JP2010039023A - Radiation-sensitive composition, its manufacturing method, and pattern forming process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive composition having excellent resistance to crack, patterning property, and heat resistance. <P>SOLUTION: This radiation-sensitive composition contains the following components (A) and (B): (A) denotes at least one selected from the group consisting of a hydrolytic silane compound expressed by the formula (1) (wherein, R<SP>1</SP>, R<SP>2</SP>, X, and A denote 1-12C alkyl group or the like, 2-30C alkylene group or the like allowed to have substituent group, a hydrolytic group, and a quadrivalent organic group, respectively, p and q are 0-2 integer and 1-3 integer being independent from each other, respectively, and p+q=3), a hydrolysate of the hydrolytic silane compound, and a condensation product of the hydrolysate; and (B) denotes photooxygen generator. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a radiation-sensitive composition, a method for producing the same, and a method for forming a cured film.

Conventionally, silane-based radiation-sensitive compositions are known as radiation-sensitive compositions. Silane radiation-sensitive compositions are characterized by high heat resistance and chemical resistance derived from siloxane bonds, and various types have been developed so far.
For example, it contains (A) at least one compound selected from the group consisting of a hydrolyzable silane compound represented by a specific formula, a hydrolyzate thereof, and a condensate thereof, and (B) a photoacid generator. A photocurable composition is disclosed (Patent Document 1). This composition has an advantage that a circuit board can be easily formed by a photocuring reaction even in the presence of oxygen.
JP 2000-144012 A

The hardened | cured material of the photocurable composition described in patent document 1 had room for improvement from a viewpoint of the physical property which is excellent in all of crack resistance, patterning property, and heat resistance.
Then, an object of this invention is to provide the radiation sensitive composition excellent in crack resistance, patterning property, and heat resistance.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that, according to the radiation-sensitive composition containing a specific silane compound having an imide group and a photoacid generator as constituent components, crack resistance, patterning The present invention was completed by finding that a cured film excellent in heat resistance and heat resistance can be formed.

［一般式（１）中、Ｒ^１は、炭素数１〜１２のアルキル基、炭素数２〜１２のアルケニル基、または炭素数６〜１２のアリール基であり、複数存在するＲ^１は同一または異なっていても良い。Ｒ^２は、単結合、置換基を有してもよい−ＣＨ_２−、置換基を有してもよい炭素数２〜３０のアルキレン基、置換基を有してもよい炭素数２〜３０のアルケニレン基、置換基を有してもよい炭素数２〜３０のアルキニレン基、または、置換基を有してもよい炭素数２〜３０の二価の芳香族基であり、複数存在するＲ^２は同一または異なっていても良い。Ｘは加水分解性基であり、複数存在するＸは同一または異なっていても良い。Ａは４価の有機基を示す。ｐは各々独立に０〜２の整数であり、ｑは各々独立に１〜３の整数であり、かつｐ＋ｑ＝３である。］
（Ｂ）光酸発生剤
［２］ 前記加水分解性シラン化合物が、（ａ１）下記一般式（２）で表されるテトラカルボン酸二無水物及びこれらの反応性誘導体からなる群より選ばれる少なくとも１種のアシル化合物と、（ａ２）下記一般式（３）で表されるアミノ基含有加水分解性シラン化合物とを反応させて得られたものである前記［１］に記載の感放射線性組成物。

［一般式（２）中、Ａは４価の有機基を示す。］

［一般式（３）中、Ｒ^１は、炭素数１〜１２のアルキル基、炭素数２〜１２のアルケニル基、または炭素数６〜１２のアリール基であり、複数存在するＲ^１は同一または異なっていても良い。Ｒ^２は、単結合、置換基を有してもよい−ＣＨ_２−、置換基を有してもよい炭素数２〜３０のアルキレン基、置換基を有してもよい炭素数２〜３０のアルケニレン基、置換基を有してもよい炭素数２〜３０のアルキニレン基、または、置換基を有してもよい炭素数２〜３０の二価の芳香族基である。Ｘは加水分解性基であり、複数存在するＸは同一または異なっていても良い。ｐは０〜２の整数であり、ｑは１〜３の整数であり、かつｐ＋ｑ＝３である。］
［３］ 前記成分（Ａ）が、前記一般式（１）で表される加水分解性シラン化合物の加水分解物の縮合物を含む前記［１］または［２］に記載の感放射線性組成物。
［４］ 前記［２］に記載の感放射線性組成物の製造方法であって、前記一般式（２）で表されるテトラカルボン酸二無水物及びこれらの反応性誘導体からなる群より選ばれる少なくとも１種のアシル化合物と、前記一般式（３）で表されるアミノ基含有加水分解性シラン化合物とを反応させて、前記一般式（１）で表される加水分解性シラン化合物を得る工程と、該加水分解性シラン化合物と光酸発生剤を混合する工程と、を含む感放射線性組成物の製造方法。
［５］ 得られた加水分解性シラン化合物を加水分解および／または加水分解縮合する工程を含む前記［４］に記載の感放射線性組成物の製造方法。
［６］ 前記［１］〜［３］のいずれかに記載の感放射線性組成物を基板に塗布して塗膜を形成した後、該塗膜の所望の領域に放射線を照射して硬化させ、次いで、現像処理によって前記塗膜の放射線照射領域以外の未硬化領域を除去することを特徴とするパターン形成方法。
［７］ 前記塗膜の放射線照射領域以外の未硬化領域を除去した後に、前記塗膜に加熱処理を施す工程を含む前記［６］に記載のパターン形成方法。 That is, the present invention provides the following [1] to [7].
[1] A radiation-sensitive composition comprising the following components (A) and (B):
(A) At least one selected from the group consisting of a hydrolyzable silane compound represented by the following general formula (1), a hydrolyzate of the hydrolyzable silane compound, and a condensate of the hydrolyzate

[In General Formula (1), R ¹ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and a plurality of R ¹ are the same or It may be different. R ² is a single bond, —CH ₂ — which may have a substituent, an alkylene group having 2 to 30 carbon atoms which may have a substituent, or 2 to 30 carbon atoms which may have a substituent. Or an alkenylene group having 2 to 30 carbon atoms which may have a substituent, or a divalent aromatic group having 2 to 30 carbon atoms which may have a substituent, and a plurality of R ² may be the same or different. X is a hydrolyzable group, and a plurality of Xs may be the same or different. A represents a tetravalent organic group. p is each independently an integer of 0 to 2, q is each independently an integer of 1 to 3, and p + q = 3. ]
(B) Photoacid generator [2] The hydrolyzable silane compound is at least selected from the group consisting of (a1) tetracarboxylic dianhydrides represented by the following general formula (2) and reactive derivatives thereof. The radiation-sensitive composition according to [1], which is obtained by reacting one kind of acyl compound with (a2) an amino group-containing hydrolyzable silane compound represented by the following general formula (3): object.

