyldiacetoxysilane, 2- (3'-methyloxetane-3'-yl) ethylphenyldimethoxysilane, 2- (3'- Methyloxetane-3′-yl) ethylphenyldiethoxysilane, 2- (3′-methyloxetane-3′-yl) ethyl Phenyldi-n-propyloxysilane, 2- (3′-methyloxetane-3′-yl) ethylphenyldi-i-propyloxysilane, 2- (3′-methyloxetane-3′-yl) ethylphenyldiacetoxy Silane, 3- (3′-methyloxetane-3′-yl) propyltrimethoxysilane, 3- (3′-methyloxetane-3′-yl) propyltriethoxysilane, 3- (3′-methyloxetane-3) '-Yl) propyltri-n-propyloxysilane, 3- (3'-methyloxetane-3'-yl) propyltri-i-propyloxysilane, 3- (3'-methyloxetane-3'-yl) Propyltriacetoxysilane, 3- (3′-methyloxetane-3′-yl) propylmethyldimethoxysilane, 3- (3′-methyl) Luoxetane-3′-yl) propylmethyldiethoxysilane, 3- (3′-methyloxetane-3′-yl) propylmethyldi-n-propyloxysilane, 3- (3′-methyloxetane-3′-yl) ) Propylmethyldi-i-propyloxysilane, 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-propyloxysilane, 3- (3′- Methyloxetane-3′-yl) propylethyldi-i-propyloxysilane, 3- (3′-methyloxetane-3′-yl) Propylethyldiacetoxysilane, 3- (3′-methyloxetane-3′-yl) propylphenyldimethoxysilane, 3- (3′-methyloxetane-3′-yl) propylphenyldiethoxysilane, 3- (3 ′ -Methyloxetane-3'-yl) propylphenyldi-n-propyloxysilane, 3- (3'-methyloxetane-3'-yl) propylphenyldi-i-propyloxysilane, 3- (3'-methyl) Oxetane-3′-yl) propylphenyldiacetoxysilane, (3′-ethyloxetane-3′-yl) methyltrimethoxysilane,

(3-ethyloxetane-3-yl) methyltriethoxysilane, (3-ethyloxetane-3-yl) methyltri-n-propyloxysilane, (3-ethyloxetane-3-yl) methyltri-i-propyloxysilane (3-ethyloxetane-3-yl) methyltriacetoxysilane, (3-ethyloxetane-3-yl) methylmethyldimethoxysilane, (3-ethyloxetane-3-yl) methylmethyldiethoxysilane, (3- Ethyl oxetane-3-yl) methylmethyldi-n-propyloxysilane, (3-ethyloxetane-3-yl) methylmethyldi-i-propyloxysilane, (3-ethyloxetane-3-yl) methylmethyldiacetoxysilane, ( 3-Ethyloxetane-3-yl) methylethyldimethoxy Silane, (3-ethyloxetane-3-yl) methylethyldiethoxysilane, (3-ethyloxetane-3-yl) methylethyldi-n-propyloxysilane, (3-ethyloxetane-3-yl) methylethyldi-i- Propyloxysilane, (3-ethyloxetane-3-yl) methylethyldiacetoxysilane, (3-ethyloxetane-3-yl) methylphenyldimethoxysilane, (3-ethyloxetane-3-yl) methylphenyldiethoxysilane (3-ethyloxetane-3-yl) methylphenyldi-n-propyloxysilane, (3-ethyloxetane-3-yl) methylphenyldi-i-propyloxysilane, (3-ethyloxetane-3-yl) ) Methylphenyldiacetoxysilane,

2- (3′-ethyloxetane-3′-yl) ethyltrimethoxysilane, 2- (3′-ethyloxetane-3′-yl) ethyltriethoxysilane, 2- (3′-ethyloxetane-3′-) Yl) ethyltri-n-propyloxysilane, 2- (3′-ethyloxetane-3′-yl) ethyltri-i-propyloxysilane, 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-propyloxysilane, 2- (3'-ethyloxetane-3'-yl) ethylmethyldi-i-propyloxy Sisilane, 2- (3′-ethyloxetane-3′-yl) ethylmethyldiacetoxysilane, 2- (3′-ethyloxetane-3′-yl) ethylethyldimethoxysilane, 2- (3′-ethyloxetane- 3'-yl) ethylethyldiethoxysilane, 2- (3'-ethyloxetane-3'-yl) ethylethyldi-n-propyloxysilane, 2- (3'-ethyloxetane-3'-yl) ethylethyldi-i -Propyloxysilane, 2- (3'-ethyloxetane-3'-yl) ethylethyldiacetoxysilane, 2- (3'-ethyloxetane-3'-yl) ethylphenyldimethoxysilane, 2- (3'- Ethyloxetane-3′-yl) ethylphenyldiethoxysilane, 2- (3′-ethyloxetane-3′-yl) ethyl Phenyldi-n-propyloxysilane, 2- (3′-ethyloxetane-3′-yl) ethylphenyldi-i-propyloxysilane, 2- (3′-ethyloxetane-3′-yl) ethylphenyldiacetoxy Silane,

3- (3′-ethyloxetane-3′-yl) propyltrimethoxysilane, 3- (3′-ethyloxetane-3′-yl) propyltriethoxysilane, 3- (3′-ethyloxetane-3′-) Yl) propyltri-n-propyloxysilane, 3- (3′-ethyloxetane-3′-yl) propyltri-i-propyloxysilane, 3- (3′-ethyloxetane-3′-yl) propyltri Acetoxysilane, 3- (3′-ethyloxetane-3′-yl) propylmethyldimethoxysilane, 3- (3′-ethyloxetane-3′-yl) propylmethyldiethoxysilane, 3- (3′-ethyloxetane) -3'-yl) propylmethyldi-n-propyloxysilane, 3- (3'-ethyloxetane-3'-yl) propylmethyl -I-propyloxysilane, 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-propyloxysilane, 3- (3'-ethyloxetane-3) '-Yl) propylethyldi-i-propyloxysilane, 3- (3'-ethyloxetane-3'-yl) propylethyldiacetoxysilane, 3- (3'-ethyloxetane-3'-yl) propylphenyl Dimethoxysilane, 3- (3′-ethyloxetane-3′-yl) propylphenyldiethoxysilane, 3- (3′- Tyloxetane-3′-yl) propylphenyldi-n-propyloxysilane, 3- (3′-ethyloxetane-3′-yl) propylphenyldi-i-propyloxysilane, 3- (3′-ethyloxetane) -3'-yl) propylphenyldiacetoxysilane and the like.

  Of these, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethyltrimethoxysilane 2- (3 ′, 4′-epoxycyclohexyl) ethyltriethoxysilane, 3- (3′-ethyloxetane-3′-yl) propyltrimethoxysilane or 3- (3′-ethyloxetane-3′-yl) ) Propyltriethoxysilane is preferably used because it increases the sensitivity of the radiation-sensitive resin composition, widens the development margin, and improves the heat resistance. These compounds (a1) are used alone or in combination.

The polysiloxane [A] preferably used in the present invention is preferably a structural unit derived from the compound (a2) based on the total of repeating units derived from the compounds (a1), (a2) and (a3). 5 to 70% by weight, particularly preferably 10 to 60% by weight. When a copolymer having a structural unit of less than 5% by weight is used, the heat resistance, surface hardness and peeling solution resistance of the interlayer insulating film and microlens obtained under firing conditions of less than 250 ° C. tend to be reduced. On the other hand, a copolymer exceeding 70% by weight tends to decrease the remaining film ratio after development or deteriorate storage stability.
Examples of the functional group capable of undergoing addition reaction with the oxiranyl group or oxetanyl group in the compound (a2) include a hydroxyl group, a mercapto group, and an amino group. This amino group is preferably a primary amino group or a secondary amino group. Examples of the hydrolyzable group include an alkoxyl group, an acyloxy group, and an alkoxyalkoxyl group. It is preferable that the alkoxyl group has 1 to 6 carbon atoms, the acyloxy group has 2 to 6 carbon atoms, and the alkoxyalkoxyl group has 2 to 8 carbon atoms.
The compound (a2) is preferably the following formula (6)

(X ² Y ² ) _d SiR ³ _e R ⁴ _f (6)

(In formula (6), X ² is a hydroxyl group, a hydroxyphenyl group, a hydroxyphenylcarbonyloxy group, a mercapto group or an amino group, and Y ² is a single bond, a methylene group, an alkylene group having 2 to 6 carbon atoms, or the following formula: (6-1)

^{-Y 3 -Z-Y 4 - (} 6-1)

(In the formula (6-1), ^{Y 3} is a methylene group, an alkylene group or an arylene group having 6 to 12 carbon atoms having 2 to 6 carbon atoms, ^{Y 4} represents a single bond, methylene group or 2 to 6 carbon atoms an alkylene group, Z is a sulfur atom or a hydroxymethylene group, provided that the left of the formula (6-1) is bonded to the group X ^2.)
R ³ is an alkoxyl group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, or an alkoxyalkoxyl group having 2 to 8 carbon atoms, and R ⁴ is 1 carbon atom. An alkyl group of ˜6 or an aryl group of 6 to 12 carbon atoms, d and e are each independently an integer of 1 to 3, and f is an integer of 0 to 2, provided that d + e + f = 4. )
It is a silane compound represented by these.

In the above formula (6), the hydroxyphenyl group represented by X ² is preferably a 4-hydroxyphenyl group, and the hydroxyphenylcarbonyloxy group is preferably a p-hydroxyphenylcarbonyloxy group. The amino group of X ² can be a primary amino group or a secondary amino group, such as a primary amino group, an N-phenylamino group, an N-2- (aminoethyl) amino group, and the like. Can be mentioned. Y ² is preferably a methylene group or an alkylene group having 2 or 3 carbon atoms. Examples of the alkylene group having 2 or 3 carbon atoms of Y ² include an ethylene group and a trimethylene group. R ³ is preferably an alkoxyl group having 1 to 3 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, or an alkoxyalkoxyl group having 2 to 6 carbon atoms. For example, methoxyl group, ethoxyl group, n-propyloxy group, i-propyl An oxy group, an acetyl group, a methoxyethoxyl group, etc. can be mentioned. R ⁴ is preferably an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a phenyl group.

  Specific examples of the compound (a2) include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, hydroxymethyltri-n-propyloxysilane, and hydroxymethyltri-i-propyloxysilane as silane compounds containing a hydroxyl group. , Hydroxymethyltriacetoxysilane, hydroxymethyltri (methoxyethoxy) silane, hydroxymethylmethyldimethoxysilane, hydroxymethylmethyldiethoxysilane, hydroxymethylmethyldi-n-propyloxysilane, hydroxymethylmethyldi-i-propyloxysilane Hydroxymethylmethyldiacetoxysilane, hydroxymethylethyldimethoxysilane, hydroxymethylethyldiethoxysilane, hydroxymethylethyldi-n-propyl Pyroxysilane, hydroxymethylethyldi-i-propyloxysilane, hydroxymethylethyldiacetoxysilane, hydroxymethylethyldi (methoxyethoxy) silane, hydroxymethylphenyldimethoxysilane, hydroxymethylphenyldiethoxysilane, hydroxymethylphenyldi- n-propyloxysilane, hydroxymethylphenyldi-i-propyloxysilane, hydroxymethylphenyldiacetoxysilane, hydroxymethylphenyldi (methoxyethoxy) silane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxyethyltri-n-propyloxysilane, 2-hydroxyethyltri-i-propyloxysilane, 2-hydroxyethyltria Toxisilane, 2-hydroxyethyltri (methoxyethoxy) silane, 2-hydroxyethylmethyldimethoxysilane, 2-hydroxyethylmethyldiethoxysilane, 2-hydroxyethylmethyldi-n-propyloxysilane, 2-hydroxyethylmethyldi- i-propyloxysilane, 2-hydroxyethylmethyldiacetoxysilane, 2-hydroxyethylethyldimethoxysilane, 2-hydroxyethylethyldiethoxysilane, 2-hydroxyethylethyldi-n-propyloxysilane, 2-hydroxyethylethyl Di-i-propyloxysilane, 2-hydroxyethylethyldiacetoxysilane, 2-hydroxyethylethyldi (methoxyethoxy) silane, 2-hydroxyethylphenyldimethoxysilane, 2-hydroxy Droxyethylphenyldiethoxysilane, 2-hydroxyethylphenyldi-n-propyloxysilane, 2-hydroxyethylphenyldi-i-propyloxysilane, 2-hydroxyethylphenyldiacetoxysilane, 2-hydroxyethylphenyldi ( Methoxyethoxy) silane,

3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-hydroxypropyltri-n-propyloxysilane, 3-hydroxypropyltri-i-propyloxysilane, 3-hydroxypropyltriacetoxysilane, 3- Hydroxypropyltri (methoxyethoxy) silane, 3-hydroxypropylmethyldimethoxysilane, 3-hydroxypropylmethyldiethoxysilane, 3-hydroxypropylmethyldi-n-propyloxysilane, 3-hydroxypropylmethyldi-i-propyloxy Silane, 3-hydroxypropylmethyldiacetoxysilane, 3-hydroxypropylethyldimethoxysilane, 3-hydroxypropylethyldiethoxysilane, 3-hydroxypropylethyl -N-propyloxysilane, 3-hydroxypropylethyldi-i-propyloxysilane, 3-hydroxypropylethyldiacetoxysilane, 3-hydroxypropylethyldi (methoxyethoxy) silane, 3-hydroxypropylphenyldimethoxysilane, 3 -Hydroxypropylphenyldiethoxysilane, 3-hydroxypropylphenyldi-n-propyloxysilane, 3-hydroxypropylphenyldi-i-propyloxysilane, 3-hydroxypropylphenyldiacetoxysilane, 3-hydroxypropylphenyldi ( Methoxyethoxy) silane,

4-hydroxyphenyltrimethoxysilane, 4-hydroxyphenyltriethoxysilane, 4-hydroxyphenyltri-n-propyloxysilane, 4-hydroxyphenyltri-i-propyloxysilane, 4-hydroxyphenyltriacetoxysilane, 4- Hydroxyphenyltri (methoxyethoxy) silane, 4-hydroxyphenylmethyldimethoxysilane, 4-hydroxyphenylmethyldiethoxysilane, 4-hydroxyphenylmethyldi-n-propyloxysilane, 4-hydroxyphenylmethyldi-i-propyloxy Silane, 4-hydroxyphenylmethyldiacetoxysilane, 4-hydroxyphenylethyldimethoxysilane, 4-hydroxyphenylethyldiethoxysilane, 4-hydroxyphenylethyl -N-propyloxysilane, 4-hydroxyphenylethyldi-i-propyloxysilane, 4-hydroxyphenylethyldiacetoxysilane, 4-hydroxyphenylethyldi (methoxyethoxy) silane, 4-hydroxyphenylphenyldimethoxysilane, 4 -Hydroxyphenylphenyldiethoxysilane, 4-hydroxyphenylphenyldi-n-propyloxysilane, 4-hydroxyphenylphenyldi-i-propyloxysilane, 4-hydroxyphenylphenyldiacetoxysilane, 4-hydroxyphenylphenyldi ( Methoxyethoxy) silane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) P) Pentillytriethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltri-n-propyloxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltri-i-propyloxysilane 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltriacetoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltri (methoxyethoxy) silane, 4-hydroxy-5- (p- Hydroxyphenylcarbonyloxy) pentylmethyldimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylmethyldiethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarb) Bonyloxy) pentylmethyldi-n-propyloxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylmethyldi-i-propyloxysilane,