[In General Formula (2), A represents a tetravalent organic group. ]

[In General Formula (3), R ¹ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and a plurality of R ¹ are the same or It may be different. R ² is a single bond, —CH ₂ — which may have a substituent, an alkylene group having 2 to 30 carbon atoms which may have a substituent, or 2 to 30 carbon atoms which may have a substituent. Or an alkenylene group having 2 to 30 carbon atoms which may have a substituent, or a divalent aromatic group having 2 to 30 carbon atoms which may have a substituent. X is a hydrolyzable group, and a plurality of Xs may be the same or different. p is an integer of 0 to 2, q is an integer of 1 to 3, and p + q = 3. ]
[3] The radiation-sensitive composition according to [1] or [2], wherein the component (A) includes a condensate of a hydrolyzate of the hydrolyzable silane compound represented by the general formula (1). .
[4] A method for producing the radiation-sensitive composition according to [2], wherein the radiation-sensitive composition is selected from the group consisting of tetracarboxylic dianhydrides represented by the general formula (2) and reactive derivatives thereof. The step of reacting at least one acyl compound with the amino group-containing hydrolyzable silane compound represented by the general formula (3) to obtain the hydrolyzable silane compound represented by the general formula (1) And a step of mixing the hydrolyzable silane compound and the photoacid generator, and a method for producing a radiation-sensitive composition.
[5] The method for producing a radiation-sensitive composition according to [4], including a step of hydrolyzing and / or hydrolytically condensing the obtained hydrolyzable silane compound.
[6] After the radiation-sensitive composition according to any one of [1] to [3] is applied to a substrate to form a coating film, a desired region of the coating film is irradiated with radiation and cured. Then, the pattern formation method characterized by removing uncured regions other than the radiation-irradiated region of the coating film by developing treatment.
[7] The pattern forming method according to [6], including a step of heat-treating the coating film after removing an uncured region other than the radiation irradiation region of the coating film.

According to the radiation sensitive composition of the present invention, a cured film having excellent crack resistance can be obtained. Specifically, a cured film having a thickness of 10 μm or more can be formed without generating cracks.
Moreover, according to the radiation sensitive composition of this invention, the outstanding patterning property can be obtained and the cured film which has a fine shape can be formed easily.
Moreover, according to the radiation sensitive composition of this invention, the hardened | cured material excellent in heat resistance can be obtained. In particular, when the component (A) contains a condensate of a hydrolyzate of a specific compound represented by the general formula (1), a siloxane bond can be introduced into the composition, which further improves crack resistance. An excellent cured product can be obtained.
Furthermore, according to the present invention, since the radiation-sensitive composition contains a component having a silanol group, development treatment with a dilute alkaline aqueous solution can be applied, and environmental burdens can be reduced.

［一般式（１）中、Ｒ^１は、炭素数１〜１２のアルキル基、炭素数２〜１２のアルケニル基、または炭素数６〜１２のアリール基であり、複数存在するＲ^１は同一または異なっていても良い。Ｒ^２は、単結合、置換基を有してもよい−ＣＨ_２−、置換基を有してもよい炭素数２〜３０のアルキレン基、置換基を有してもよい炭素数２〜３０のアルケニレン基、置換基を有してもよい炭素数２〜３０のアルキニレン基、または、置換基を有してもよい炭素数２〜３０の二価の芳香族基であり、複数存在するＲ^２は同一または異なっていても良い。Ｘは加水分解性基であり、複数存在するＸは同一または異なっていても良い。Ａは４価の有機基を示す。ｐは各々独立に０〜２の整数であり、ｑは各々独立に１〜３の整数であり、かつｐ＋ｑ＝３である。］
このような加水分解性シラン化合物、その加水分解物、及び加水分解物の縮合物（以下、加水分解縮合物ともいう。）からなる群より選ばれる少なくとも１種を用いることにより、クラック耐性に優れた硬化膜を得ることができる。このことは、一般式（１）で表される加水分解性シラン化合物が分子間凝集力の強いイミド基を含有するためと推察される。
特にクラック耐性の観点から、（Ａ）成分は、前記加水分解性シラン化合物の加水分解縮合物を含むことが好ましい。
なお、本明細書において、加水分解性シラン化合物の加水分解物とは、加水分解反応により加水分解性シラン化合物の加水分解性基の一部又は全部がシラノール基に変化した加水分解反応混合物を意味する。加水分解性シラン化合物の加水分解縮合物とは、該加水分解反応混合物中のシラノール基同士又はシラノール基と加水分解性基との縮合反応により得られるシロキサン縮合物を意味する。
また、成分（Ａ）は、完全加水分解縮合物換算のイミド基濃度が０．１ｍｍｏｌ／ｇ〜１０ｍｍｏｌ／ｇであることが好ましく、０．５ｍｍｏｌ／ｇ〜８ｍｍｏｌ／ｇであることがより好ましく、０．８ｍｍｏｌ／ｇ〜５ｍｍｏｌ／ｇであることがさらに好ましく、１ｍｍｏｌ／ｇ〜５ｍｍｏｌ／ｇであることが特に好ましい。イミド基濃度が０．１ｍｍｏｌ／ｇ未満である場合には、十分なクラック耐性が得られない場合があり、イミド基濃度が１０ｍｍｏｌ／ｇを超える場合には、十分な耐熱性が得られない場合がある。
さらに、成分（Ａ）の量は、本発明の感放射線性組成物の固形分を１００質量部とした場合に、１０質量部以上１００質量部未満であることが好ましく、３０質量部〜９９.９９質量部であることがより好ましく、５０質量部〜９９．９質量部であることがさらに好ましく、８０質量部〜９９．９質量部であることが特に好ましい。 The radiation sensitive composition of this invention contains (A) component, (B) component, and another arbitrary component.
Hereinafter, each component will be described.
[(A) component]
The component (A) constituting the radiation-sensitive composition of the present invention includes a hydrolyzable silane compound represented by the following general formula (1), a hydrolyzate of the hydrolyzable silane compound, and the hydrolyzate of the hydrolyzate. It is at least one selected from the group consisting of condensates. In the present invention, a part of the hydrolyzable silane compound represented by the following general formula (1) has two amide acid structures instead of two imide groups present in the molecule, or It may have one imide group and one amic acid structure.

[In General Formula (1), R ¹ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and a plurality of R ¹ are the same or It may be different. R ² is a single bond, —CH ₂ — which may have a substituent, an alkylene group having 2 to 30 carbon atoms which may have a substituent, or 2 to 30 carbon atoms which may have a substituent. Or an alkenylene group having 2 to 30 carbon atoms which may have a substituent, or a divalent aromatic group having 2 to 30 carbon atoms which may have a substituent, and a plurality of R ² may be the same or different. X is a hydrolyzable group, and a plurality of Xs may be the same or different. A represents a tetravalent organic group. p is each independently an integer of 0 to 2, q is each independently an integer of 1 to 3, and p + q = 3. ]
By using at least one selected from the group consisting of such hydrolyzable silane compounds, hydrolysates thereof, and condensates of hydrolysates (hereinafter also referred to as hydrolysis condensates), the crack resistance is excellent. A cured film can be obtained. This is presumably because the hydrolyzable silane compound represented by the general formula (1) contains an imide group having a strong intermolecular cohesive force.
In particular, from the viewpoint of crack resistance, the component (A) preferably contains a hydrolysis condensate of the hydrolyzable silane compound.
In the present specification, the hydrolyzate of the hydrolyzable silane compound means a hydrolysis reaction mixture in which part or all of the hydrolyzable groups of the hydrolyzable silane compound are changed to silanol groups by the hydrolysis reaction. To do. The hydrolysis condensate of a hydrolyzable silane compound means a siloxane condensate obtained by a condensation reaction between silanol groups or silanol groups and hydrolyzable groups in the hydrolysis reaction mixture.
Moreover, as for a component (A), it is preferable that the imide group density | concentration of complete hydrolysis-condensation product is 0.1 mmol / g-10 mmol / g, It is more preferable that it is 0.5 mmol / g-8 mmol / g, It is more preferably 0.8 mmol / g to 5 mmol / g, and particularly preferably 1 mmol / g to 5 mmol / g. When the imide group concentration is less than 0.1 mmol / g, sufficient crack resistance may not be obtained. When the imide group concentration exceeds 10 mmol / g, sufficient heat resistance may not be obtained. There is.
Furthermore, the amount of the component (A) is preferably 10 parts by mass or more and less than 100 parts by mass when the solid content of the radiation-sensitive composition of the present invention is 100 parts by mass, and 30 parts by mass to 99. It is more preferably 99 parts by mass, further preferably 50 parts by mass to 99.9 parts by mass, and particularly preferably 80 parts by mass to 99.9 parts by mass.

［一般式（２）中、Ａは４価の有機基を示す。］

［一般式（３）中、Ｒ^１は、炭素数１〜１２のアルキル基、炭素数２〜１２のアルケニル基、または、炭素数６〜１２のアリール基であり、複数存在するＲ^１は同一または異なっていても良い。Ｒ^２は、単結合、置換基を有してもよい−ＣＨ_２−、置換基を有してもよい炭素数２〜３０のアルキレン基、置換基を有してもよい炭素数２〜３０のアルケニレン基、置換基を有してもよい炭素数２〜３０のアルキニレン基、または、置換基を有してもよい炭素数２〜３０の二価の芳香族基である。Ｘは加水分解性基であり、複数存在するＸは同一または異なっていても良い。ｐは０〜２の整数であり、ｑは１〜３の整数であり、かつｐ＋ｑ＝３である。］ The hydrolyzable silane compound represented by the general formula (1) is (a1) at least one selected from the group consisting of tetracarboxylic dianhydrides represented by the following general formula (2) and reactive derivatives thereof. (A2) an amino group-containing hydrolyzable silane compound represented by the following general formula (3) to make a hydrolyzable silane compound having an amic acid structure, Can be obtained by imidization.
Here, the reactive derivative is a compound that can be changed into a tetracarboxylic dianhydride, for example, a compound having two carboxyl groups in place of the anhydride of the aliphatic tetracarboxylic dianhydride, these 2 A compound in which one or both of one carboxyl group is an esterified product, or an acid chloride in which one or both of these two carboxyl groups are chlorinated is preferably used.

[In General Formula (2), A represents a tetravalent organic group. ]

[In General Formula (3), R ¹ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and a plurality of R ¹ are the same. Or it may be different. R ² is a single bond, —CH ₂ — which may have a substituent, an alkylene group having 2 to 30 carbon atoms which may have a substituent, or 2 to 30 carbon atoms which may have a substituent. Or an alkenylene group having 2 to 30 carbon atoms which may have a substituent, or a divalent aromatic group having 2 to 30 carbon atoms which may have a substituent. X is a hydrolyzable group, and a plurality of Xs may be the same or different. p is an integer of 0 to 2, q is an integer of 1 to 3, and p + q = 3. ]

<(A1) component; specific acyl compound>
Examples of the tetracarboxylic dianhydride represented by the general formula (2) used in the present invention include butanetetracarboxylic dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride. 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2, 3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3 , 4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3, 5-tri Ruboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5 , 9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro -5-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro -5-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro -7-methyl-5- (tetrahydro Dro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5- ( Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- ( Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5- ( Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5 -(Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, -C] furan-1,3-dione, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] An aliphatic or alicyclic tetracarboxylic dianhydride such as oct-7-ene-2,3,5,6-tetracarboxylic dianhydride;
Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4
'-Bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4′-biphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthal Acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4 '-Diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate), 1,4-buta Diol-bis (anhydro trimellitate), 1,6-hexanediol-bis (anhydro trimellitate), 1,8-octanediol-bis (anhydro trimellitate), 2,2-bis (4 And aromatic tetracarboxylic dianhydrides such as -hydroxyphenyl) propane-bis (anhydrotrimellitate).
Of these, aromatic tetracarboxylic dianhydrides are preferred, more preferably pyromellitic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4'-perfluoroisopropylidene diphthalic dianhydride (4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride), 4,4'-oxydiphthalic dianhydride, 4,4'- Biphthalic dianhydride.
As the component (a1), these tetracarboxylic dianhydrides and their reactive derivatives can be used singly or in combination of two or more.

<(A2) component; amino group-containing hydrolyzable silane compound>
In General Formula (3), R ¹ is a non-hydrolyzable organic group, which represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms. . When two or more R ¹ are present, they may be the same or different. In general formula (3), R ¹ is preferably an alkyl group or a phenyl group.
In General Formula (3), R ² has a single bond, —CH ₂ — which may have a substituent, an alkylene group having 2 to 30 carbon atoms which may have a substituent, or a substituent. May be an alkenylene group having 2 to 30 carbon atoms, an alkynylene group having 2 to 30 carbon atoms which may have a substituent, or a divalent aromatic group having 2 to 30 carbon atoms which may have a substituent. Indicates.
Examples of —CH ₂ — that may have a substituent include a methylene group and a fluoromethylene group. Examples of the alkylene group having 2 to 30 carbon atoms that may have a substituent include an ethylene group, a propylene group, a tetramethylene group, and a tetrafluoroethylene group. Examples of the alkenylene group having 2 to 30 carbon atoms which may have a substituent include a vinylene group, a propenylene group and a butadienylene group. Examples of the alkynylene group having 2 to 30 carbon atoms which may have a substituent include an ethynylene group, a propynylene group, and a butynylene group. Examples of the divalent aromatic group that may have a substituent include a phenylene group, a naphthylene group, a biphenylene group, an anthracenedil group, a pyridinedyl group, a thiophenedilyl group, a fluorophenylene group, a chlorophenylene group, Examples thereof include a methylphenylene group, a silylphenylene group, a hydroxyphenylene group, an aminophenylene group, a phenylenemethylenephenylene group, a phenyleneoxyphenylene group, a phenylenepropylidenephenylene group, and a phenylene (hexafluoropropylidene) phenylene group.
In general formula (3), R ² is preferably an aliphatic alkylene group having 1 to 20 carbon atoms or a phenylene group.