4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylmethyldiacetoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylethyldimethoxysilane, 4-hydroxy-5- (p-hydroxyphenyl) Carbonyloxy) pentylethyldiethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylethyldi-n-propyloxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylethyldi -I-propyloxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylethyldiacetoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylethyl Di (methoxyethoxy) silane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylphenyldimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylphenyldiethoxysilane, 4-hydroxy- 5- (p-hydroxyphenylcarbonyloxy) pentylphenyldi-n-propyloxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylphenyldi-i-propyloxysilane, 4-hydroxy-5 (P-hydroxyphenylcarbonyloxy) pentylphenyldiacetoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylphenyldi (methoxyethoxy) silane, the following formula (a2-1)

^{HO-Y 3 -S-Y 4} -Si (OR) 3 (a2-1)

(In Formula (2a-1), Y ³ and Y ⁴ have the same meaning as in Formula (6-1) above, and R is independently an alkyl group having 1 to 6 carbon atoms or 2 to 6 carbon atoms. An acyl group)) and the like;

Examples of silane compounds containing a mercapto group include mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyltri-n-propyloxysilane, mercaptomethyltri-i-propyloxysilane, mercaptomethyltriacetoxysilane, mercaptomethyl Tri (methoxyethoxy) silane, mercaptomethylmethyldimethoxysilane, mercaptomethylmethyldiethoxysilane, mercaptomethylmethyldi-n-propyloxysilane, mercaptomethylmethyldi-i-propyloxysilane, mercaptomethylmethyldiacetoxysilane, mercapto Methylethyldimethoxysilane, mercaptomethylethyldiethoxysilane, mercaptomethylethyldi-n-propyloxysilane, merca Tomethylethyldi-i-propyloxysilane, mercaptomethylethyldiacetoxysilane, mercaptomethylethyldi (methoxyethoxy) silane, mercaptomethylphenyldimethoxysilane, mercaptomethylphenyldiethoxysilane, mercaptomethylphenyldi-n-propyloxysilane, mercapto Methylphenyldi-i-propyloxysilane, mercaptomethylphenyldiacetoxysilane, mercaptomethylphenyldi (methoxyethoxy) silane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethyltri-n -Propyloxysilane, 2-mercaptoethyltri-i-propyloxysilane, 2-mercaptoethyltriacetoxysilane, 2-merca Toethyltri (methoxyethoxy) silane, 2-mercaptoethylmethyldimethoxysilane, 2-mercaptoethylmethyldiethoxysilane, 2-mercaptoethylmethyldi-n-propyloxysilane, 2-mercaptoethylmethyldi-i-propyloxysilane, 2-mercaptoethylmethyldiacetoxysilane, 2-mercaptoethylethyldimethoxysilane, 2-mercaptoethylethyldiethoxysilane, 2-mercaptoethylethyldi-n-propyloxysilane, 2-mercaptoethylethyldi-i-propyloxy Silane, 2-mercaptoethylethyldiacetoxysilane, 2-mercaptoethylethyldi (methoxyethoxy) silane, 2-mercaptoethylphenyldimethoxysilane, 2-mercaptoethylphenyldie Toxisilane, 2-mercaptoethylphenyldi-n-propyloxysilane, 2-mercaptoethylphenyldi-i-propyloxysilane, 2-mercaptoethylphenyldiacetoxysilane, 2-mercaptoethylphenyldi (methoxyethoxy) silane,

3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propyloxysilane, 3-mercaptopropyltri-i-propyloxysilane, 3-mercaptopropyltriacetoxysilane, 3- Mercaptopropyltri (methoxyethoxy) silane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropylmethyldi-n-propyloxysilane, 3-mercaptopropylmethyldi-i-propyloxy Silane, 3-mercaptopropylmethyldiacetoxysilane, 3-mercaptopropylethyldimethoxysilane, 3-mercaptopropylethyldiethoxysilane, 3-mercaptopropylethyl -N-propyloxysilane, 3-mercaptopropylethyldi-i-propyloxysilane, 3-mercaptopropylethyldiacetoxysilane, 3-mercaptopropylethyldi (methoxyethoxy) silane, 3-mercaptopropylphenyldimethoxysilane, 3 -Mercaptopropylphenyldiethoxysilane, 3-mercaptopropylphenyldi-n-propyloxysilane, 3-mercaptopropylphenyldi-i-propyloxysilane, 3-mercaptopropylphenyldiacetoxysilane, 3-mercaptopropylphenyldi ( Methoxyethoxy) silane and the like;

Examples of silane compounds containing amino groups include aminomethyltrimethoxysilane, aminomethyltriethoxysilane, aminomethyltri-n-propyloxysilane, aminomethyltri-i-propyloxysilane, aminomethyltriacetoxysilane, aminomethyl Tri (methoxyethoxy) silane, aminomethylmethyldimethoxysilane, aminomethylmethyldiethoxysilane, aminomethylmethyldi-n-propyloxysilane, aminomethylmethyldi-i-propyloxysilane, aminomethylmethyldiacetoxysilane, amino Methylethyldimethoxysilane, aminomethylethyldiethoxysilane, aminomethylethyldi-n-propyloxysilane, aminomethylethyldi-i-propyloxysilane, aminomethylethyl Acetoxysilane, aminomethylethyldi (methoxyethoxy) silane, aminomethylphenyldimethoxysilane, aminomethylphenyldiethoxysilane, aminomethylphenyldi-n-propyloxysilane, aminomethylphenyldi-i-propyloxysilane, aminomethyl Phenyldiacetoxysilane, aminomethylphenyldi (methoxyethoxy) silane, 2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane, 2-aminoethyltri-n-propyloxysilane, 2-aminoethyltri-i -Propyloxysilane, 2-aminoethyltriacetoxysilane, 2-aminoethyltri (methoxyethoxy) silane, 2-aminoethylmethyldimethoxysilane, 2-aminoethylmethyldiethoxysilane 2-aminoethylmethyldi-n-propyloxysilane, 2-aminoethylmethyldi-i-propyloxysilane, 2-aminoethylmethyldiacetoxysilane, 2-aminoethylethyldimethoxysilane, 2-aminoethylethyldiethoxy Silane, 2-aminoethylethyldi-n-propyloxysilane, 2-aminoethylethyldi-i-propyloxysilane, 2-aminoethylethyldiacetoxysilane, 2-aminoethylethyldi (methoxyethoxy) silane, 2 -Aminoethylphenyldimethoxysilane, 2-aminoethylphenyldiethoxysilane, 2-aminoethylphenyldi-n-propyloxysilane, 2-aminoethylphenyldi-i-propyloxysilane, 2-aminoethylphenyldiacetoxysilane , 2-A Minoethylphenyldi (methoxyethoxy) silane,

3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltri-n-propyloxysilane, 3-aminopropyltri-i-propyloxysilane, 3-aminopropyltriacetoxysilane, 3- Aminopropyltri (methoxyethoxy) silane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldi-n-propyloxysilane, 3-aminopropylmethyldi-i-propyloxy Silane, 3-aminopropylmethyldiacetoxysilane, 3-aminopropylethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, 3-aminopropylethyldi-n-propyloxysilane, 3-aminopropylethyldi i-propyloxysilane, 3-aminopropylethyldiacetoxysilane, 3-aminopropylethyldi (methoxyethoxy) silane, 3-aminopropylphenyldimethoxysilane, 3-aminopropylphenyldiethoxysilane, 3-aminopropylphenyldi -N-propyloxysilane, 3-aminopropylphenyldi-i-propyloxysilane, 3-aminopropylphenyldiacetoxysilane, 3-aminopropylphenyldi (methoxyethoxy) silane,

N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltri-n -Propyloxysilane, N-2- (aminoethyl) -3-aminopropyltri-i-propyloxysilane, N-2- (aminoethyl) -3-aminopropyltriacetoxysilane, N-2- (aminoethyl) ) -3-Aminopropyltri (methoxyethoxy) silane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N- 2- (Aminoethyl) -3-aminopropylmethyldi-n-propyloxysilane, N-2- (aminoethyl) -3 Aminopropylmethyldi-i-propyloxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiacetoxysilane, N-2- (aminoethyl) -3-aminopropylethyldimethoxysilane, N-2- (Aminoethyl) -3-aminopropylethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropylethyldi-n-propyloxysilane, N-2- (aminoethyl) -3-aminopropylethyl Di-i-propyloxysilane, N-2- (aminoethyl) -3-aminopropylethyldiacetoxysilane, N-2- (aminoethyl) -3-aminopropylethyldi (methoxyethoxy) silane, N-2 -(Aminoethyl) -3-aminopropylphenyldimethoxysilane, N-2- (aminoethyl) -3 Aminopropylphenyldiethoxysilane, N-2- (aminoethyl) -3-aminopropylphenyldi-n-propyloxysilane, N-2- (aminoethyl) -3-aminopropylphenyldi-i-propyloxysilane N-2- (aminoethyl) -3-aminopropylphenyldiacetoxysilane, N-2- (aminoethyl) -3-aminopropylphenyldi (methoxyethoxy) silane,

N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltri-n-propyloxysilane, N-phenyl-3-aminopropyltri- i-propyloxysilane, N-phenyl-3-aminopropyltriacetoxysilane, N-phenyl-3-aminopropyltri (methoxyethoxy) silane, N-phenyl-3-aminopropylmethyldimethoxysilane, N-phenyl-3 -Aminopropylmethyldiethoxysilane, N-phenyl-3-aminopropylmethyldi-n-propyloxysilane, N-phenyl-3-aminopropylmethyldi-i-propyloxysilane, N-phenyl-3-aminopropyl Methyldiacetoxysilane, N-pheny -3-aminopropylethyldimethoxysilane, N-phenyl-3-aminopropylethyldiethoxysilane, N-phenyl-3-aminopropylethyldi-n-propyloxysilane, N-phenyl-3-aminopropylethyldi- i-propyloxysilane, N-phenyl-3-aminopropylethyldiacetoxysilane, N-phenyl-3-aminopropylethyldi (methoxyethoxy) silane, N-phenyl-3-aminopropylphenyldimethoxysilane, N-phenyl -3-aminopropylphenyldiethoxysilane, N-phenyl-3-aminopropylphenyldi-n-propyloxysilane, N-phenyl-3-aminopropylphenyldi-i-propyloxysilane, N-phenyl-3- Aminopropylphenyl diace Kishishiran, N- phenyl-3-aminopropyl-phenyl di (methoxyethoxy) silane, etc., can be exemplified respectively.

  Of these, hydroxymethyltrimethoxysilane, hydroxyethyltrimethoxysilane, trimethoxysilylpropyl-1- (4′-hydroxyphenyl) propylthioether, trimethoxysilylpropyl-1- (2′-hydroxyphenyl) propylthioether, Trimethoxysilylpropyl-2- (4′-hydroxyphenyl) propylthioether, trimethoxysilylpropyl-2- (2′-hydroxyphenyl) propylthioether, trimethoxysilylethyl- (4′-hydroxyphenyl) thioether, trimethoxy Silylpropyl- (4′-hydroxyphenyl) thioether, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane or aminomethyltrimethoxysilane Emissions is, the heat resistance of the resulting interlayer insulating film, or microlens, transparency, can be suitably used from the viewpoint of stripping solution resistance.

The polysiloxane [A] preferably used in the present invention is preferably a structural unit derived from the compound (a3) based on the total of repeating units derived from the compounds (a1), (a2) and (a3). 10 to 90% by weight, particularly preferably 20 to 80% by weight. When this structural unit is less than 10% by weight, the storage stability of the radiation-sensitive resin composition tends to be reduced. On the other hand, when the amount of this structural unit exceeds 90% by weight, the resulting interlayer insulating film or The heat resistance, surface hardness, and stripping solution resistance of the microlens may be insufficient.
The compound (a3) is preferably the following formula (7)

SiR ⁵ _g R ⁶ _h (7)

(In the formula (7), R ⁵ is an alkoxyl group having 1 to 6 carbon atoms or an aryloxy group having 6 to 18 carbon atoms, provided that part or all of the hydrogen atoms of the aryloxy group are halogen atoms, cyano groups, R ⁶ may be substituted by a nitro group or an alkyl group having 1 to 6 carbon atoms, and R ⁶ is an alkyl group having 1 to ⁶ carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or A (meth) acryloxy group, wherein some or all of the hydrogen atoms of the aryl group may be substituted with a halogen atom, a cyano group, a nitro group or an alkyl group having 1 to 6 carbon atoms, and (meth) acryloxy The group may be bonded via a methylene group or an alkylene group having 2 to 6 carbon atoms, g is an integer of 1 to 4, h is an integer of 0 to 3, provided that g + h = 4. .)
It is a silane compound represented by these.

R ⁵ in the above formula (7) is preferably an alkoxyl group having 1 to 4 carbon atoms or an aryloxy group having 6 to 12 carbon atoms, such as a methoxyl group, an ethoxyl group, an n-propyloxy group, or an i-propyloxy group. Phenoxy group, naphthyloxy group, 4-chlorophenoxy group, 4-cyanophenoxy group, 4-nitrophenoxy group, 4-toluyloxy group and the like. R ⁶ is an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a direct bond or a methylene group or an alkylene group having 2 to 3 carbon atoms. (Meth) acryloxy group, specific examples thereof include, for example, methyl group, ethyl group, phenyl group, 4-chlorophenyl group, 4-cyanophenyl group, 4-nitrophenyl group, 4-toluyl group, naphthyl group , Vinyl group, allyl group, (meth) acryloxy group, (meth) acryloxymethyl group, 2- (meth) acryloxyethyl group, 3- (meth) acryloxypropyl group and the like.