In general formula (3), X represents a hydrolyzable group, and when two or more X exist, they may be the same or different from each other. The hydrolyzable group may be any group that can be hydrolyzed to form a silanol group, or a group that can form a siloxane condensate, such as a hydrogen atom or an alkoxy having 1 to 12 carbon atoms. Group, halogen atom, amino group, carboxyl group and the like.
Preferable examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group and an ethoxy group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Preferable examples of the amino group include an amino group and a dimethylamino group. Preferable examples of the carboxyl group include an acetoxy group and a ptiloyloxy group.
(A2) Specific examples of the amino group-containing hydrolyzable silane compound represented by the general formula (3) include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 4-aminobutyltriethoxysilane. 3- (m-aminophenoxy) propyltrimethoxysilane, m-aminophenyltrimethoxysilane, p-aminophenyltrimethoxysilane, 3- (m-aminophenoxy) propyltrimethoxysilane, 3-aminopropylmethyldiethoxy Examples thereof include silane, 3-aminopropylethyldiethoxysilane, and 3-aminopropyldiethyldiethoxysilane.
Of these, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, and 4-aminobutyltriethoxysilane are preferably used.

[Preparation of component (A)]
As a method for obtaining the component (A), at least one acyl compound selected from the group consisting of tetracarboxylic dianhydrides represented by the general formula (2) and reactive derivatives thereof, and the general formula ( 3) reacting the amino group-containing hydrolyzable silane compound represented by 3) to obtain the hydrolyzable silane compound represented by the general formula (1), and if necessary, The method of including the process 2 of hydrolyzing and / or hydrolytically condensing the hydrolysable silane compound obtained in the process 1 is mentioned.

(Process 1)
First, in step 1, at least one acyl compound selected from the group consisting of tetracarboxylic dianhydrides represented by the general formula (2) and reactive derivatives thereof, and the general formula (3) By reacting with the amino group-containing hydrolyzable silane compound represented to obtain a hydrolyzable silane compound having an amic acid structure, the imidation of the amic acid structure is performed, whereby the general formula (1) The hydrolyzable silane compound represented is obtained.
As a method for obtaining a hydrolyzable silane compound having an amic acid structure by reacting the component (a1) and the component (a2), it was obtained after dissolving at least one component (a2) in an organic solvent. A method of adding at least one (a1) component to the solution and stirring at a temperature of 0 to 100 ° C. for 1 to 60 hours can be mentioned.
Examples of the organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, N, N′-dimethylimidazolidinone, and tetramethyl. Examples include aprotic polar solvents such as urea; phenolic solvents such as cresol, xylenol, and halogenated phenol. Of these, N-methyl-2-pyrrolidone and N, N-dimethylacetamide are preferable.
These solvents can be used alone or in combination of two or more.
The total amount of (a1) acyl compound and (a2) amino group-containing hydrolyzable silane compound in the reaction solution is preferably 5 to 50% by mass of the total amount of the reaction solution.

  The ratio of (a1) acyl compound to (a2) amino group-containing hydrolyzable silane compound is such that 1 equivalent of acid anhydride group of component (a1) and 0.9 to 1.1 of amino group of component (a2). The ratio which becomes an equivalent is preferable, and the ratio which becomes 0.9-1.0 equivalent is more preferable. When the amount of the amino group of the component (a2) is less than 0.9 equivalent or exceeds 1.1 equivalent with respect to 1 equivalent of the acid anhydride group of the component (a1), the unreacted component (a1) or (a2 ) Since the component remains, the reliability of the cured product may be reduced.

  The amido acid structure is an acid having a structure containing —CO—NH— and —CO—OH, which is generated by a reaction between an acid anhydride group and an amino group, or a derivative thereof (specifically, , For example, CO—NH— and —CO—OR (where R is an alkyl group or the like). The hydrolyzable silane compound having an amic acid structure has a cyclic chemical structure (—CO—N—CO—) by dehydrating H of —CO—NH— and OH of —CO—OH by heating or the like. It becomes an imide group-containing hydrolyzable silane compound.

Next, the hydrolyzable silane compound having an amic acid structure thus obtained is imidized by dehydrating and ring-closing, and as this method, a method using a dehydrating agent (chemical imidization) or 60 ° C. to 220 ° C. A heat treatment method (thermal imidization) can be mentioned.
Examples of the dehydrating agent in chemical imidization include acid anhydrides such as acetic anhydride, propionic anhydride, and benzoic anhydride, or corresponding acid chlorides, carbodiimide compounds such as dicyclohexylcarbodiimide, and the like. In addition, it is preferable to heat at the temperature of 60-120 degreeC in the case of chemical imidation.
In the case of thermal imidization, it is preferable to carry out while removing water generated by the dehydration reaction out of the system. At this time, water can be removed azeotropically using benzene, toluene, xylene or the like.
In the imidization, a base catalyst such as pyridine, isoquinoline, trimethylamine, triethylamine, N, N-dimethylaminopyridine, or imidazole can be used as necessary.
The dehydrating agent or the base catalyst is preferably used in an amount of 0.1 to 8 moles per mole of the acyl compound.
As the imidization method, chemical imidization is preferable because imidization can be performed by heating at a lower temperature.
The imidization is carried out so as to imidize at least a part of the hydrolyzable silane compound having an amic acid structure, preferably 75 mol% or more, more preferably 85 mol% or more, and particularly preferably 95 mol% or more. Is called.
The solution containing the obtained imide group-containing hydrolyzable silane compound and the organic solvent can be used as it is, but after isolating the imide group-containing hydrolyzable silane compound and the like, it is dissolved again in the organic solvent. It can also be used. Examples of the organic solvent to be redissolved include the same organic solvents as described above, ketone solvents such as methyl isobutyl ketone, methyl amyl ketone, and cyclohexanone, and proton solvents such as propylene glycol monomethyl ether and ethyl lactate. As a method for isolating the imide group-containing hydrolyzable silane compound, etc., the solution containing the imide group-containing hydrolyzable silane compound and the like and the organic solvent is concentrated by drying, etc. The method of isolate | separating is mentioned. By performing such an operation, it is possible to remove the dehydration catalyst (imidization catalyst) used in the imidization.

(Process 2)
In step 2, the hydrolyzable silane compound obtained in step 1 is hydrolyzed and / or hydrolyzed, preferably hydrolyzed.
By performing step 2, since a hydrolyzate and / or a hydrolyzed condensate (preferably a hydrolyzed condensate) is contained in the component (A), a cured film having better crack resistance can be obtained.
Although it does not specifically limit as a method of hydrolyzing and / or hydrolytically condensing a hydrolysable silane compound, For example, the method which consists of the process of following 1) -3) can be mentioned.
1) The hydrolyzable silane compound represented by the general formula (1) is accommodated in a container equipped with a stirrer.
2) Next, an organic solvent is further accommodated in the container while adjusting the viscosity of the obtained solution to obtain a mixed solution. A catalyst may be added as necessary.
3) After stirring the obtained mixed solution at a temperature not higher than the boiling point of the organic solvent or hydrolyzable silane compound in an air atmosphere, at 0 to 150 ° C. for 1 to 24 hours. Stir with heating. In addition, during heating and stirring, it is also preferable to concentrate the mixed solution by distillation or replace the organic solvent as necessary.

  The catalyst is not particularly limited as long as it promotes a hydrolysis reaction and a condensation reaction, and examples thereof include an acid or base catalyst. Examples of the acid include monovalent or polyvalent organic acids such as formic acid, acetic acid and oxalic acid; inorganic acids such as hydrochloric acid, phosphoric acid and sulfuric acid; inorganic salts such as Ti, Zr, Al and B, alkoxides and carboxylates And Lewis acid. Examples of the base include hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide; inorganic bases such as ammonia; amines such as trimethylamine, triethylamine, monoethanolamine and diethanolamine Is mentioned. These may be used alone or in combination of two or more. The amount of catalyst used in the case of using a catalyst varies depending on the type of catalyst used, but is usually preferably in the range of 0.001 to 5 mass% with respect to the total silane compound, and 0.002 to The range of 1% by mass is more preferable.

Usually, the solvent is preferably an organic solvent having a boiling point in the range of 50 to 200 ° C. under atmospheric pressure and capable of uniformly dissolving each component, for example, ether; ester; Examples include ketones; hydrocarbons such as aliphatic hydrocarbons and aromatic hydrocarbons; alcohols such as monohydric alcohols and polyhydric alcohols; heteroatom-containing compounds such as nitrogen-containing compounds and sulfur-containing compounds. These solvents may be used alone or in combination of two or more.
It is preferable that it is 1-1000 mass parts with respect to 100 mass parts of hydrolysable silane compounds, and, as for the usage-amount of a solvent, it is more preferable that it is 10-100 mass parts.

Here, in order to adjust the curability, viscosity, etc. of the radiation-sensitive composition, a hydrolyzable silane compound other than the hydrolyzable silane compound represented by the general formula (1) is mixed to obtain a siloxane oligomer. It can also be prepared. In this case, the hydrolyzable silane compound of the general formula (1) and the other hydrolyzable silane compound are added and mixed in the step 1), and then heated and reacted.
Examples of the other silane compounds include compounds represented by the following general formula (4) or (5).
R ³ _a Si (OR ⁴ ) _4-a (4)
(In General Formula (4), R ³ represents a hydrogen atom, a fluorine atom or a monovalent organic group, and a plurality of R ³ may be the same or different. R ⁴ represents a monovalent organic group, and R ⁴ present may be the same or different, and a represents an integer of 0 to 3.)
_{^{R 5 b (R 6 O)}} 3-b Si- (R 9) d -O e -Si (OR 7) 3-c R 8 c ··· (5)
(In General Formula (5), R ^{5 to} R ⁸ are the same or different, and each represents a hydrogen atom, a fluorine atom, or a monovalent organic group, b and c are the same or different, and each represents a number of 0 to 2, R ⁹ represents a phenylene group or a group represented by — (CH ₂ ) _m — (wherein m is an integer of 1 to 6), and d and e represent 0 or 1.)

In the general formula (4), examples of the monovalent organic group represented by R ³ and R ⁴ include an alkyl group, an alkenyl group, an aryl group, and a glycidyl group. Among them, the monovalent organic group represented by R ³ and R ⁴ is preferably an alkyl group or a phenyl group.
The alkyl group preferably has 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. These alkyl groups may be chain-like or branched, and a hydrogen atom may be substituted with a fluorine atom or the like. Examples of the alkenyl group include a vinyl group, a propenyl group, a 3-butenyl group, a 3-pentenyl group, and a 3-hexenyl group. Examples of the aryl group include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group.
In the general formula (4), examples of a = 0 compounds include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec. -Butoxysilane, tetra-tert-butoxysilane, tetraphenoxysilane and the like can be mentioned. Particularly preferred are tetramethoxysilane and tetraethoxysilane.
In the general formula (4), examples of the compound of a = 1 include, for example, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane. , Ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, n-butyltrimethoxysilane, iso-butyltrimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenethyltrimethoxysilane, Examples thereof include benzyltriethoxysilane.
In the general formula (4), examples of the compound of a = 2 include, for example, methyldimethoxysilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, and cyclohexylmethyldimethoxysilane. , Diphenyldimethoxysilane, diphenyldiethoxysilane, and the like.
In the general formula (4), examples of the compound of a = 3 include, for example, dimethylmethoxysilane, dimethylethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethyl-n-propoxysilane, triethylmethoxysilane, triethylethoxysilane, Examples include triethyl-n-propoxysilane, triphenylmethoxysilane, triphenyl-ethoxysilane, triphenyl-n-propoxysilane, and the like.
These can be used alone or in combination of two or more.

In the general formula (5), examples of the monovalent organic group represented by R ^{5 to} R ⁸ include the same groups as those exemplified as R ³ and R ^{4 in} the general formula (4).
In the general formula (5), preferred examples of the compound in which d = e = 0 include hexamethoxydisilane, hexaethoxydisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1, 1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyl Examples include disilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, and the like.
In the general formula (5), preferable examples of the compound where d = 1 and e = 0 are bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, 1,2-bis (trimethoxysilyl). Ethane, 1,2-bis (triethoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) methane, -(Dimethoxymethylsilyl) -2- (trimethoxysilyl) ethane, 1- (diethoxymethylsilyl) -2- (triethoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (diethoxymethylsilyl) ethane, bis (trimethoate) Sisilyl) hexane, 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,3-bis (trimethoxysilyl) benzene, 1,3-bis (triethoxysilyl) Examples thereof include benzene, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 1,4-bis (trimethoxysilylethylbenzene) and the like.
In the general formula (5), preferred examples of the compound where d = 1 and e = 1 are 1- (trimethoxysilyl) -1- (trimethoxysiloxy) methane, 1- (trimethoxysilyl) -2. Examples include-(trimethoxysiloxy) ethane, 1- (triethoxysilyl) -1- (trimethoxysiloxy) methane, 1- (triethoxysilyl) -2- (trimethoxysiloxy) ethane, and the like.
The above-mentioned compounds can be used alone or in combination of two or more.
The blending ratio of the other silane compound is preferably 80% by mass or less, more preferably 70% by mass or less, and particularly preferably 60% by mass or less in the total amount with the hydrolyzable silane compound represented by the general formula (1). is there.

[Component (B)]
The component (B) is a photoacid generator. Here, the photoacid generator is photocured (crosslinked) by irradiating energy rays such as light to (A) component (the hydrolyzable silane compound, hydrolyzate thereof, and hydrolyzed condensate thereof). Defined as a compound capable of releasing possible acidic active substances. In addition, visible light, ultraviolet rays, infrared rays, X-rays, α-rays, β-rays, γ-rays and the like can be given as light energy rays irradiated to decompose the photoacid generator and generate cations. Among them, it is preferable to use ultraviolet rays because it has a constant energy level, has a high (fast) curing rate, and the irradiation device is relatively inexpensive and compact.

  Moreover, it is also preferable to use together the radical generator mentioned later with a photoacid generator with a radiation sensitive composition. The radical which is a neutral active substance does not promote the condensation reaction of the silanol group, but when the radically polymerizable functional group is contained in the component (A), it promotes the polymerization of the functional group. Can do. Therefore, the photocurable composition can be cured more efficiently.