Specific examples of the compound (a3) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propyloxysilane, tetraisopropyloxysilane, tetra-n-butoxysilane; methyltrimethoxysilane, methyl Monoalkyltrialkoxysilanes such as triethoxysilane, methyltri-n-propyloxysilane, ethyltriethoxysilane, cyclohexyltriethoxysilane;
Monoaryltrialkoxysilanes such as phenyltriethoxysilane, naphthyltriethoxysilane, 4-chlorophenyltriethoxysilane, 4-cyanophenyltriethoxysilane, 4-nitrophenyltriethoxysilane, 4-methylphenyltriethoxysilane;
Monoaryloxy such as phenoxytriethoxysilane, naphthyloxytriethoxysilane, 4-chlorophenyloxytriethoxysilane, 4-cyanophenyltrioxyethoxysilane, 4-nitrophenyloxytriethoxysilane, 4-methylphenyloxytriethoxysilane Trialkoxysilane;
Dialkyl dialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propyloxysilane, methyl (ethyl) diethoxysilane, methyl (cyclohexyl) diethoxysilane;
Monoalkylmonoaryl dialkoxysilanes such as methyl (phenyl) diethoxysilane; diaryl dialkoxysilanes such as diphenyldiethoxysilane;
Diaryloxy dialkoxysilanes such as diphenoxydiethoxysilane;
Monoalkyl monoaryloxy dialkoxysilanes such as methyl (phenoxy) diethoxysilane;
Monoaryl monoaryloxy dialkoxysilanes such as phenyl (phenoxy) diethoxysilane;

Trialkylmonoalkoxysilanes such as trimethylethoxysilane, trimethyl-n-propyloxysilane, dimethyl (ethyl) ethoxysilane, dimethyl (cyclohexyl) ethoxysilane;
Dialkyl monoaryl monoalkoxysilanes such as dimethyl (phenyl) ethoxysilane;
Monoalkyldiarylmonoalkoxysilanes such as methyl (diphenyl) ethoxysilane;
Triaryloxymonoalkoxysilanes such as triphenoxyethoxysilane;
Monoalkyldiaryloxymonoalkoxysilanes such as methyl (diphenoxy) ethoxysilane; monoaryldiaryloxymonoalkoxysilanes such as phenyl (diphenoxy) ethoxysilane;
Dialkylmonoaryloxymonoalkoxysilanes such as dimethyl (phenoxy) ethoxysilane;
Diarylmonoaryloxymonoalkoxysilanes such as diphenyl (phenoxy) ethoxysilane;
Monoalkylmonoarylmonoaryloxymonoalkoxysilanes such as methyl (phenyl) (phenoxy) ethoxysilane;
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propyloxysilane, vinyltri-i-propyloxysilane, vinyltriacetoxysilane, vinyltri (methoxyethoxy) silane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldi -N-propyloxysilane, vinylmethyldi-i-propyloxysilane, vinylmethyldiacetoxysilane, vinylethyldimethoxysilane, vinylethyldiethoxysilane, vinylethyldi-n-propyloxysilane, vinylethyldi-i-propyloxysilane, vinylethyl Diacetoxysilane, vinylethyldi (methoxyethoxy) silane, vinylphenyldimethoxysilane, vinylphenyldiethoxysilane, vinylphenyl -n- propyl silane, vinyl phenyl di -i- propyl silane, vinyl phenyl diacetoxy silane, vinyl group-containing alkoxysilane such as vinyl phenyl di (methoxyethoxy) silane;

Allyltrimethoxysilane, allyltriethoxysilane, allyltri-n-propyloxysilane, allyltri-i-propyloxysilane, allyltriacetoxysilane, allyltri (methoxyethoxy) silane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldi -N-propyloxysilane, allylmethyldi-i-propyloxysilane, allylmethyldiacetoxysilane, allylethyldimethoxysilane, allylethyldiethoxysilane, allylethyldi-n-propyloxysilane, allylethyldi-i-propyloxysilane, allylethyl Diacetoxysilane, allylethyldi (methoxyethoxy) silane, allylphenyldimethoxysilane, allylphenyldiethoxysilane, allylphenyl -n- propyl silane, allyl phenyl di -i- propyl silane, allyl phenyl diacetoxy silane, such as an allyl group-containing silane allyl phenyl di (methoxyethoxy) silane;
(Meth) acryloxymethyltrimethoxysilane, (meth) acryloxymethyltriethoxysilane, (meth) acryloxymethyltri-n-propyloxysilane, (meth) acryloxymethyltri-i-propyloxysilane, (meta ) Acryloxymethyltriacetoxysilane, (meth) acryloxymethylmethyldimethoxysilane, (meth) acryloxymethylmethyldiethoxysilane, (meth) acryloxymethylmethyldi-n-propyloxysilane, (meth) acryloxymethyl Methyldi-i-propyloxysilane, (meth) acryloxymethylmethyldiacetoxysilane, (meth) acryloxymethylethyldimethoxysilane, (meth) acryloxymethylethyldiethoxysilane, (meth) acryloxymethylethyldi n-propyloxysilane, (meth) acryloxymethylethyldi-i-propyloxysilane, (meth) acryloxymethylethyldiacetoxysilane, (meth) acryloxymethylphenyldimethoxysilane, (meth) acryloxymethylphenyldi Ethoxysilane, (meth) acryloxymethylphenyldi-n-propyloxysilane, (meth) acryloxymethylphenyldi-i-propyloxysilane, (meth) acryloxymethylphenyldiacetoxysilane,

2- (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 2- (meth) acryloxyethyltri-n-propyloxysilane, 2- (meth) acryloxyethyltri- i-propyloxysilane, 2- (meth) acryloxyethyltriacetoxysilane, 3- (meth) acryloxyethylmethyldimethoxysilane, 2- (meth) acryloxyethylmethyldiethoxysilane, 2- (meth) acryloxy Ethylmethyldi-n-propyloxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n-propyloxysilane, 3- (Meth) acryloxypropyltri-i-propi Oxysilane, 3- (meth) acryloxypropyltriacetoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropylmethyldi- n-propyloxysilane, 3- (meth) acryloxypropylmethyldi-i-propyloxysilane, 3- (meth) acryloxypropylmethyldiacetoxysilane, 3- (meth) acryloxypropylethyldimethoxysilane, 3- (Meth) acryloxypropylethyldiethoxysilane, 3- (meth) acryloxypropylethyldi-n-propyloxysilane, 3- (meth) acryloxypropylethyldi-i-propyloxysilane, 3- (meth) Acryloxypropylethyldia Toxisilane, 3- (meth) acryloxypropylphenyldimethoxysilane, 3- (meth) acryloxypropylphenyldiethoxysilane, 3- (meth) acryloxypropylphenyldi-n-propyloxysilane, 3- (meth) acryl Examples include (meth) acrylic group-containing silanes such as loxypropylphenyldi-i-propyloxysilane and 3- (meth) acryloxypropylphenyldiacetoxysilane.

Of these compounds (a3), tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyl Diethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane or 3- (meth) acryloxypropyltriethoxysilane react From the standpoints of heat resistance, transparency of the interlayer insulating film or microlens to be obtained, transparency, and resistance to stripping solution.
Specific examples of polysiloxane [A] preferably used in the present invention include, for example, 3-glycidoxypropyltrimethoxysilane / 2-hydroxyethyltrimethoxysilane / dimethyldimethoxysilane cocondensate, 2- (3 ′, 4 '-Epoxycyclohexyl) ethyltrimethoxysilane / 3-mercaptopropyltrimethoxysilane / phenyltrimethoxysilane cocondensate or 3- (3'-ethyloxetane-3'-yl) propyltrimethoxysilane / trimethoxysilylpropyl- Mention may be made of 2- (4′-hydroxyphenyl) propylthioether / methyltrimethoxysilane cocondensate.

The polysiloxane [A] preferably used in the present invention is obtained by hydrolyzing and condensing the compounds (a1), (a2) and (a3) as described above, preferably in a solvent, preferably in the presence of a catalyst. Can be synthesized.
Examples of the solvent that can be used for the synthesis of polysiloxane [A] include alcohol, ether, glycol ether, ethylene glycol monoalkyl ether acetate, diethylene glycol, diethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether, propylene glycol alkyl ether. Acetates, propylene glycol alkyl ether propionates, aromatic hydrocarbons, ketones, esters and the like can be mentioned.
Specific examples thereof include alcohols such as methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, and 3-phenyl-1-propanol; ethers such as tetrahydrofuran;
Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Examples of ethylene glycol monoalkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
Examples of diethylene glycol include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether;
Examples of diethylene glycol monoalkyl ether acetate include diethylene glycol monoethyl ether acetate;

Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
As propylene glycol monoalkyl ether propionate, for example, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate, etc .;
Examples of the propylene glycol monoalkyl ether acetate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;
Aromatic hydrocarbons such as toluene, xylene, etc .;
Examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone;

Examples of esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxy Ethyl acetate, hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy -3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, propoxy Methyl acetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid Propyl, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate Propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropyl Butyl pionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropionate Examples thereof include propyl acid, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

Of these solvents, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether or propylene glycol alkyl ether acetate are preferred, and in particular, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol methyl. Ether acetate or methyl 3-methoxypropionate is preferred. The amount of the solvent used is preferably such that the total amount of the compounds (a1), (a2) and (a3) in the reaction solution is 10 to 50% by weight, and 15 to 40% by weight. More preferably.
The hydrolysis and condensation reaction for synthesizing the polysiloxane [A] is preferably an acid catalyst (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, acidic ion exchange resin, Various Lewis acids, etc.) or base catalysts (eg, ammonia, primary amines, secondary amines, tertiary amines, nitrogen-containing aromatic compounds such as pyridine; basic ion exchange resins; hydroxides such as sodium hydroxide) Carbonates such as potassium carbonate; carboxylates such as sodium acetate; various Lewis bases, etc.). The amount of the catalyst to be used is preferably 0.2 mol or less, more preferably 0.00001 to 0.1 mol, relative to 1 mol in total of the compounds (a1), (a2) and (a3).
The amount of water used, the reaction temperature and the reaction time are appropriately set. For example, the following conditions can be adopted.
The amount of water used is preferably 0.1 to 3 with respect to 1 mol of the total amount of the group R ^{1 in} the compound (a1), the group R ³ in the compound (a2) and the group R ^{5 in} the compound (a3). Mol, more preferably 0.3 to 2 mol, still more preferably 0.5 to 1.5 mol.
The reaction temperature is preferably 40 to 200 ° C, more preferably 50 to 150 ° C.
The reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours.
The compounds (a1), (a2) and (a3) and water may be added at once to carry out the hydrolysis and condensation reaction in one step, or the compounds (a1), (a2) and (a3) and water may be added. The hydrolysis and condensation reaction may be performed in multiple stages by adding them stepwise.

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

[B] Component The [B] component used in the present invention is a 1,2-quinonediazide compound that generates a carboxylic acid upon irradiation with radiation, and is a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus having a hydroxyl group”). Or a condensate of a mother nucleus having an amino group and 1,2-naphthoquinonediazide sulfonic acid halide.
Examples of the mother nucleus having a hydroxyl group include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nucleus having a hydroxyl group.
Specific examples thereof include trihydroxybenzophenone such as 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone;
As tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3,4 2,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, etc .;
Examples of pentahydroxybenzophenone include 2,3,4,2 ′, 6′-pentahydroxybenzophenone;
Examples of hexahydroxybenzophenone include 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone and the like;

Examples of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, and 1,1,1-tri (p-hydroxyphenyl). ) Ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-4) -Hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl- 4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5 6,7,5 ′, 6 ′, 7′-hexanol, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan and the like;
Examples of other mother nucleus having a hydroxyl group include 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 2- [bis {(5-isopropyl-4 -Hydroxy-2-methyl) phenyl} methyl], 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl]- 3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis {1- (4- And hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene.
Examples of the mother nucleus having an amino group include compounds in which the hydroxyl group of the mother nucleus having the hydroxyl group is substituted with an amino group.
Among these mother nuclei, 2,3,4,4′-tetrahydroxybenzophenone, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] Bisphenol is preferred.

As the 1,2-naphthoquinonediazidesulfonic acid halide, 1,2-naphthoquinonediazidesulfonic acid chloride is preferable, and specific examples thereof include 1,2-naphthoquinonediazide-4-sulfonic acid chloride and 1,2-naphthoquinonediazide- 5-sulfonic acid chloride can be mentioned, and among these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferably used.
In the condensation reaction, 1 corresponds to preferably 30 to 85 mol%, more preferably 50 to 70 mol%, based on the number of hydroxyl groups in the phenolic compound or alcoholic compound or the number of amino groups in the mother nucleus having an amino group. , 2-Naphthoquinonediazide sulfonic acid halide can be used.
The condensation reaction can be carried out by a known method.
These [B] components can be used individually or in combination of 2 or more types.
[B] The usage-amount of a component becomes like this. Preferably it is 1-25 weight part with respect to 100 weight part of [A] component, More preferably, it is 5-20 weight part. If this proportion is less than 1 part by weight, the difference in solubility between the irradiated portion and the unirradiated portion in the alkaline aqueous solution that is the developer may be small, and patterning may be difficult. Alternatively, the heat resistance and solvent resistance of the microlens may be insufficient. On the other hand, when this ratio exceeds 25 parts by weight, the solubility in the alkaline aqueous solution may be insufficient in the radiation-irradiated portion, and development may be difficult.

[C] component [C] component in this invention is a compound which generate | occur | produces an acid by exposure of radiation, such as visible light, an ultraviolet-ray, a far-ultraviolet ray, a charged particle beam, and an X-ray, or a heating.

In the formula (1) representing the onium salt constituting the present invention, A represents an element from Group VIA to Group VIIA (CAS notation), and combines with organic groups R and D to form onium [A ′]. Of the elements of Group VIA to Group VIIA, S, I and Se which are excellent in cationic polymerization initiating ability are preferable, and S and I are particularly preferable. m represents the valence of the element A and is 1 or 2.
R is an organic group bonded to A, and is an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or Represents an alkynyl group having 2 to 30 carbon atoms, and these are alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, It may be substituted with at least one selected from the group consisting of alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups and halogen. The number of R is m + n (m−1) +1, and each R may be the same as or different from each other. In addition, two or more R's are each directly or —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR′—, —CO—, —COO—, —CONH—, carbon number A ring structure containing the element A may be formed by bonding via 1 to 3 alkylene groups or phenylene groups. Here, R ′ is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

 In the above, the aryl group having 6 to 30 carbon atoms includes monocyclic aryl groups such as a phenyl group and condensed polycyclic rings such as naphthyl, anthracenyl, phenanthrenyl, bienyl, chrysenyl, naphthacenyl, benzoanthracenyl, anthraquinolyl, fluorenyl, naphthoquinolyl, and the like. And a formula aryl group.

Examples of the heterocyclic group having 4 to 30 carbon atoms include cyclic groups containing 1 to 3 heteroatoms such as oxygen, nitrogen, and sulfur, which may be the same or different. Are monocyclic heterocyclic groups such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, biridyl, birimidyl, pyrazinyl and indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, Condensed polycyclic heterocycles such as quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, dibenzofuranyl And the like.

Examples of the alkyl group having 1 to 30 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and the like, isopropyl, isobutyl, sec-butyl, tert-butyl. , Branched alkyl groups such as isopentyl, neopentyl, tert-pentyl and isohexyl, and cycloalkyl groups such as cyclopropyl, cycloptyl, cyclopentyl and cyclohexyl.
Examples of the alkenyl group having 2 to 30 carbon atoms include vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, and 1-methyl-2- Propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-2-butenyl, Linear or branched such as 3-methyl-2-butenyl, 1,2-dimethyl-1-propenyl, 1-decenyl, 2-decenyl, 8-decenyl, 1-dodecenyl, 2-dodecenyl, 10-dodecenyl Is mentioned. Further, examples of the alkynyl group having 2 to 30 carbon atoms include ethynyl, 1-provinyl, 2-provinyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-1-provinyl, and 1-methyl-2-provinyl. 2-methyl-1-provinyl, 2-methyl-2-provinyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-1-butynyl, 2-methyl-2-butynyl, Linear or branched such as 3-methyl-2-butynyl, 1,2-dimethyl-1-provinyl, 1-decynyl, 2-decynyl, 8-decynyl, 1-dodecynyl, 2-dodecynyl, 10-dodecynyl Is mentioned.