Examples of the photoacid generator include onium salts having a structure represented by the general formula (6) (first group of compounds) and sulfonic acid derivatives having a structure represented by the general formula (7) (second group of compounds). ).
_{^{[R 10 a R 11 b R}} 12 c R 13 d W] + m [MZ m + n] -m (6)
[In General Formula (6), the cation is an onium ion, W is S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, or —N≡N, and R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are the same or different organic groups, a, b, c and d are each an integer of 0 to 3, and (a + b + c + d) is equal to (valence of W + m). M is a metal or metalloid constituting the central atom of the halide complex [MX _{m + n} ], for example, B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, and Co. Z is, for example, a halogen atom or an aryl group such as F, Cl, Br, etc., m is the net charge of the halide complex ion, and n is the valence of M. ]
Q _s − [S (═O) ₂ —R ¹⁴ ] _t (7)
[In General Formula (7), Q is a monovalent or divalent organic group, R ¹⁴ is a monovalent organic group having 1 to 12 carbon atoms, s is 0 or 1, and t is 1 or 2. ]

［一般式（８）中、Ｒ^１５およびＲ^１６は、それぞれ独立して水素原子又はアルキル基、Ｒ^１７は水酸基または−ＯＲ^１７（但し、Ｒ^１７は１価の有機基である。）を示し、ａは４〜７の整数、ｂは１〜７の整数である。ナフタレン環への各置換基の結合位置は特に限定されない。］
［Ｒ^１８−Ａｒ^１−Ｉ^＋−Ａｒ^２−Ｒ^１９］［Ｙ⁻］ （９）
［一般式（９）中、Ｒ^１８およびＲ^１９は、それぞれ１価の有機基であり、同一でも異なっていてもよく、Ｒ^１８およびＲ^１９の少なくとも一方は炭素数が４以上のアルキル基を有しており、Ａｒ^１およびＡｒ^２はそれぞれ芳香族基であり、同一でも異なっていてもよく、Ｙ⁻は１価の陰イオンであり、周期律表３族、５族のフッ化物陰イオンもしくは、ＣｌＯ_４ ⁻、ＣＦ_３ ⁻、ＳＯ_３ ⁻から選ばれる陰イオンである。］
一般式（８）で表される化合物としては、４−ヒドロキシ−１−ナフチルテトラヒドロチオフェニウムトリフルオロメタンスルホネート、４−ブトキシ−１−ナフチルテトラヒドロチオフェニウムトリフルオロメタンスルホネート、１−（４，７−ジヒドロキシ）−ナフチルテトラヒドロチオフェニウムトリフルオロメタンスルホネート、１−（４，７−ジ−ｔ−ブトキシ）−ナフチルテトラヒドロチオフェニウムトリフルオロメタンスルホネートなどが挙げられる。
さらに、ジアリールヨードニウム塩としては、具体的に、（４−ｎ−デシロキシフェニル）フェニルヨードニウムヘキサフルオロアンチモネート、〔４−（２−ヒドロキシ−ｎ−テトラデシロキシ）フェニル〕フェニルヨードニウムヘキサフルオロアンチモネート、〔４−（２−ヒドロキシ−ｎ−テトラデシロキシ）フェニル〕フェニルヨードニウムトリフルオロスルホネート、〔４−（２−ヒドロキシ−ｎ−テトラデシロキシ）フェニル〕フェニルヨードニウムヘキサフルオロホスフェート、〔４−（２−ヒドロキシ−ｎ−テトラデシロキシ）フェニル〕フェニルヨードニウムテトラキス（ペンタフルオロフェニル）ボレート、ビス（４−ｔ−ブチルフェニル）ヨードニウムヘキサフルオロアンチモネート、ビス（４−ｔ−ブチルフェニル）ヨードニウムヘキサフルオロフォスフェート、ビス（４−ｔ−ブチルフェニル）ヨードニウムトリフルオロスルホネート、ビス（４−ｔ−ブチルフェニル）ヨードニウムテトラフルオロボレート、ビス（ドデシルフェニル）ヨードニウムヘキサフルオロアンチモネート、ビス（ドデシルフェニル）ヨードニウムテトラフルオロボレート、ビス（ドデシルフェニル）ヨードニウムヘキサフルオロフォスフェート、ビス（ドデシルフェニル）ヨードニウムトリフルオロメチルスルフォネート等の１種または２種以上の組み合わせを挙げることができる。 First, an onium salt that is a compound of the first group is a compound that can release an acidic active substance by receiving light. Specific examples of the anion [MZ _{m + n} ] in the general formula (6) include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarsenate ( AsF ₆ ^-), hexa-chloro antimonate (SbCl ₆ ^-), tetraphenylborate, tetrakis (trifluoromethylphenyl) borate, tetrakis (pentafluorophenyl methylphenyl)
Examples include borate.
Further, instead of the anion _{[MZ m + n]} in the general formula (6), the general formula ^- it is also preferable to use the anion represented by _[MZ n OH]. Furthermore, perchlorate ion (ClO ₄ ⁻ ), trifluoromethane sulfonate ion (CF ₃ SO ₄ ⁻ ), fluorosulfonate ion (FSO ₄ ⁻ ), toluene sulfonate ion, trinitrobenzene sulfonate anion, trinitrotoluene sulfonate Onium salts having other anions such as anions can also be used.
Among the compounds of the first group, more effective onium salts are aromatic onium salts, particularly preferably triarylsulfonium salts, compounds represented by the following general formula (8), and represented by the following general formula (9). Diaryl iodonium salt or triaryl iodonium salt.

[In General Formula (8), R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an alkyl group, R ¹⁷ represents a hydroxyl group or —OR ¹⁷ (where R ¹⁷ is a monovalent organic group). , A is an integer of 4-7, b is an integer of 1-7. The bonding position of each substituent to the naphthalene ring is not particularly limited. ]
^{[R 18 -Ar 1 -I + -Ar} 2 -R 19] [Y -] (9)
[In General Formula (9), R ¹⁸ and R ¹⁹ are each a monovalent organic group, which may be the same or different, and at least one of R ¹⁸ and R ¹⁹ represents an alkyl group having 4 or more carbon atoms. Each of Ar ¹ and Ar ² is an aromatic group, which may be the same or different, and Y ⁻ is a monovalent anion, and is a group 3 or group 5 fluoride anion of the periodic table. Alternatively, it is an anion selected from ClO ₄ ⁻ , CF ₃ ⁻ and SO ₃ ⁻ . ]
Examples of the compound represented by the general formula (8) include 4-hydroxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1- (4,7- And dihydroxy) -naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1- (4,7-di-t-butoxy) -naphthyltetrahydrothiophenium trifluoromethanesulfonate, and the like.
Further, as the diaryl iodonium salt, specifically, (4-n-decyloxyphenyl) phenyl iodonium hexafluoroantimonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyl iodonium hexafluoroantimonate [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium trifluorosulfonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluorophosphate, [4- (2 -Hydroxy-n-tetradecyloxy) phenyl] phenyliodonium tetrakis (pentafluorophenyl) borate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) Iodonium hexafluorophosphate, bis (4-t-butylphenyl) iodonium trifluorosulfonate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) Examples thereof include one or a combination of two or more of iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium trifluoromethylsulfonate, and the like.