The aryl group having 6 to 30 carbon atoms, the heterocyclic group having 4 to 30 carbon atoms, the alkyl group having 1 to 30 carbon atoms, the alkenyl group having 2 to 30 carbon atoms, or the alkynyl group having 2 to 30 carbon atoms is at least It may have one type of substituent, and examples of the substituent include straight chain having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, okdadecyl, and the like. Alkyl groups; branched alkyl groups having 1 to 18 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. A cycloalkyl group having 3 to 18 carbon atoms; a hydroxy group; methoxy, ethoxy, propoxy, A linear or branched alkoxy group having 1 to 18 carbon atoms such as sopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy; acetyl, propionyl, butanoyl, 2-methylpropionyl, hebutanoyl, C2-C18 linear or branched alkylcarbonyl groups such as 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl and octadecanoyl; aryls having 7 to 11 carbon atoms such as benzoyl and naphthoyl Carbonyl group; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, o C2-C19 linear or branched alkoxycarbonyl groups such as tyloxycarbonyl, tetradecyloxycarbonyl, octadecyloxycarbonyl, etc .; C7-10 aryloxycarbonyl groups such as phenoxycarbonyl, naphthoxycarbonyl, etc. An arylthiocarbonyl group having 7 to 11 carbon atoms such as phenylthiocarbonyl and naphthoxythiocarbonyl; acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isoptylcarbonyloxy, sec-butylcarbonyloxy , Tert-butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyloxy, octadecylcarbonyloxy, etc., linear or branched acyloxy having 2 to 19 carbon atoms Si group; phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1- Naphthylthio, 2-naphthylthio, 4- [4- (phenylthio) benzoyl] phenylthio, 4- [4- (phenylthio) phenoxy] phenylthio, 4- [4- (phenylthio) phenyl] phenylthio, 4- (phenylthio) phenylthio, 4 -Benzoylpheny Thio, 4-benzoyl-2-chlorophenylthio, 4-benzoyl-3-chlorophenylthio, 4-benzoyl-3-methylthiophenylthio, 4-benzoyl-2-methylthiophenylthio, 4- (4-methylthiobenzoyl) phenylthio, 4- (2-methylthiobenzoyl) phenylthio, 4- (p-methylbenzoyl) phenylthio, 4- (p-ethylbenzoyl) phenylthio, 4- (p-isopropylbenzoyl) phenylthio, 4- (p-tert-butylbenzoyl) Arylthio groups having 6 to 20 carbon atoms such as phenylthio; methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, t straight chain or branched alkylthio groups having 1 to 18 carbon atoms such as rt-pentylthio, octylthio, decylthio, dodecylthio; aryl groups having 6 to 10 carbon atoms such as phenyl, tolyl, dimethylphenyl, naphthyl; thienyl, furanyl, pyranyl, Pyrrolyl, oxazolyl, thiazolyl, biridyl, birimidyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thiantenyl, phenoxazinyl, phenoxazinyl, Heterocyclic groups having 4 to 20 carbon atoms such as isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, dibenzofuranyl; phenoxy, naphthyloxy An aryloxy group having 6 to 10 carbon atoms such as thio; methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isoptylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, Straight chain or branched alkylsulfinyl groups having 1 to 18 carbon atoms such as pentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl; arylsulfinyl groups having 6 to 10 carbon atoms such as funilylsulfinyl, tolylsulfinyl, naphthylsulfinyl; methylsulfonyl , Ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfur A linear or branched alkylsulfonyl group having 1 to 18 carbon atoms such as nyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, octylsulfonyl; phenylsulfonyl, tolylsulfonyl (tosyl group) ), An arylsulfonyl group having 6 to 10 carbon atoms such as naphthylsulfonyl;

An alkyleneoxy group represented by the general formula (8) (Q represents a hydrogen atom or a methyl group, k is an integer of 1 to 5); an unsubstituted amino group and an alkyl group and / or carbon having 1 to 5 carbon atoms; Amino group mono- or di-substituted by an aryl group of several 6 to 10 (specific examples of alkyl groups having 1 to 5 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl and pentyl; isopropyl , Isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, etc., branched alkyl groups; , Cyano group; nitro group; fluorine, chlorine, bromine, iodine And the like halogen such as.

In addition, two or more R's are each directly or —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR′— (R ′ is an alkyl group having 1 to 5 carbon atoms or carbon Specific examples of the alkyl group having 1 to 5 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, isopropyl, isoptyl, sec-butyl, tert- Examples include branched alkyl groups such as butyl, isopentyl, neopentyl, tert-pentyl, etc., cycloalkyl groups such as cyclopropyl, cycloptyl, cyclopentyl, etc. Specific examples of aryl groups having 6 to 10 carbon atoms include phenyl, naphthyl, and the like. ), -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms or a phenylene group to bond element A The following can be mentioned as an example which formed the ring structure containing.

[A is Group VIA to Group VIIA (CAS notation), L is —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR′—, —CO—, —COO—, — CONH-. R ′ is the same as described above. ]

In the formula (1), m + n (m−1) +1 R bonded to the element A of the valence m group VIA to VIIA (CAS notation) may be the same or different, At least one of R, more preferably all of R, is an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 4 to 30 carbon atoms, which may have the substituent.

D in the formula (1) is represented by the structure of the formula (2), and E in the formula (2) is a linear, branched or cyclic alkylene having 1 to 8 carbon atoms such as methylene, ethylene and propylene. Groups: arylene groups having 6 to 20 carbon atoms such as phenylene, xylylene, naphthylene, biphenylene, anthracenylene; dibenzofurandiyl, dibenzothiophenediyl, xanthenediyl, phenoxathiindiyl, thianthrangeyl, bithiophenediyl, bifuranyl, thioxanthone It represents a divalent group of a heterocyclic compound having 8 to 20 carbon atoms such as diyl, xanthonediyl, carbazolediyl, acridinediyl, phenothiazinediyl, phenazinediyl. Here, the divalent group of the heterocyclic compound refers to a divalent group formed by removing one hydrogen atom from two different ring carbon atoms of the heterocyclic compound.

The divalent group of the alkylene group, arylene group or heterocyclic compound may have at least one substituent. Specific examples of the substituent include methyl, ethyl, propyl, butyl,
Straight chain alkyl group having 1 to 8 carbon atoms such as pentyl and octyl; branched alkyl group having 1 to 8 carbon atoms such as isopropyl, isoptyl, sec-butyl and tert-butyl; and 3 carbon atoms such as cyclopropyl and cyclohexyl A cycloalkyl group having 8 to 8 carbon atoms; an alkoxy group having 1 to 8 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, and hexyloxy; an aryl group having 6 to 10 carbon atoms such as phenyl and naphthyl; a hydroxy group; a cyano group; a nitro group Alternatively, halogen such as fluorine, chlorine, bromine and iodine can be used.

G in the formula (2) represents —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR′— (R ′ is the same as above), —CO—, —COO—. , -CONH-, an alkylene group having 1 to 3 carbon atoms or a phenylene group. Examples of the alkylene group having 1 to 3 carbon atoms include linear or branched alkylene groups such as methylene, ethylene, and propylene.

A in Formula (2) is an integer of 0-5. a + 1 E and a G may be the same as or different from each other. A typical example of D represented by the formula (2) is shown below. If a = 0,

If a = 1,

If a = 2,

If a = 3,

Of these D, the following groups are particularly preferred.

N in Formula (1) represents the number of repeating units of the [D-A ⁺ R _m-1 ] bond, and is an integer of 0 to 3, preferably 0 or 1.

Preferred examples of the onium ion [A ⁺ ] in the formula (1) include sulfonium, iodonium, and selenium. Typical examples include the following.

Examples of the sulfonium ions include triphenylsulfonium, tri-p-tolylsulfonium, tri-O-tolylsulfonium, tris (4-methoxyphenyl) sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris (4-fluorofuyu Nyl) sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris (4-hydroxyphenyl) sulfonium, 4- (phenylthio) phenyldiphenylsulfonium, 4- (p-tolylthio) phenyldi-p-tolylsulfonium, 4- (4-methoxyphenylthio) phenylbis (4-methoxyphenyl) sulfonium, 4- (phenyl (4-fluorophenyl) sulfonium, 4- (phenylthio) phenylbis (4- Toxifunyl) sulfonium, 4- (phenylthio) funilyl-p-tolylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, bis [4- (bis [4- (2-hydroxyethoxy) phenyl] sulfonio) phenyl] Sulfide, bis (4- [bis (4-fluorophenyl) sulfonio] phenyl) sulfide, bis (4- [bis (4-methylphenyl) sulfonio] funilyl) sulfide, bis (4- [bis (4-methoxyphenyl) sulfide Sulfonio] phenyl) sulfide, 4- (4-benzoyl-2-chlorofuunylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenyldiphenylsulfonium, 4- (4- Benzoylphenylthio) Nylbis (4-fluorophenyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl) sulfonio] thioxanthone, 2-[(diphenyl) sulfonio] thioxanthone, 4 -[4- (4-tert-Ptylbenzoyl) phenylthio] phenyldi-pL tolylsulfonium, 4- [4- (4-tert-Ptylbenzoyl) phenylthio] phenyldiphenylsulfonium, 4- [4- (benzoylphenylthio)] Phenyldi-p- Tolylsulfonium, 4- [4- (benzoylphenylthio)] phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiaanthrhenium, 5-phenylthiaanthrhenium, 5-tolylthiaanthrhenium, 5- (4-ethoxy Triarylsulfonium such as phenyl) thiaanthrhenium, 5- (2,4,6-trimethylphenyl) thiaanthrhenium; diaryl such as diphenylphenacylsulfonium, diphenyl4-nitrophenacylsulfonium, diphenylbenzylsulfonium, diphenylmethylsulfonium Sulfonium; phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyph Nylmethylbenzylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, funilylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacyl Monoarylsulfonium such as sulfonium, 4-acetocarbonyloxyphenylmethylphenacylsulfonium, 2-naphthylmethylphenacylsulfonium, 2-naphthyloctadecylphenacylsulfonium, 9-anthracenylmethylphenacylsulfonium; dimethylphenacylsulfonium, phena Siltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, octadecylmethylphenol Examples include trialkylsulfonium such as enacilsulfonium, and these are described in the following documents.

  Regarding triarylsulfonium, U.S. Pat. No. 4,231,951, U.S. Pat. No. 4,256,828, JP-A-7-61964, JP-A-8-165290, JP-A-7-10914, JP-A-7-25922, JP-A-8- 27208, JP-A-8-27209, JP-A-8-165290, JP-A-8-301991, JP-A-9-143212, JP-A-9-278813, JP-A-10-7680, JP-A-10-287463. JP-A-10-245378, JP-A-8-157510, JP-A-10-204083, JP-A-8-245656, JP-A-8-157451, JP-A-7-324069, JP-A-9-268205. JP, 9-278935, JP 2001-288205, JP 11-80118, JP JP-A-10-182825, JP-A-10-330353, JP-A-10-152495, JP-A-5-239213, JP-A-7-333834, JP-A-9-12537, JP-A-8-325259, JP-A-8-160606. JP, 2000-186071 (US Pat. No. 6,368,769), etc .; Regarding diarylsulfonium, JP-A-7-300504, JP-A-64-45357, JP-A-64-29419, etc .; Monoarylsulfonium JP-A-6-345726, JP-A-8-325225, JP-A-9-118663 (US Pat. No. 6,097,753), JP-A-2-196812, JP-A-2-1470, and JP-A-2-196812. JP-A-3-237107, JP-A-3-17101, JP-A-6-22 No. 086, JP-A-10-152469, JP-A-7-300505, JP-A-2003-277353, JP-A-2003-277352, etc .; regarding trialkylsulfonium, JP-A-4-308563, JP-A-5-140210, JP-A-5-140209, JP-A-5-230189, JP-A-6-271532, JP-A-58-37003, JP-A-2-178303, JP-A-10-338688, JP-A-9-328506, JP-A-11-228534, JP-A-8-27102, JP-A-7-333834, JP-A-5-222167, JP-A-11-21307, JP-A-11-35613, US Pat. It is done.

Examples of the iodonium ion include diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, and bis (4-decyloxyphenyl). ) Iodonium, 4- (2-hydroxytetradecyloxy) phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium, isobutylphenyl (p-tolyl) iodonium, and the like, which are described in Macromolecules, 10, 1307 ( 1977), JP-A-6-184170, U.S. Pat. No. 4,256,828, U.S. Pat. No. 4,351,708, JP-A-56-135519, JP-A-58-38350, JP-A-10-195117, JP-A-2001-13953. 9, JP-A 2000-510516, JP-A 2000-119306, and the like.

Examples of selenium ions include triphenyl selenium, tri-p-tolyl selenium, tri-0-tolyl selenium, tris (4-methoxyphenyl) selenium, 1-naphthyldiphenyl selenium, tris (4-fluorophenyl) selenium, tri-1 -Triaryl selenium such as naphthyl selenium, tri-2-naphthyl selenium, tris (4-hydroxyphenyl) selenium, 4- (phenylthio) phenyl diphenyl selenium, 4- (p-tolylthio) phenyl di-p-tolyl selenium; diphenylphena Diaryl selenium such as silselenium, diphenylbenzyl selenium, diphenylmethyl selenium; phenylmethylbenzyl selenium, 4-hydroxyphenylmethylbenzyl selenium, pheny Monoaryl selenium such as methylphenacyl selenium, 4-hydroxyphenylmethyl phenacyl selenium, 4-methoxyphenyl methyl phenacyl selenium; Examples thereof include trialkyl selenium such as octadecylmethylphenacyl selenium, and these are described in JP-A-50-151997, JP-A-50-151976, JP-A-53-22597, and the like.

Of these oniums, preferred are sulfonium and iodonium, and particularly preferred are triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonio). Phenyl] sulfide, bis [4- (bis [4- (2-hydroxyethoxy) phenyl] sulfonio) funilyl] sulfide, bis (4- [bis (4-fluorophenyl) sulfonio] phenyl) sulfide, 4- (4- Benzoyl-2-chlorophenylthio) phenylbis (4-fluorofunilyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene- 21 Di-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl) sulfonio] thioxanthone, 2-[( Diphenyl) sulfonio] thioxanthone, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- [4- (benzoylphenylthio)] phenyldiphenylsulfonium, 5- (4-methoxyphenyl) ) Thiaanthrhenium, 5-phenylthiaanthrhenium, diphenylphenacylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, 4-hydroxyphenylmethylphenacyl Sulfonium ions such as rufonium and octadecylmethylphenacylsulfonium, and diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, And iodonium ions such as bis (4-decyloxy) phenyliodonium, 4- (2-hydroxytetradecyloxy) phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium and 4-isobutylphenyl (p-tolyl) iodonium. It is done.