  Examples of the sulfonic acid derivative represented by the general formula (7) as the second group of compounds include disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imidosulfonates, benzoin. Examples include sulfonates, sulfonates of 1-oxy-2-hydroxy-3-propyl alcohol, pyrogallol trisulfonates, and benzyl sulfonates. Of these, imide sulfonates are preferable, and among imide sulfonates, trifluoromethyl sulfonate derivatives are more preferable.

  In the radiation-sensitive composition of the present invention, the blending ratio of component (A) (imino group-containing hydrolyzable compound, hydrolyzate thereof, hydrolysis condensate thereof) and component (B) (photoacid generator) is Although it does not restrict | limit in particular, It is preferable that (B) component shall be the value within the range of 0.1-15 mass parts with respect to 100 mass parts of (A) component. When the amount of component (B) added is less than 0.1 parts by mass, the curability of the radiation-sensitive composition is lowered, and a sufficient curing rate may not be obtained. On the other hand, when the addition amount of (B) component exceeds 15 mass parts, the weather resistance and heat resistance of the obtained hardened | cured material may fall. From the viewpoint of a better balance between curability and the weather resistance of the resulting cured product, the component (B) has a value within the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (A). More preferably, the value is most preferably in the range of 0.1 to 5 parts by mass.

In addition to the above-described components (A) and (B), the radiation-sensitive composition of the present invention includes a radical photopolymerization initiator, a photosensitizer, an organic solvent, and a polymerization agent in addition to the components described above. Addition of inhibitors, polymerization initiation aids, leveling agents, wettability improvers, surfactants, plasticizers, UV absorbers, antioxidants, antistatic agents, silane coupling agents, inorganic fillers, pigments, dyes, etc. An agent can be further contained.
The radiation sensitive curable composition of this invention can be prepared by mixing the said (A) component, (B) component, and another arbitrary component by a conventional method.

[Pattern formation method]
In the method of forming a pattern using the radiation-sensitive composition of the present invention, the positive radiation-sensitive composition of the present invention is first applied to a substrate, semi-cured by heating, and subjected to pattern exposure, followed by a neutralization reaction. A post-exposure bake is performed to remove the exposed portion with a developer.
Hereinafter, a specific example will be described.
(1) Preparation of substrate First, a substrate having a flat surface is prepared. The type of the substrate is not particularly limited, and for example, a silicon substrate or a glass substrate can be used.
(2) Formation of coating film Next, the radiation-sensitive composition is applied to a substrate and dried or heated to form a coating film. Here, as a coating method of the radiation sensitive composition, a spin coating method, a dipping method, a spray method, a bar coating method, a roll coating method, a curtain coating method, a gravure printing method, a silk screen method, an ink jet method or the like is used. Can be used. Among these, it is more preferable to employ the spin coat method because a coating film having a uniform thickness can be obtained.
Moreover, it is preferable to pre-bake the coating film which consists of a radiation sensitive composition at 50-200 degreeC after application | coating, for example for 0.1 minute-1 hour. Here, the coating film is desirably in a semi-cured state in which the coating film dissolves in the developing solution and does not cause tackiness, and thus a range of 50 to 150 ° C. is more preferable.
(3) Radiation irradiation The upper surface of the coating film is irradiated with radiation according to a predetermined pattern, for example, through a photomask having a predetermined line pattern. Here, the type of radiation to be irradiated is not particularly limited, and visible light, ultraviolet light, infrared light, X-rays, and the like can be used. Usually, light in the ultraviolet to visible region of 200 to 450 nm is used. Preferably, light including ultraviolet light having a wavelength of 365 nm is used. Irradiation at a wavelength of 200 to 450 nm is such that the illuminance is 1 to 1,000 mW / cm ² and the irradiation amount is 0.01 to 5,000 mJ / cm ² , preferably 0.1 to 1,000 mJ / cm ^2. Done and exposed. For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, or an excimer lamp is preferably used as a radiation (ultraviolet) irradiation device.
(4) Heat treatment Next, it is preferable to perform heat treatment after exposure. The heating conditions vary depending on the composition of the radiation-sensitive composition, the type of additive, and the like, but are usually 30 to 200 ° C, preferably 50 to 150 ° C.
(5) Development The thin film that has been subjected to pattern exposure according to a predetermined pattern and selectively cured in this manner can be developed using the difference in solubility between the cured portion and the uncured portion. it can. Therefore, after pattern exposure, while removing an uncured portion and leaving a cured portion, a pattern can be formed as a result.
Here, the developer is an organic solvent, or sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine. , Methyldiethylamine, N-methylpyrrolidone, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene An aqueous alkali solution composed of alkalis such as 1,5-diazabicyclo [4.3.0] -5-nonane can be used.
Moreover, when using alkali water solubility, it is preferable to make the density | concentration into the value within the range of 0.05-25 mass% normally, Preferably it is 0.1-3.0 mass%.
In addition, it is also preferable to add an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like to such an alkaline aqueous solution and use it as a developer.
The developing time is usually 30 to 600 seconds, and a known method such as a liquid piling method, a dipping method, or a shower developing method can be adopted as the developing method.
When an organic solvent is used as the developer, it is air-dried as it is, and when an alkaline aqueous solution is used, it is washed with running water, for example, for 30 to 90 seconds, and then air-dried with compressed air, compressed nitrogen, etc. By removing the moisture, a patterned film is formed.
(6) Heat treatment after development Then, in order to further cure the patterning portion, when the heat treatment is performed at a temperature of, for example, 30 to 350 ° C. for 5 to 600 minutes using a heating device such as a hot plate or an oven, the cured coating film is formed. It is formed. The heating temperature is preferably 100 ° C to 340 ° C, more preferably 150 ° C to 330 ° C, and particularly preferably 200 ° C to 320 ° C. The thickness of the cured coating film is not particularly limited, but is preferably 0.1 μm to 100 μm, more preferably 1 μm to 50 μm, still more preferably 3 μm to 30 μm, and particularly preferably 5 μm to 20 μm. It is. According to the present invention, a cured coating film having a thickness of 10 μm or more can be obtained without generating cracks.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[Preparation of component (A)]
(Synthesis of raw material alkoxysilane)
Under a nitrogen stream, 3-aminopropyltriethoxysilane (22.14 g) and dimethylacetamide (61.37 g) were placed in a flask and stirred. Next, pyromellitic dianhydride (10.91 g) was added while cooling the flask in a water bath under a nitrogen stream, stirred at room temperature for 6 hours, and then allowed to stand at room temperature for 18 hours. Next, acetic anhydride (15.31 g) and pyridine (19.78 g) were added, and the mixture was stirred at 110 ° C. for 6 hours. After the reaction, the catalyst and the solvent were removed with an evaporator. This is designated as “Compound-1”.
In the same manner, “Compound-2” to “Compound-4” were synthesized as shown in Table 1.
(Synthesis of siloxane oligomer solution)
To a flask equipped with a stirrer and a reflux tube, compound-1 (19.77 g), phenyltrimethoxysilane (25.10), and 1-methoxy-2-propanol (21.82 g) were added and stirred. The temperature was heated to 60 ° C. Then, distilled water (12.3 g) was added dropwise, and after completion of the addition, the solution was stirred at 120 ° C. for 3 hours. And the 1-methoxy-2-propanol solution of (A) component which finally adjusted solid content to 50 mass% was obtained. This is designated as “siloxane oligomer solution A-1.”
In the same manner, as shown in Table 2, “A-2” to “A-7”, “A′-1”, and “A′-2” were synthesized.