The ligand Ll of the formula (4) representing the fluorinated alkylfluorophosphate of the transition metal complex of the present invention mainly contains an aromatic compound having 6 to 24 carbon atoms or a heteroatom such as oxygen, nitrogen and sulfur. It is a C4-C20 heterocyclic compound containing three, and they may be the same or different. Examples of the aromatic compound having 6 to 24 carbon atoms include monocyclic compounds such as benzene, and naphthalene, anthracene, phenanthrene, bilene, chrysene, naphthacene, benzoanthracene, anthraquinone, naphthoquinone, indene, biphenylene, fluorene, triphenylene, coronene, etc. The condensed polycyclic type can be mentioned.
Examples of the heterocyclic compound having 4 to 20 carbon atoms include monocyclic compounds such as thiophene, furan, pyran, pyrrole, oxazole, thiazole, pyridine, birimidine, pyrazine, indole, benzofuran, benzothiophene, quinoline, isoquinoline, and quinoxaline. , Quinazoline, carbazole, acridine, funothiazine, phenazine, xanthene, thianthrene, phenoxazine, phenoxathiin, chroman, isochroman, dibenzothiophene, xanthone, thioxanthone, dibenzofuran and the like.

These aromatic compounds or heterocyclic compounds may be substituted with at least one selected from the following substituents. Examples of the substituents include methyl, ethyl, propyl, butyl, pentyl, octyl, decyl. A linear alkyl group having 1 to 12 carbon atoms such as isopropyl, isoptyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl and the like; a branched alkyl group having 1 to 12 carbon atoms; cyclopropyl C3-C6 cycloalkyl group such as cyclopropyl, cyclopentyl, cyclohexyl, etc .; C1-C6 such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, etc. Linear and branched alkoxy groups; methylthio, Linear and branched alkylthio groups having 1 to 6 carbon atoms such as tilthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio; arylthio groups having 6 to 12 carbon atoms such as phenylthio and naphthylthio groups; Linear and branched alkylcarbonyl groups having 2 to 7 carbon atoms such as acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, Linear and branched alkoxycarbonyl groups having 2 to 7 carbon atoms such as isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, secc-butoxycarbonyl, tert-butoxycarbonyl; fluorine, chlorine Halogen such as bromine, iodine; phenyl group; benzoyl group; cyano group or nitro group.

Specific examples of the aromatic compound having the above substituent include toluene, xylene, ethylbenzene, cumene, mesitylene, methoxybenzene, ethoxybenzene, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,4-dimethoxy. Benzene, 1,3,5-trimethoxybenzene, acetylbenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 2-chlorotoluene, 3-chlorotoluene, 4- Chlorotoluene, bromobenzene, 1,2-dipromobenzene, 1,3-dipromobenzene, 1,4-dipromobenzene, 2-bromotoluene, 3-bromotoluene, 4-bromotoluene, 1-methylnaphthalene, 2-methylnaphthalene, 1-methoxynaphthalene, 2-methoxy Futaren, 1-chloronaphthalene, 2-chloronaphthalene, 1-bromonaphthalene, 2-bromonaphthalene, biphenyl, diphenyl ether, diphenyl sulfide, etc. triphenylene and the like.

Examples of the ligand L2 of the formula (4) include an anion of indene, fluorene or cyclopentadiene. When two L2s are present, they may be the same or different. These may be substituted with at least one of the same substituents as in the case of the above-mentioned ligand L1, and examples thereof include 2-methylindene, 2-ethylindene, 4-methylindene, 4-chloroindene. Anions of indene derivatives such as: anions of fluorene derivatives such as 1-methylfluorene, 4-methylfluorene, 4-methoxyfluorene, 1-chlorofluorene; methylcyclopentadiene, pentamethylcyclopentadiene, phenylcyclopentadiene, chlorocyclopentadiene, etc. And an anion of the cyclopentadiene derivative.

In formula (4), M is one type of transition metal element selected from group VIB to group VIII (CAS notation), and examples thereof include Cr, Mo, W, Mn, Fe, and Co. Of these, Fe is preferred.

Examples of the transition metal complex cation represented by the general formula (4) include (η ⁵ -cyclopentadienyl) (η ⁶ -toluene) Cr ⁺ , (η ⁵ -cyclopentadienyl) (η ⁶ -xylene). ) ^Cr +, (η ⁵ - cyclopentadienyl) (η ⁶ -1- methylnaphthalene) ^Cr +, (η ⁵ - cyclopentadienyl) (η ⁶ - cumene) ^Cr +, (η ⁵ - cyclopentadienyl Genis (Η) ⁶ -mesitylene) Cr ⁺ , (η ⁵ -cyclopentadienyl) (η ⁶ -birene) Cr ⁺ , (η ⁵ -fluorenyl) (η ⁶ -cumene) Cr ⁺ , (η ⁵ -indenyl) (Η ⁶ -cumene) Cr ⁺ , bis (η ⁶ -mesitylene) Cr ²⁺ , bis (η ⁶ -xylene) Cr ²⁺ , bis (η ⁶ -cumene) Cr ²⁺ , bis (η ⁶ -toluene) Cr ²⁺ , ( η ⁶ - torr Down) (eta ⁶ - xylene) ^{Cr 2+,} (η ⁶ - cumene) (eta ⁶ - naphthalene) ^{Cr 2+,} bis (eta ⁵ - cyclopentadienyl) Cr ^+, bis (eta ⁵ - indenyl) ^Cr +, ( Cr compounds such as η ⁵ -cyclopentadienyl) (η ⁵ -fluorenyl) Cr ⁺ and (η ⁵ -cyclopentadienyl) (η ⁵ -indenyl) Cr ⁺
Further, (η ⁵ -cyclopentadienyl) (η ⁶ -toluene) Fe ⁺ , (η ⁵ -cyclopentadienyl) (η ⁶ -xylene) Fe ⁺ , (η ⁵ -cyclopentadienyl) (η ^6- 1-methylnaphthalene) Fe ⁺ , (η ⁵ -cyclopentadienyl) (η ⁶ -cumene) Fe ⁺ , (η ⁵ -cyclopentadienyl) (η ⁶ -mesitylene) Fe ⁺ , (η ⁵ -cyclopenta Dienyl) (η ⁶ -birene) Fe ⁺ , (η ⁵ -fluorenyl) (η ⁶ -cumene) Fe ⁺ , (η ⁵ -indenyl) (η ⁶ -cumene) Fe ⁺ , bis (η ⁶ -mesitylene) Fe ²⁺ , bis (η ⁶ -xylene) Fe ²⁺ , bis (η-cumene) Fe ²⁺ , bis (η-toluene) Fe ²⁺ , (η ⁶ -toluene) (η ⁶ -xylene) Fe ²⁺ , (η ⁶ -cumene ) (Η ⁶ -N Futaren) ^{Fe 2+,} bis (eta ⁵ - cyclopentadienyl) ^{Fe 2+,} bis (eta ⁵ - indenyl) ^Fe +, (η ⁵ - cyclopentadienyl) (η ⁵ - fluorenyl) Fe ⁺ and (eta ⁵ - And Fe compounds such as cyclopentadienyl) (η ⁵ -indenyl) Fe ⁺ .

These are described in Macromol. Chem. 81, 86 (1965), Angew. Makromol. Chem. , 50, 9 (1976) acromol. Chem. , 153, 229 (1972), J. et al. Polym. Sci. , Polym. Chem. Edn. , 14, 1547 (1976), Chem. Ztg. 108, 345 (1984); Imaging. Sci. , 30, 174 (1986), chem. Photobiol. A: Chem. 77 (1994); Rad. Curing. , 26 (1986), Adv. Polym. Sci. , 78, 61 (1986), U.S. Pat. JP-A-58-210904 (US Pat. No. 4,868,288), JP-A-59-108003, JP-A-2000-226396, JP-A-2-284903, and the like.

Among the above transition metal complex cations, preferred are (η ⁵ -cyclopentadienyl) (η ⁶ -toluene) Fe ⁺ , (η ⁵ -cyclopentadienyl) (η ⁶ -xylene) Fe ⁺ , ( eta ⁵ - cyclopentadienyl) (η ⁶ -1- methyl naphthalene) ^Fe +, (η ⁵ - cyclopentadienyl) (η ⁶ - cumene) ^Fe +, (η ⁵ - cyclopentadienyl) (eta ⁶ -Mesitylene) Fe ⁺ , (η ⁵ -cyclopentadienyl) (η ⁶ -birene) Fe ⁺ , (η ⁵ -fluorenyl) (η ⁶ -cumene) Fe ⁺ , (η ⁵ -indenyl) (η ⁶ -cumene ) Fe ⁺ , bis (η ⁶ -mesitylene) Fe ²⁺ , bis (η ⁶ -xylene) Fe ²⁺ , bis (η ⁶ -cumene) Fe ²⁺ , (η ⁶ -toluene) (η ⁶ -xylene) Fe ²⁺ , ( η ⁶ − Cumene) (η ⁶ -naphthalene) Fe ²⁺ , bis (η ⁵ -cyclopentadienyl) Fe ⁺ , bis (η ⁵ -indenyl) Fe ⁺ , (η ⁵ -cyclopentadienyl) (η ⁵ -fluorenyl) Fe ^{+ And} (η ⁵ -cyclopentadienyl) (η ⁵ -indenyl) Fe ⁺ .

In Formula (1) and Formula (4), X ⁻ is a counter ion. In formula (1), the number is n + 1 per molecule, and in formula (4), the number is e per molecule, of which at least one is a fluorinated alkyl represented by formula (3) It may be a fluorophosphate anion and the rest may be other anions. The other anion may be any conventionally known anion, for example, halogen ions such as F ⁻ , CI ⁻ , Br ⁻ and I ⁻ ; OH ⁻ , ClO ₄ ⁻ , FSO ₃ ⁻ , CISO ₃ ⁻ , Sulfonic acid ions such as CH ₃ SO ₃ ⁻ , C ₆ H ₅ SO ₃ ⁻ , CF ₃ SO ₃ ^— ; Sulfate ions such as HSO ₄ ⁻ and SO ₄ ²⁻ ; HCO ₃ ⁻ and CO ₃ ²⁻ Carbonate ions; Phosphate ions such as H ₂ PO ⁴⁻ , HPO ₄ ²⁻ , PO ₄ ³⁻ ; Fluorophosphate ions such as PF ₆ − and PF ₅ OH ⁻ ; BF ₄ ⁻ , B (C ₆ Boric acid ions such as F ₅ ) ₄ ⁻ and B (C ₆ H ₄ CF ₃ ) ₄ ^— ; AICI ₄ ⁻ ; BiF ₆ ^{— and the} like. Other examples include fluoroantimonate ions such as SbF ₆ ⁻ and SbF ₅ OH ^— or fluoroarsenate ions such as AsF ₆ ⁻ and AsF ₅ OH ⁻ , which are preferable because they contain toxic elements. Absent.

In the fluorinated alkylfluorophosphate anion represented by the formula (3), Rf represents an alkyl group substituted with a fluorine atom, preferably having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl and tert-butyl; and cyclopropyl, cyclobutyl and cyclopentyl. And the ratio of the hydrogen atom of the alkyl group substituted by a fluorine atom is usually 80% or more, preferably 90% or more, and more preferably 100%. When the fluorine atom substitution rate is less than 80%, the cationic polymerization initiating ability of the onium salt and transition metal complex salt of the present invention decreases.

Particularly preferred Rf is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100%. Specific examples include CF ₃ , CF ₃ CF ₂ , (CF _{3 ) 2 CF, CF 3 CF 2} CF 2, CF 3 CF 2 CF 2 CF 2, (CF 3) 2 CFCF 2, CF 3 CF 2 (CF 3) CF, include ^(CF ₃₎ 3 C.

In the formula (3), the number b of Rf is an integer of 1 to 5, preferably 2 to 4, particularly preferably 2 or 3. The b Rf's may be the same or different.

Specific examples of preferred fluorinated alkyl fluorophosphate anions include [(CF ₃ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) _2. PF ₄ ] ⁻ , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ] ⁻ and [ (CF ₃ CF ₂ CF ₂ CF ₂ ) ₃ PF ₃ ] ⁻ , and among these, [(CF ₃ CF ₂ ) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₃ P F ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ⁻ and [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ^- is particularly preferred.

The fluorinated alkyl fluorophosphates of the onium or transition metal complexes of the present invention can be prepared by a metathesis method. The metathesis method is, for example, New Experimental Chemistry Course 14-I (1978, Maruzen) p-448; Advancein Polymer Science, 62, 1-48 (1984); New Experimental Chemistry Course 14-III (1978, Maruzen) p1838. -1846; Organic sulfur chemistry (Synthetic Reactions, 1982, Kagaku Dojin), Chapter 8, p237-280; Nihon Kagaku Kagaku, 87, (5), 74 (1966) J. Chem. Org. Chem. , 32, 2580 (1967); Tetrahedron Letters, 36, 3437 (1973); Bulletindela Societe Chimiquede France, 1, 228 (1976); Bulletindela Societe Chimiquede Francell, 2571 (1975); Inorg. Chem. , 10, 1559 (1971); Chem. Ber. , 93, 2729 (1960);]. anomet. Chem. 54, 255 (1973); “organometallicSyntheses”, VOL. 1, AcademicPress, P138 (1965); Tetrahedron, 39, 4027 (1983);]. Amer. Chem. Soc. , 103, 758 (1981);]. Chem. Soc. Chem. Commun. , 1971, 930 (71);]. Amer. Chem. Soc. , 92, 7207 (1970); JP-A-64-45357, JP-A-61-212554, JP-A-61-100557, JP-A-5-4996, JP-A-7-82244, JP-A-7- 82245, JP-A 58-210904, JP-A 6-184170, etc. First, halogen ion salts of onium or transition metal complexes such as F ⁻ , CI ⁻ , Br ⁻ and I ⁻ ; OH ^- salt; ClO ₄ ^{- _{salt; FSO 3 -, CISO 3 -}} , CH 3 SO 3 -, C 6 H 5 SO 3 -, CF 3 SO 3 - salts with sulfonic acid ion such _as; ^HSO 4 -, SO ₄ Salts with sulfate ions such as ^2- ; Salts with carbonate ions such as HCO ₃ ⁻ and CO ₃ ²⁻ ; Phosphate ions such as H ₂ PO ₄ ⁻ , HPO ₄ ²⁻ and PO ₃ ⁴⁻ To produce salt and so on This and alkali metal salts, alkaline earth metal salts or quaternary ammonium salts of the fluorinated alkyl fluorophosphate anion represented by the formula (3), if _{necessary, KPF 6, KBF 4, LiB} (C 6 F 5) ₄ is added to an aqueous solution containing other anionic components such as ₄ or more in the theoretical amount to cause metathesis. Since the salt of the present invention thus produced is separated in the form of crystals or oil, the crystals can be recovered by filtration, and the liquid can be recovered by liquid separation or extraction with an appropriate solvent. The onium or transition metal complex salt of the present invention thus obtained can be purified by a method such as recrystallization or washing with water or a solvent, if necessary.

The structure of the fluorinated alkyl fluorophosphates of the onium and transition metal complexes obtained in this way can be analyzed by a general analytical method such as ¹ H, ¹³ C, ¹⁹ F, and ¹³ P nuclear magnetic resonance spectra. It can be identified by infrared absorption spectrum or elemental analysis.

As the fluorinated alkyl fluorophosphate used in the above metathesis reaction, an alkali metal salt is preferable. This salt is obtained by reacting a precursor fluorinated alkylfluorophosphorane with an alkali metal fluoride in an aprotic solvent such as dimethyl ether, ketoxyethane, acetonitrile or a mixture thereof at −35 to 60 ° C. (US Pat. No. 6,210,830). The precursor fluorinated alkylfluorophosphorane is obtained, for example, by a method of electrochemically fluorinating alkylphosphine with hydrofluoric acid at a temperature of −15 to 20 ° C. under normal pressure (US Pat. No. 6,264,818). . The progress of electrochemical fluorination is proportional to the amount of electricity, and the fluorination is usually terminated when 90 to 150%, particularly 110 to 130% of the theoretical amount of electricity is consumed. As a result, a fluorinated alkylfluorophosphorane in which 80% or more, preferably 90% or more of the hydrogen atoms in the alkyl group are substituted with fluorine is obtained. The target fluorinated alkyl fluorophosphorane is separated from the electrolyte, and is recovered by liquid separation. If necessary, it is purified by distillation.

The onium and transition metal complex fluorinated alkyl fluorophosphates of the present invention may be used alone as a cationic polymerization initiator or in combination of two or more. Moreover, you may use together with another conventionally well-known cationic polymerization initiator. Examples of other cationic initiators include salts of onium ions such as sulfonium, iodonium, selenium, ammonium, phosphonium, or transition metal complex ions and various anions. Examples of anions include F ⁻ , CI ⁻ , Halogen ions such as Br ⁻ and I ^— ; sulfonate ions such as OH ⁻ ; ClO ₄ ⁻ ; FSO ₃ ⁻ , CISO ₃ ⁻ , CH ₃ SO ₃ ⁻ , C ₆ H ₅ SO ₃ ⁻ and CF ₃ SO ₃ ^{−. _{; HSO 4 -, SO 4 2}} - sulfate ions such _{^{as; HCO 3 -, CO 3 2}} - carbonate ions such _{^{as; H 2 PO 4 -, HPO}} 4 2-, PO 4 3- phosphate ions such as Fluorophosphate ions such as PF ₆ ⁻ and PF ₅ OH ⁻ ; BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , B (C ₆ H ₄ CF ₃ ) ₄ ^- borate ions such _{^{as; AICI 4 -; BiF 6 -}} ; SbF 6 -, SbF 5 OH - fluoro antimonate ion such _{^{as; AsF 6 -, AsF 5 OH}} - and fluoroarsenate periodate ions such as Can be mentioned. Further, it may be used in combination with ammonium or phosphonium fluorinated alkyl fluorophosphate. However, fluoroantimonate ions and fluoroarsenate ions are not preferable because they contain toxic elements.

The sulfonium ion, iodonium ion, or selenium ion includes all known ones, and typical examples and references are described in [0085] to [0088] in the present specification.

Examples of the ammonium ion include tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, tetraethylammonium, trimethyl-n-propylammonium, trimethylisopropylammonium, trimethyl-n-butylammonium, trimethylisobutylammonium, Tetraalkylammonium such as trimethyl-t-butylammonium, trimethyl-n-hexylammonium, dimethyldi-n-propylammonium, dimethyldiisopropylammonium, dimethyl-n-propylisopropylammonium, methyltri-n-propylammonium, methyltriisopropylammonium N, N-dimethylpyrrolidinium, N- Pyrrolidinium such as til-N-methylpyrrolidinium, N, N-diethylpyrrolidinium; N, N′-dimethylimidazolinium, N, N′-diethylimidazolinium, N-ethyl-N′-methylimidazole Linium, 1,2,3-trimethylimidazolinium, 1,3,4-trimethylimidazolinium, 1,3-diethyl-2-methylimidazolinium, 1,3-diethyl-4-methylimidazolinium , 1,2,3,4-tetramethylimidazolinium and the like; N, N′-dimethyltetrahydrovirimidinium, N, N′-diethyltetrahydrovirimidinium, N-ethyl-N′-methyl Tetrahydrobilimidinium, tetrahydrobilimidinium such as 1,2,3-trimethyltetrahydrovirimidinium; N, N′- Morpholinium such as methylmorpholinium, N-ethyl-N-methylmorpholinium, N, N-diethylmorpholinium; N, N-dimethylpiperidinium, N-ethyl-N′-methylpiperidinium, N Piperidinium such as N, -diethylpiperidinium; N-methylbilidinium, N-ethylbilidinium, Nn-propylbilidinium, N-isopropylviridinium, Nn-butylpyridinium, N -Viridinium such as benzyl viridinium, N-phenacyl pyridium; N, N'-dimethylimidazolium, N-ethyl-N-methylimidazolium, N, N'-diethylimidazolium, 1,2-diethyl- 3-methylimidazolium, 1,3-diethyl-2-methylimidazolium, 1-methyl-3-n-propyl-2 Imidazolium such as 4-dimethylimidazolium; N-methylquinolium, N-ethylquinolium, Nn-propylquinolium, N-isopropylquinolium, Nn-butylquinolium, N-benzylquinolium, Quinolium such as N-phenacylquinolium; N-methylisoquinolium, N-ethylisoquinolium, Nn-propylisoquinolium, N-isopropylisoquinolium, Nn-butylisoquinolium, N -Isoquinolium such as benzylisoquinolium and N-phenacylisoquinolium; thiazonium such as benzylbenzothiazonium and phenacylbenzothiazonium; and acridium such as benzylacridium and phenacylacridium.
These include US Pat. No. 4069055, Japanese Patent No. 2519480, Japanese Patent Laid-Open No. 5-222112, Japanese Patent Laid-Open No. 5-222111, Japanese Patent Laid-Open No. 5-262613, Japanese Patent Laid-Open No. 5-255256, Japanese Patent Laid-Open No. 7-109303, Kaihei 10-101718, JP-A-2-268173, JP-A-9-328507, JP-A-5-132461, JP-A-9-221652, JP-A-7-43854, JP-A-7-43901, JP-A-7-43901 No. 5-26213, JP-A-4-327574, JP-A-2-43202, JP-A-60-203628, JP-A-57-209931, JP-A-9-221652, and the like.

Examples of the phosphonium ion include tetraarylphosphonium, tetra-p-tolylphosphonium, tetrakis (2-methoxyphenyl) phosphonium, tetrakis (3-methoxyphenyl) phosphonium, tetrakis (4-methoxyphenyl) phosphonium, and the like. Phosphonium; triarylphosphonium such as triphenylbenzylphosphonium, triphenylphenacylphosphonium, triphenylmethylphosphonium, triphenylptylphosphonium; triethylbenzylphosphonium, tryptylbenzylphosphonium, tetraethylphosphonium, tetraptylphosphonium, tetrahexylphosphonium, triethyl Tetraamines such as phenacylphosphonium and triptylphenacylphosphonium Kiruhosuhoniumu and the like. These are described in JP-A-6-157624, JP-A-5-105692, JP-A-7-82283, JP-A-9-202873, and the like.

Representative examples and references of the above transition metal complex ions are described in [0095] to [0096] in the present specification.

The component [C] of the present invention may be dissolved in advance in a solvent that does not inhibit cationic polymerization in order to facilitate dissolution in the cationic polymerizable compound. Examples of the solvents include propylene carbonate, ethylene, and the like. Carbonates such as carbonate, 1,2-butylene carbonate, dimethyl carbonate, and diethyl carbonate; esters such as ethyl acetate, ethyl lactate, β-probiolactone, β-butyrolactone, γ-butyrolactone, ∂-valerolactone, and -caprolactone Monoalkyl ethers such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, such as monomethyl ether, monoethyl ether, monobutyl ether Matter dialkyl Ether chromatography include, for example, dimethyl ether, diethyl ether, dibutyl ether, more like glycols such as acetic acid esters of the monoalkyl ethers. When these solvents are used, the use ratio is usually 15 to 1000 parts, preferably 30 to 500 parts, with respect to 100 parts of the [C] component.

In the present invention, the proportion of the component [C] used is usually 0.05 to 10 parts, preferably 0.1 to 5 parts, based on 100 parts by weight of the copolymer [A]. It is determined by considering various factors such as the nature of the cationically polymerizable compound, the type and dose of energy rays, temperature, curing time, humidity, and coating thickness. When the amount of the component [C] used is less than 0.05 part, the polymerization of the cationic polymerizable compound is insufficient, and when it is more than 10 parts, the properties of the cured product are deteriorated due to the unreacted cationic polymerization initiator or its decomposition product. There is a case.

A conventionally known sensitizer can be used in combination with the radiation-sensitive resin composition of the present invention, if necessary. Examples of such sensitizers are described in JP-A-11-279212, JP-A-9-183960, and the like. Specifically, anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxy Anthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-tert-butyl-9,10-dimethoxyanthracene, 2,3-dimethyl-9,10-dimethoxyanthracene, 9-methoxy-10-methylanthracene, 9, 10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-tert-butyl-9,10-diethoxyanthracene, 2,3-dimethyl-9,10-diethoxyanthracene, 9-ethoxy- 10-methylanthracene, 9,10-dipropoxyanthracene, 2-ethyl-9, 0-dipropoxyanthracene, 2-tert-butyl-9,10-dipropoxyanthracene, 2,3-dimethyl-9,10-dipropoxyanthracene, 9-isopropoxy-10-methylanthracene, 9,10-dibenzyl Oxyanthracene, 2-ethyl-9,10-dibenzyloxyanthracene, 2-tert-9,10-dibenzyloxyanthracene, 2,3-dimethyl-9,10-dibenzyloxyanthracene, 9-benzyloxy-10- Methyl anthracene, 9,10-di α-methylbenzyloxyanthracene, 2-ethyl-9,10-di α-methylbenzyloxyanthracene, 2-tert-9,10-di α-methylbenzyloxyanthracene, 2,3- Dimethyl-9,10-di-α-methylbenz Ruoxyanthracene, 9- (α-methylbenzyloxy) -10-methylanthracene, 9,10-diphenylanthracene, 9-methoxyanthracene, 9-ethoxyanthracene, 9-methylanthracene, 9-bromoanthracene, 9-methylthioanthracene Anthracene such as 9-ethylthioanthracene; bilene; 1,2-benzoanthracene; perylene; tetracene; coronene; thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2, Thioxanthones such as 4-diethylthioxanthone; phenothiazine; xanthone; 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dihydroxy Naphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,7-dimethoxynaphthalene, 1,1′-thiobis (2-naphthol), 1,1′-pea (2 -Naphthol), naphthalenes such as 4-methoxy-1-naphthol; dimethoxyacetophenone, ethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2 -Methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tert-ptyldichloroacetophenone, p- tert-ptyltrichloroacetophenone, p -Azidobenzalacetophenone, 1-hydroxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isoptyl ether, 1- [4- (2-hydroxy Ethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, benzophenone, methyl 0-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, 4- Ketones such as benzoyl-4′-methyldiphenyl sulfide; carbazoles such as N-phenylcarbazole, N-ethylcarbazole, poly-N-vinylcarbazole, N-glycidylcarbazole; Chrysene such as 1,4-dimethoxychrysene, 1,4-detoxychrysene, 1,4-dipropoxychrysene, 1,4-dibenzyloxychrysene, 1,4-diα-methylbenzyloxychrysene; 9-hydroxy Phenanthrene, 9-methoxyphenanthrene, 9-ethoxyphenanthrene, 9-benzyloxyphenanthrene, 9,10-dimethoxyphenanthrene, 9,10-jetoxyphenanthrene, 9,10-dipropoxyphenanthrene, 9,10-dibenzyloxyphenanthrene, Examples include phenanthrenes such as 9,10-di-α-methylbenzyloxyphenanthrene, 9-hydroxy-10-methoxyphenanthrene, and 9-hydroxy-10-ethoxyphenanthrene.

The use ratio in the case of using these sensitizers is 0.005-20 parts normally with respect to 100 weight part of copolymer [A] of this invention, Preferably it is 0.01-10 parts.

Other Components The radiation-sensitive resin composition of the present invention contains the above-mentioned copolymer [A], [B], and [C] components as essential components, but [D] at least 1 as necessary. A polymerizable compound having one ethylenically unsaturated double bond, an epoxy resin other than the [E] copolymer [A], a [F] surfactant, or a [G] adhesion aid.

  Examples of the above-mentioned [D] polymerizable compound having at least one ethylenically unsaturated double bond (hereinafter sometimes referred to as “[D] component”) include monofunctional (meth) acrylate and bifunctional (meta) ) Acrylate or tri- or higher functional (meth) acrylate can be preferably mentioned.

  Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl. And 2-hydroxypropyl phthalate. As these commercial products, for example, Aronix M-101, M-111, M-114 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S, TC-120S (above, Nippon Kayaku Co., Ltd.) ) Co., Ltd.), Biscoat 158, 2311 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.).

  Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange acrylate. As these commercial products, for example, Aronix M-210, M-240, M-6200 (above, manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, HX-220, R-604 (above, Nippon Kayaku) Medicine Co., Ltd.), Viscoat 260, 312 and 335HP (above, Osaka Organic Chemical Industries, Ltd.).

  Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, and pentaerythritol tetra (meth) acrylate. , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like, and as commercially available products thereof, for example, Aronix M-309, M-400, M-405, M-450, M-7100, M-8030, M-8060 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (Nippon Kayaku Co., Ltd.), screw Over DOO 295, the 300, the 360, the GPT, said 3PA, the 400 (manufactured by Osaka Organic Chemical Industry Ltd.) and the like.

Of these, trifunctional or higher functional (meth) acrylates are preferably used, and among them, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are particularly preferable.
These monofunctional, bifunctional, or trifunctional or higher (meth) acrylates are used alone or in combination. The proportion of the component [D] used is preferably 50 parts by weight or less, more preferably 30 parts by weight or less with respect to 100 parts by weight of the copolymer [A].
By including the component [D] at such a ratio, the heat resistance and surface hardness of the interlayer insulating film or microlens obtained from the radiation-sensitive resin composition of the present invention can be improved. When the amount used exceeds 50 parts by weight, film roughening may occur in the step of forming a coating film of the radiation sensitive resin composition on the substrate.

  The epoxy resin other than the [E] copolymer [A] (hereinafter sometimes referred to as “[E] component”) is not limited as long as the compatibility is not affected. Preferably, bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, heterocyclic epoxy resin, glycidyl methacrylate ) Polymerized resins and the like can be mentioned. Of these, bisphenol A type epoxy resins, cresol novolac type epoxy resins, glycidyl ester type epoxy resins and the like are particularly preferable.

[E] The usage-amount of a component becomes like this. Preferably it is 30 weight part or less with respect to 100 weight part of copolymers [A]. By containing the component [E] at such a ratio, the heat resistance and surface hardness of the protective film or insulating film obtained from the radiation-sensitive resin composition of the present invention can be further improved. When this ratio exceeds 30 parts by weight, the film thickness uniformity of the coating film may be insufficient when a coating film of the radiation sensitive resin composition is formed on the substrate.
The copolymer [A] can also be referred to as an “epoxy resin”, but differs from the component [E] in that it has alkali solubility. [E] component is alkali-insoluble.

  In the radiation sensitive resin composition of the present invention, the above-mentioned [F] surfactant can be used in order to further improve the coating property. As the [F] surfactant that can be used here, fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants can be suitably used.