[Preparation of radiation-sensitive composition]
1- (4,7-di-t-butoxy) -naphthyltetrahydrothiophenium trifluoromethanesulfonate ((B) with respect to 30.00 g (solid content and organic solvent) of the siloxane oligomer solution A-1 (component (A)) ) Component) 0.15 g and diglycerin EO adduct perfluorononinel ether 0.03 g were added and mixed uniformly to obtain “Composition 1”.
In the same manner, as shown in Table 3, “Composition 2” to “Composition 9” were prepared.

[Examples 1 to 7, Comparative Examples 1 and 2]
Using the obtained composition, crack resistance, patterning property, and heat resistance were evaluated by the following methods.
[Crack resistance]
The composition was applied by a spin coater to a thickness of 10μm on a silicon substrate, and thereafter the coated film was dried for 1 minute at 120 ° C., 1 minute wavelength 365 nm, the ultraviolet intensity 20 mW / cm ² at an exposure machine Irradiated, then heated at 300 ° C. for 1 hour and naturally cooled to prepare a cured film of the composition. The obtained cured film was observed for occurrence of cracks with an optical microscope, and the case where no crack was confirmed was designated as “◯”, and the case where the crack was confirmed was designated as “X”.
[Patternability]
The composition was applied on a silicon substrate with a spin coater to a thickness of 10 μm, and after drying this coating film at 100 ° C. for 3 minutes, using a photomask engraved with a pattern of width 50 μm, wavelength 365 nm, illuminance Exposure was performed by irradiating with 20 mW / cm ² of ultraviolet rays with an exposure machine for 1 minute. Thereafter, the substrate was heated at 80 to 120 ° C. for 1 minute, and then immersed in a developer composed of a 5% tetramethylammonium hydroxide (TMAH) aqueous solution to dissolve unexposed portions, and then washed with water. . Then, it heated at 300 degreeC for 1 hour, naturally cooled, and formed the pattern which consists of hardened | cured material of a composition. The substrate was cleaved to expose the end face of the pattern, and the pattern shape was observed with an optical microscope. The case where the shape was a rectangle was “◯”, and the shape was trapezoidal, the pattern top was round, or the case where patterning was not possible was “x”.
[Heat-resistant]
The composition was applied by a spin coater to a thickness of 10μm on a silicon substrate, and thereafter the coated film was dried for 1 minute at 120 ° C., 1 minute wavelength 365 nm, the ultraviolet intensity 20 mW / cm ² at an exposure machine Irradiated, then heated at 300 ° C. for 1 hour and naturally cooled to prepare a cured film of the composition. The cured product was shaved from the substrate with a cutter knife or the like, and the thermal weight reduction was examined with TG-DTA. The case where the 3% weight loss temperature was 300 ° C. or higher was “◯”, and the case other than that was “X”.

  From Table 4, it can be seen that according to the composition of the present invention, a cured film excellent in crack resistance, patterning property and heat resistance can be obtained (Examples 1 to 7). On the other hand, in Comparative Examples 1 and 2 using a silane compound that does not correspond to the component (A) of the present invention, it is understood that crack resistance (Comparative Examples 1 and 2) and patterning property (Comparative Example 2) are inferior.

Claims (7)

A radiation-sensitive composition comprising the following components (A) and (B):
(A) At least one selected from the group consisting of a hydrolyzable silane compound represented by the following general formula (1), a hydrolyzate of the hydrolyzable silane compound, and a condensate of the hydrolyzate

[In General Formula (1), R ¹ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and a plurality of R ¹ are the same or It may be different. R ² is a single bond, —CH ₂ — which may have a substituent, an alkylene group having 2 to 30 carbon atoms which may have a substituent, or 2 to 30 carbon atoms which may have a substituent. Or an alkenylene group having 2 to 30 carbon atoms which may have a substituent, or a divalent aromatic group having 2 to 30 carbon atoms which may have a substituent, and a plurality of R ² may be the same or different. X is a hydrolyzable group, and a plurality of Xs may be the same or different. A represents a tetravalent organic group. p is each independently an integer of 0 to 2, q is each independently an integer of 1 to 3, and p + q = 3. ]
(B) Photoacid generator The hydrolyzable silane compound is (a1) at least one acyl compound selected from the group consisting of tetracarboxylic dianhydrides represented by the following general formula (2) and reactive derivatives thereof: (a2) The radiation-sensitive composition according to claim 1, which is obtained by reacting with an amino group-containing hydrolyzable silane compound represented by the following general formula (3).

[In General Formula (2), A represents a tetravalent organic group. ]

[In General Formula (3), R ¹ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and a plurality of R ¹ are the same or It may be different. R ² is a single bond, —CH ₂ — which may have a substituent, an alkylene group having 2 to 30 carbon atoms which may have a substituent, or 2 to 30 carbon atoms which may have a substituent. Or an alkenylene group having 2 to 30 carbon atoms which may have a substituent, or a divalent aromatic group having 2 to 30 carbon atoms which may have a substituent. X is a hydrolyzable group, and a plurality of Xs may be the same or different. p is an integer of 0 to 2, q is an integer of 1 to 3, and p + q = 3. ]   The radiation sensitive composition of Claim 1 or 2 in which the said component (A) contains the condensate of the hydrolyzate of the hydrolysable silane compound represented by the said General formula (1). It is a manufacturing method of the radiation sensitive composition of Claim 2, Comprising:
At least one acyl compound selected from the group consisting of a tetracarboxylic dianhydride represented by the general formula (2) and a reactive derivative thereof, and an amino group-containing water represented by the general formula (3). A step of reacting a decomposable silane compound to obtain a hydrolyzable silane compound represented by the general formula (1);
Mixing the hydrolyzable silane compound and a photoacid generator;
The manufacturing method of the radiation sensitive composition containing this.   The manufacturing method of the radiation sensitive composition of Claim 4 including the process of hydrolyzing and / or hydrolytically condensing the obtained hydrolysable silane compound.   A radiation-sensitive composition according to any one of claims 1 to 3 is applied to a substrate to form a coating film, and then a desired region of the coating film is irradiated with radiation to be cured, and then developed. An uncured region other than the radiation-irradiated region of the coating film is removed by treatment.   The pattern formation method of Claim 6 including the process of heat-processing the said coating film, after removing uncured area | regions other than the radiation irradiation area | region of the said coating film.