  Specific examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether. , Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1 , 2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2,8 , 8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc. Sodium Zensuruhon acid; fluoroalkyl polyoxyethylene ethers; fluoroalkyl ammonium iodide, fluoroalkyl polyoxyethylene ethers, perfluoroalkyl polyoxyethylene ethanol; can be exemplified fluorine-based alkyl esters; perfluoroalkyl alkoxylates. Examples of these commercially available products include BM-1000, BM-1100 (manufactured by BM Chemie), MegaFuck F142D, F172, F173, F183, F178, F191, F191 (and above, Dainippon Ink). Chemical Industries, Ltd.), Fluorad FC-170C, FC-171, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.) ), F-top EF301, 303, and 352 (manufactured by Shin-Akita Kasei Co., Ltd.).

  Examples of the silicone surfactant include DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032 (above, Toray Dow Corning)・ Silicon Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above, GE Toshiba Silicone Co., Ltd.) are commercially available. You can list what you have.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether Polyoxyethylene aryl ethers such as polyoxyethylene dilaurate, polyoxyethylene dialkyl esters such as polyoxyethylene distearate, etc .; (meth) acrylic acid copolymer polyflow Nos. 57 and 95 (Kyoeisha Chemical Co., Ltd.) ))) Can be used.

These surfactants can be used alone or in combination of two or more.
These [F] 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 copolymer [A]. [F] When the amount of the surfactant used exceeds 5 parts by weight, the coating film may be easily formed when the coating film is formed on the substrate.

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

Radiation-sensitive resin composition The radiation-sensitive resin composition of the present invention is a uniform mixture of the above-mentioned copolymer [A], [B] and [C] components and other components optionally added as described above. To be prepared. Usually, the radiation-sensitive resin composition of the present invention is preferably used in a solution state after being dissolved in an appropriate solvent. For example, preparing a radiation-sensitive resin composition in a solution state by mixing the copolymer [A], [B] and [C] components and other optionally added components in a predetermined ratio. Can do.

As a solvent used for the preparation of the radiation sensitive resin composition of the present invention, each component of the copolymer [A], [B] and [C] components and other components optionally blended is uniformly dissolved. And what does not react with each component is used.
As such a solvent, the thing similar to what was illustrated as a solvent which can be used in order to manufacture copolymer [A] mentioned above can be mentioned.

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

Furthermore, in order to improve the in-plane uniformity of the film thickness together with the solvent, a high boiling point solvent can be used in combination. Examples of the high boiling point solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether. , Dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl Examples include cellosolve acetate. Of these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.
When a high boiling point solvent is used in combination as the solvent of the radiation sensitive resin composition of the present invention, the amount used is preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 30%, based on the total amount of the solvent. It can be made into weight% or less. If the amount of the high-boiling solvent used exceeds this amount, the coating film thickness uniformity, sensitivity, and residual film rate may decrease.

When the radiation-sensitive resin composition of the present invention is prepared in a solution state, components other than the solvent in the solution (that is, the copolymer [A], [B] and [C] components and other optionally added) The ratio of the total amount of the components can be arbitrarily set according to the purpose of use, the value of the desired film thickness, etc., but is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, Preferably it is 15 to 35% by weight.
The composition solution thus prepared can be used after being filtered using a Millipore filter having a pore size of about 0.2 μm.

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

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

(2) Step of irradiating at least a part of the coating film In the step (2), the developer is applied after irradiating the formed coating film with radiation through a mask having a predetermined pattern. The patterning is performed by removing the irradiated portion using the development process. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
Examples of the ultraviolet rays include g-line (wavelength 436 nm), i-line (wavelength 365 nm), and the like. Examples of the far ultraviolet rays include KrF excimer laser. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include an electron beam.
Among these, ultraviolet rays are preferable, and radiation containing g-line and / or i-line is particularly preferable.
The exposure amount, 50~1,500J / ^{m 2} In the case of forming an interlayer insulating film, in the case of forming a micro-lens is preferably set to 50~2,000J / ^{m 2.}

(3) Development process Examples of the developer used in the development process include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, N-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene An aqueous solution of an alkali (basic compound) such as 1,5-diazabicyclo [4,3,0] -5-nonane can be used. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous alkali solution described above, or various organic solvents that dissolve the composition of the present invention can be used as a developing solution. Furthermore, as a developing method, for example, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time at this time varies depending on the composition of the composition, but can be, for example, 30 to 120 seconds.

(4) Heating step (3) After the development step, which is performed as described above, the patterned thin film is preferably rinsed by, for example, running water washing, and more preferably irradiated with radiation from a high-pressure mercury lamp or the like. (After post-exposure), the 1,2-quinonediadito compound remaining in the thin film is decomposed, and then the thin film is heated (post-baked) with a heating device such as a hot plate or an oven. Thus, the thin film is cured. The exposure amount in the post-exposure step is preferably about 2,000 to 5,000 J / m ² . In addition, as the heating temperature in the heat treatment step, conventionally, a treatment temperature of preferably about 200 to 250 ° C. has been adopted, but in the radiation-sensitive resin composition of the present invention, a treatment of about 170 to 200 ° C. is adopted. An interlayer insulating film or a microlens having various performances even at a temperature can be formed. As for the heating time, conventionally, when using a hot plate, a treatment time of preferably 15 to 30 minutes, and when using an oven, preferably 60 to 90 minutes has been adopted, but in the resin composition of the present invention, If the heating temperature is 200 ° C. or higher, the hot plate is used for 10 to 20 minutes, if the oven is used, 30 to 60 minutes. If the heating temperature is less than 200 ° C., the hot plate is used for 20 to 30 minutes. In the case of use, an interlayer insulating film or microlens having sufficient performance can be formed even if the processing time is 40 to 80 minutes. At this time, a step baking method or the like in which a heating process is performed twice or more can be used.
In this way, a patterned thin film corresponding to the target interlayer insulating film or microlens can be formed on the surface of the substrate.

Interlayer Insulating Film The interlayer insulating film of the present invention formed as described above has good adhesion to a substrate even at a post baking temperature of 200 ° C. or less, excellent solvent resistance and heat resistance, and an electronic component. It can be suitably used as an interlayer insulating film.

The microlens of the present invention formed as described above has good adhesion to the substrate, excellent solvent resistance and heat resistance, and high transmittance even at a post-bake temperature of 200 ° C. or less. It has a good melt shape and can be suitably used as a microlens for a solid-state imaging device.
The shape of the microlens of the present invention is a semi-convex lens shape as shown in FIG.

The present invention will be described more specifically with reference to synthesis examples and examples. However, the present invention is not limited to the following examples.
Synthesis of component [C] According to the examples of WO 05/116038 pamphlet, 4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate (hereinafter referred to as “C-1”). ), 4- (phenylthio) phenyldiphenylsulfonium tris (heptafluoropropyl) trifluorophosphate (hereinafter referred to as “C-2”) and (η ⁵ -cyclopentagenyl) (η ⁶ -toluene) Fe ( II) Tris (pentafluoroethyl) trifluorophosphate (hereinafter referred to as “C-3”) was synthesized.

Synthesis example of component [A] Synthesis example 1
Into a 500 mL three-necked flask equipped with a fractionating tube, 33.3 g of 2-hydroxyethyltrimethoxysilane and 72.1 g of dimethyldimethoxysilane were added and dissolved by adding 76.8 g of diethylene glycol methyl ethyl ether. The solution was warmed to 40 ° C. over 30 minutes while stirring with a magnetic stirrer. To this, 43.3 g of ion exchange water containing 1.4 g of oxalic acid was continuously added over 30 minutes. And after making it react at 40 degreeC for 2 hours, the obtained reaction liquid was pressure-reduced to 10 Torr, and methanol of a by-product was distilled off. Thereafter, the reaction solution was heated to 100 ° C. over 1 hour, and reacted at 100 ° C. for 2 hours while distilling off by-product water. The reaction solution thus obtained was cooled to 60 ° C., and 47.2 g of 3-glycidoxypropyltrimethoxysilane was first continuously added over 30 minutes, and then 10.8 g of 0.4 g of oxalic acid was contained. Ion exchange water was continuously added over 30 minutes and reacted at 60 ° C. for 3 hours. By-product methanol and water were distilled off from the reaction solution under reduced pressure, and the resin solution [A-1] obtained by adding diethylene glycol methyl ethyl ether to a solid content concentration of 40% had a weight average molecular weight of 2. , 600.

Synthesis example 2
In a 500 mL three-necked flask equipped with a fractionating tube, 39.3 g of 3-mercaptopropyltrimethoxysilane and 119.0 g of phenyltrimethoxysilane were added and dissolved by adding 76.8 g of diethylene glycol methyl ethyl ether. The mixed solution was heated to 40 ° C. over 30 minutes while stirring with a magnetic stirrer. To this, 43.3 g of ion exchange water containing 1.4 g of oxalic acid was continuously added over 30 minutes. And after making it react at 40 degreeC for 2 hours, the obtained reaction liquid was pressure-reduced to 10 Torr, and methanol of a by-product was distilled off. Thereafter, the reaction solution was heated to 100 ° C. over 1 hour, and reacted at 100 ° C. for 2 hours while distilling off by-product water. The reaction solution thus obtained was cooled to 60 ° C., and 49.3 g of 2- (3 ′, 4′-epoxycyclohexyl) ethyltrimethoxysilane was first continuously added over 30 minutes, and then 0.4 g of oxalic acid was added. Was added continuously over 30 minutes, and reacted at 60 ° C. for 3 hours. By-product methanol and water were distilled off from the reaction solution under reduced pressure, and the resin solution [A-2] obtained by adding diethylene glycol methyl ethyl ether to a solid content concentration of 40% had a weight average molecular weight of 2. , 500.

Synthesis example 3
In a 500 mL three-necked flask, 55.7 g of 3- (3′-ethyloxetane-3′-yl) propyltrimethoxysilane, 66.1 g of trimethoxysilylpropyl-2- (4′-hydroxyphenyl) propylthioether, methyl 40.3 g of trimethoxysilane was taken, 139.7 g of methyl isobutyl ketone was added and dissolved, and the resulting mixed solution was heated to 60 ° C. while stirring with a magnetic stirrer. To this, 54.0 g of ion-exchanged water containing 1.0 g of triethylamine was continuously added over 1 hour. And after making it react at 60 degreeC for 3 hours, the obtained reaction liquid was cooled to room temperature. Thereafter, 200 g of a 1% by weight oxalic acid aqueous solution was added, the organic phase was separated, and the same operation was repeated. The organic layer thus obtained was washed with 200 g of ion exchange water. From the obtained organic layer, alcohol and water as reaction by-products were distilled off from the reaction solution under reduced pressure. The weight average molecular weight of this polymer [A-3] was 2,400.

Comparative Synthesis Example 1
Into a 500 mL three-necked flask equipped with a fractionating tube, 88.5 g of methyltrimethoxysilane and 69.4 g of phenyltrimethoxysilane are added and dissolved by adding 138.9 g of diacetone alcohol. While stirring with a tic stirrer, 54.0 g of ion-exchanged water containing 0.2 g of phosphoric acid was continuously added over 30 minutes. And after making it react at 40 degreeC for 30 minutes, it heated up to 100 degreeC over 1 hour, and was made to react for 2 hours, distilling off methanol and water. Then, it diluted so that solid content might be 35 weight% and diacetone alcohol / gamma-butyrolactone = 90/10, and resin solution [a-1] was obtained. The weight average molecular weight of this polymer [a-1] was 2,900.

Example 1
[Preparation of radiation-sensitive resin composition]
A solution containing the polymer [A-1] as the component [A] synthesized in Synthesis Example 1 was added in an amount corresponding to 100 parts by weight (solid content) of the polymer [A-1], and 4 as the component [B]. , 4 ′-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride ( 2.0 mol) of the condensate (B-1) 30 parts by weight and 4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate (C-1) 3 parts by weight, After dissolving in diethylene glycol ethyl methyl ether so that the partial concentration becomes 30% by weight, the solution is filtered through a membrane filter having a diameter of 0.2 μm to obtain a solution of the radiation sensitive resin composition ( -1) was prepared.

Examples 2-10, 12-18, Comparative Examples 1-7
[Preparation of radiation-sensitive resin composition]
In Example 1, it implemented like Example 1 except having used the kind and quantity as shown in Table 1 as [A], [B], and [C] component, and the radiation sensitive resin composition Product solutions (S-2) to (S-10), (S-12) to (S-18) and (s-1) to (s-7) were prepared.
In Examples 2, 3, 13, and 14, the description of the component [B] represents that two types of 1,2-quinonediazide compounds were used in combination.
Example 11
In Example 1, it was dissolved in diethylene glycol ethyl methyl ether / propylene glycol monomethyl ether acetate = 6/4 so that the solid content concentration was 20% by weight, and [F] SH-28PA (Toray Dow Corning Silicone ( The composition was prepared in the same manner as in Example 1 except that the product (made by Co., Ltd.) was added, and a solution (S-11) of the radiation sensitive resin composition was prepared.

In Table 1, the abbreviations of the components have the following meanings.
(B-1): 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide -5-Sulphonic acid chloride (2.0 mol) condensate (B-2): 4,4 ′, 4 ″ -ethylidinetris (phenol) (1.0 mol) and 1,2-naphthoquinonediazide— Condensate (B-3) of 5-sulfonic acid chloride (2.0 mol): 2,3,4,4′-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid Ester (2.44 mol)
(C-1): 4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate (C-2): 4- (phenylthio) phenyldiphenylsulfonium tris (heptafluoropropyl) trifluorophosphate (C- 3): (η ⁵ -cyclopentadienyl) (η ⁶ -toluene) Fe (II) tris (pentafluoroethyl) trifluorophosphate (C-4): 4- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate ( Product Name DTS-102 Midori Chemical Co., Ltd.)
(C-5): 4-acetoxyphenyl-dimethylsulfonium hexafluoroantimonate (trade name: SI-150, manufactured by Sanshin Chemical Industry Co., Ltd.)
(C-6): N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide (trade name: NAI-105, manufactured by Midori Chemical Co., Ltd.)

Examples 1-11, Comparative Examples 1-5
<Performance evaluation as interlayer insulation film>
Using the radiation-sensitive resin composition prepared as described above, various characteristics as an interlayer insulating film were evaluated as follows.
[Evaluation of sensitivity]
About Examples 1-10 and Comparative Examples 1-5 on a silicon substrate, after apply | coating the composition of Table 2 using a spinner, it prebaked on a hotplate for 2 minutes at 100 degreeC, and is film thickness. A coating film of 4.0 μm was formed. About Example 11, it apply | coated with the slit die coater, After vacuum-drying at 0.5 Torr, it prebaked on the hotplate for 2 minutes at 100 degreeC, and formed the coating film with a film thickness of 4.0 micrometers. The obtained coating film was exposed by changing the exposure time with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. through a pattern mask having a predetermined pattern, and then 2.38% by weight. And developed with a liquid piling method at 25 ° C. for 80 seconds. The substrate was washed with ultrapure water for 1 minute and dried to form a pattern on the wafer. The amount of exposure required to completely dissolve the 3.0 μm line-and-space (10 to 1) space pattern was measured. This value is shown in Table 2 as sensitivity. It can be said that the sensitivity is good when this value is 1,000 J / m ² or less.

[Evaluation of solvent resistance]
About Example 1-10 and Comparative Examples 1-5 on a silicon substrate, after apply | coating the composition of Table 2 using a spinner, it prebaked on a hotplate for 2 minutes at 100 degreeC, and is a coating film. Formed. About Example 11, it apply | coated with the slit die coater, After vacuum-drying at 0.5 Torr, it prebaked on the hotplate for 2 minutes at 100 degreeC, and formed the coating film. The obtained coating film was exposed to a cumulative irradiation amount of 3,000 J / m ² with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc., and this silicon substrate was exposed to 220 in a clean oven. Heated at 0 ° C. for 1 hour to obtain a cured film having a thickness of 3.0 μm. The film thickness (T1) of the obtained cured film was measured. And after immersing the silicon substrate in which this cured film was formed in dimethyl sulfoxide temperature-controlled at 70 degreeC for 20 minutes, the film thickness (t1) of the said cured film was measured, and the film thickness change rate by immersion { | T1-T1 | / T1} × 100 [%] was calculated. The results are shown in Table 2. When this value is 5% or less, the solvent resistance is good.
Further, the post-baking temperature was changed from 220 ° C. to 180 ° C., and the solvent resistance was similarly evaluated. If the film thickness change rate is 5% or less and the film thickness change rate is the same as when the post bake temperature is 220 ° C., it can be determined that the solvent resistance is sufficient even at a post bake temperature of 150 ° C.
In the evaluation of solvent resistance, patterning of the film to be formed is unnecessary, and thus the development process was omitted.

[Evaluation of heat resistance]
Similarly to the evaluation of the solvent resistance, a cured film was formed under post-baking conditions of 220 ° C./1 hour and 180 ° C./1 hour, and the thickness (T2) of the obtained cured film was measured. Next, after this cured film substrate was additionally baked in a clean oven at 240 ° C. for 1 hour, the film thickness (t2) of the cured film was measured, and the rate of change in film thickness by additional baking {| t2-T2 | / T2 } × 100 [%] was calculated. The results are shown in Table 2. When this value is 5% or less, the heat resistance is good. Further, when the post-baking temperature is 150 ° C., the post-baking temperature of 180 ° C. is sufficient if the film thickness changing rate is 5% or less and if the post-baking temperature is 220 ° C. It can be judged that there is a good heat resistance.

[Evaluation of transparency]
In the above-described solvent resistance evaluation, a glass substrate “Corning 7059 (manufactured by Corning)” was used instead of the silicon substrate, and the post-baking conditions were 220 ° C./1 hour and 180 ° C./1 hour. A cured film was formed for each. The light transmittance of the glass substrate having this cured film was measured at a wavelength in the range of 400 to 800 nm using a spectrophotometer “150-20 type double beam (manufactured by Hitachi, Ltd.)”. Table 2 shows the values of the minimum light transmittance at that time. When this value is 90% or more, it can be said that the transparency is good.

[Evaluation of relative permittivity]
On Examples 1-10 and Comparative Examples 1-5 on a polished SUS304 substrate, the composition described in Table 2 was applied using a spinner, and then prebaked on a hot plate at 100 ° C. for 2 minutes. Thus, a coating film having a thickness of 3.0 μm was formed. About Example 11, it apply | coated with the slit die coater, After vacuum-drying at 0.5 Torr, it prebaked on the hotplate for 2 minutes at 100 degreeC, and formed the coating film with a film thickness of 3.0 micrometers. The obtained coating film was exposed to a cumulative irradiation amount of 3,000 J / m ² with a Canon-made PLA-501F exposure machine (extra-high pressure mercury lamp), and this substrate was placed in a clean oven at 220 ° C. And cured at 180 ° C. for 1 hour to obtain a cured film. About this cured film, the Pt / Pd electrode pattern was formed by the vapor deposition method, and the sample for dielectric constant measurement was created. The relative dielectric constant of the substrate was measured at a frequency of 10 kHz by a CV method using an HP16451B electrode manufactured by Yokogawa-Hewlett-Packard Co., Ltd. and an HP4284A precision LCR meter. The results are shown in Table 2. When this value is 3.4 or less, it can be said that the dielectric constant is good.
In the evaluation of the relative dielectric constant, the patterning of the film to be formed is unnecessary, and thus the development process is omitted.

Examples 12-18, Comparative Examples 6-7
<Performance evaluation as a micro lens>
Using the radiation-sensitive resin composition prepared as described above, various characteristics as a microlens were evaluated as follows. For the evaluation of solvent resistance, evaluation of heat resistance, and evaluation of transparency, refer to the results of performance evaluation as the interlayer insulating film.
[Evaluation of sensitivity]
For Examples 12 to 18 and Comparative Examples 6 to 7 on a silicon substrate, the composition described in Table 3 was applied using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes. A 2.0 μm coating film was formed. The obtained coating film was exposed through a pattern mask having a predetermined pattern with an NSR1755i7A reduction projection exposure machine (NA = 0.50, λ = 365 nm) manufactured by Nikon Corporation, and exposed in Table 3. Development was carried out with a tetramethylammonium hydroxide aqueous solution having the stated concentration at 25 ° C. for 1 minute. It was rinsed with water and dried to form a pattern on the wafer. The exposure time required for the space line width of the 0.8 μm line and space pattern (1 to 1) to be 0.8 μm was measured. This value is shown in Table 3 as sensitivity. It can be said that the sensitivity is good when this value is 2,000 J / m ² or less.

[Formation of microlenses]
For Examples 12 to 18 and Comparative Examples 6 to 7 on a silicon substrate, the composition described in Table 3 was applied using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to obtain a film thickness of 2 A coating film of 0.0 μm was formed. The obtained coating film was passed through a pattern mask having 4.0 [mu] m dots and 2.0 [mu] m space pattern with the NSR1755i7A reduction projection exposure machine (NA = 0.50, [lambda] = 365 nm) manufactured by Nikon Corporation. Exposure is performed with an exposure amount corresponding to the sensitivity value measured in [Evaluation of Sensitivity], and 25 ° C. is applied in a tetramethylammonium hydroxide aqueous solution having a concentration described as the developer concentration in the sensitivity evaluation in Table 3. Development was carried out by a puddle method for 1 minute. It was rinsed with water and dried to form a pattern on the wafer. Then, it exposed so that an integrated irradiation amount might be set to 3,000 J / m < ² > with the PLA-501F exposure machine (extra-high pressure mercury lamp) by Canon. Thereafter, the pattern was melt-flowed by heating at 130 ° C. for 10 minutes on a hot plate and further at 200 ° C. for 10 minutes to form a microlens.
Table 3 shows the size (diameter) and cross-sectional shape of the bottom (surface in contact with the substrate) of the formed microlens. It can be said that the microlens bottom portion is good when it is larger than 4.0 μm and smaller than 5.0 μm. In addition, when this dimension is 5.0 μm or more, the adjacent lenses are in contact with each other, which is not preferable. Further, the cross-sectional shape is good when it is a semi-convex lens shape as shown in (a) in the schematic diagram shown in FIG. 1, and it is bad when it is on a substantially trapezoidal shape as shown in (b).

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

Claims (17)

[A] a polysiloxane having at least one group selected from the group consisting of an oxiranyl group and an oxetanyl group and a functional group capable of undergoing an addition reaction with the oxiranyl group or the oxetanyl group,
[B] containing at least one compound selected from the group consisting of a 1,2-quinonediazide compound, and [C] a compound represented by the general formula (1) and a compound represented by the general formula (4). A radiation-sensitive resin composition.

[In the formula (1), A represents an element having a valence m of VIA group to VIIA group (CAS notation), and m is 1 or 2. n represents the number of repeating units of the structure in parentheses and is an integer of 0 to 3. R is an organic group bonded to A, and is an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or Represents an alkynyl group having 2 to 30 carbon atoms, and R represents alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy , Alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups, and at least one selected from the group consisting of halogen may be substituted. The number of R is m + n (m−1) +1, and each R may be the same as or different from each other. In addition, two or more R's are each directly or —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR′—, —CO—, —COO—, —CONH—, carbon number A ring structure containing element A may be formed by bonding via 1 to 3 alkylene groups or phenylene groups. Here, R ′ is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.
D is a structure represented by the following general formula (2),

In the formula (2), E represents a divalent group of an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a heterocyclic compound having 8 to 20 carbon atoms, and E represents 1 to 1 carbon atoms. It may be substituted with at least one selected from the group consisting of 8 alkyls, C 1-8 alkoxys, C 6-10 aryls, hydroxy, cyano, nitro groups and halogens. G represents —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR′—, —CO—, —COO—, —CONH—, an alkylene group having 1 to 3 carbon atoms, or phenylene. Represents a group. a is an integer of 0-5. a + 1 E and a G may be the same or different. Here, R ′ is the same as described above.
X ⁻ is a counter ion of onium. The number thereof is n + 1 per molecule, at least one of which is a fluorinated alkyl fluorophosphate anion represented by the general formula (3),

The rest may be other anions. In the general formula (3), Rf represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms. b shows the number and is an integer of 1-5. The b Rf's may be the same or different. ]

[In Formula (4), M is one type of transition metal element selected from Group VIB to Group VIII (CAS notation), and L1 and L2 are ligands of transition metal element M. L1 is an aromatic compound having 6 to 24 carbon atoms or a heterocyclic compound having 4 to 20 carbon atoms, L2 is an indene, fluorene or cyclopentagen anion, and these L1 and L2 are further alkyl, alkoxy, alkylthio, arylthio , Alkylcarbonyl, alkoxycarbonyl, phenyl, benzoyl, cyano, nitro, and at least one selected from the group consisting of halogen. c and d represent the numbers of L1 and L2, respectively, both are integers of 0 to 2, and the total number (c + d) is 2. When both of the two ligands are L1 or both, they may be the same as or different from each other. The total charge e of the charges of the ligands L1 and L2 and the charge of the transition metal element M is positive and is 1 or 2. X ^- X in formula (1) ^- which is synonymous. ] [A] Polysiloxane is
(A1) a silane compound having at least one group selected from the group consisting of an oxiranyl group and an oxetanyl group and a hydrolyzable group,
(A2) a silane compound having a hydrolyzable group and a functional group capable of undergoing addition reaction with an oxiranyl group or oxetanyl group, and a hydrolysis condensate of a hydrolyzable silane compound other than (a3), (a1), and (a2) The radiation sensitive resin composition of Claim 1 which exists. [A] The radiation-sensitive resin composition according to claim 1 or 2, wherein the functional group capable of undergoing addition reaction with the oxiranyl group or oxetanyl group in the polysiloxane is a hydroxyl group, a mercapto group, or an amino group.   A in the general formula (1) is S or I, and at least one of R is an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 4 to 30 carbon atoms, and these are alkyl, hydroxy, alkoxy, Alkylcarbonyl, arylcarbol, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano The radiation sensitive resin composition of Claims 1-3 which may be substituted by at least 1 sort (s) chosen from the group which consists of each group of nitro, and halogen. All of m + n (m−1) +1 R in the general formula (1) are an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 4 to 30 carbon atoms, and these are alkyl, hydroxy, alkoxy, alkyl Carbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro The radiation-sensitive resin composition according to claim 1, which may be substituted with at least one selected from the group consisting of each group and halogen, and may be the same as or different from each other. D in the general formula (1) is

The radiation sensitive resin composition of Claims 1-5 which is at least 1 type of group chosen from the group represented by these. N in the general formula (1) is 0 or 1, and the onium ion is triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide Bis [4- (bis [4- (2-hydroxyethoxy) phenyl] sulfonio) phenyl] sulfide, bis (4- [bis (4-fluorophenyl) sulfonio] phenyl) sulfide, 4- (4-benzoyl-2 -Chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi- p-Tolylsulfonium, 7-Isopropyl Pyr-9-oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl) sulfonio] thioxanthone, 2-[(diphenyl) sulfonio] thioxanthone, 4- [ 4- (4-tert-butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiaanthrhenium, 5-phenylthiaanthrhenium Diphenylphenacylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, octadecylmethylphenacylsulfonium Diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4-decyloxy) phenyliodonium, 4 The radiation-sensitive resin composition according to claim 1, which is-(2-hydroxytetradecyloxy) phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium or 4-isobutylphenyl (p-tolyl) iodonium. object. The radiation sensitive resin composition of Claims 1-7 whose M is 1 type chosen from the group of Cr, Mo, W, Mn, Fe, and Co in General formula (4). In the general formula (4), the ligand L1 is toluene, xylene, ethylbenzene, cumene, mesitylene, methoxybenzene, acetylbenzene, chlorobenzene, 2-chlorotoluene, 3-chlorotoluene, 4-chlorotoluene, naphthalene, 1- The radiation-sensitive resin composition according to claim 1, which is methylnaphthalene, 1-methoxynaphthalene, 2-methoxynaphthalene, 1-chloronaphthalene, 2-chloronaphthalene, biphenyl, indene, bilene or diphenyl sulfide. The radiation sensitive resin composition of Claims 1-9 whose ligand L2 is an anion of indene, fluorene, or cyclopentadiene in General formula (4). The transition metal complex of the general formula (4) is (η ⁵ -cyclopentadienyl) (η ⁶ -toluene) Fe ⁺ , (η ⁵ -cyclopentadienyl) (η ⁶ -xylene) Fe ⁺ , (η ⁵ -Cyclopentadienyl) (η ⁶ -1-methylnaphthalene) Fe ⁺ , (η ⁵ -cyclopentadienyl) (η ⁶ -cumene) Fe ⁺ , (η ⁵ -cyclopentadienyl) (η ⁶ -mesitylene ) Fe ⁺ , (η ⁵ -cyclopentadienyl) (η ⁶ -birene) Fe ⁺ , (η ⁵ -fluorenyl) (η ⁶ -cumene) Fe ⁺ , (η ⁵ -indenyl) (η ⁶ -cumene) Fe ⁺ , Bis (η ⁶ -mesitylene) Fe ²⁺ , bis (η ⁶ -xylene) Fe ²⁺ , bis (η ⁶ -cumene) Fe ²⁺ , (η ⁶ -toluene) (η ⁶ -xylene) Fe ²⁺ , (η ⁶ - cumene) (eta ⁶ - naphthalene) ^{Fe 2+,} bis (eta ⁵ - Shi Ropentajieniru) Fe ^+, bis (eta ⁵ - indenyl) ^Fe +, (η ⁵ - cyclopentadienyl) (η ⁵ - fluorenyl) Fe ⁺ or (eta ⁵ - cyclopentadienyl) (η ⁵ - indenyl) Fe ⁺ The radiation sensitive resin composition of Claims 1-10 which are these. The radiation sensitive resin composition of Claims 1-11 whose carbon number of Rf is 1-8 in General formula (3), and the ratio by which the hydrogen atom was substituted by the fluorine atom is 90% or more. The radiation sensitive resin composition according to claim 1, wherein in General Formula (3), Rf is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms. The fluorinated alkyl fluorophosphate anion represented by the general formula (3) is [(CF ₃ CF ₂ ) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CFCF _{2) 2} PF _4] ^- a is, the radiation-sensitive resin composition of claim 1 to 13. The radiation-sensitive resin composition according to claim 1, which is used for forming an interlayer insulating film or a microlens. A method for forming an interlayer insulating film or a microlens comprising the following steps in the order described below.
(1) The process of forming the coating film of the radiation sensitive resin composition of Claim 15 on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) Development step, and (4) Heating step.   An interlayer insulating film or microlens formed by the method of claim 16.

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