JP2008203613A - Polyorganosiloxane composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive polyorganosiloxane composition excellent in lithography characteristics by development relative to a base substrate and in adhesiveness after heat curing while retaining good low-temperature curability, degassing property and volumetric shrinkage of a cured film at the time of forming an insulating material of electronic parts or a surface protective film, an interlayer insulation film, a planarizing film or the like in a semiconductor device. <P>SOLUTION: The polyorganosiloxane composition contains (a) 100 parts by mass of a polyorganosiloxane obtained by mixing a specific silanol compound and a specific alkoxysilane compound and polymerizing the mixture in the presence of a catalyst without adding water, (b) 0.2-20 parts by mass of a photopolymerization initiator, and (c) 0.05-20 parts by mass of a specific organosilicon compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention provides a photosensitive polyorganosiloxane excellent in adhesion to a base substrate during development and after heat-curing when forming an insulating material for electronic parts or a surface protective film, an interlayer insulating film, a planarizing film, etc. in a semiconductor device The present invention relates to a composition, a semiconductor device manufactured using the composition, and the like.

Patent Document 1 discloses a photosensitive polyorganosiloxane composition as a coating material that has good storage stability, can be cured with UV, has high permeability, and can have a thickness of 1 to 150 μm. Specifically, ORMOCER ONE, a coating material made by Fraunhofer ISC, Germany, comprising an organosilane having a polymerizable group and an organosilane having a hydrolysis reaction point using Ba (OH) ₂ (barium hydroxide) as a catalyst. There is. ORMOCER ONE can be cured at a low temperature of 150 ° C., and its cured product has excellent characteristics such as heat resistance of 300 ° C. or higher, residual low stress of 10 Mpa or lower, and flatness within 3%.
However, only the technique disclosed in Patent Document 1 uses a photosensitive polyorganosiloxane composition as a permanent material such as a surface protective film, an interlayer insulating film, an α-ray shielding film, a partition wall, and a planarizing film for electronic parts and semiconductor devices. It is difficult to achieve physical performances such as, for example, adhesion to a base material and mechanical properties at a practical level.

  On the other hand, a semiconductor device in which an element having an optical function or a mechanical function is mounted in an integrated circuit or separately from it is put into practical use. In many of these, after elements such as transistors are formed on a crystal substrate such as silicon using a conventionally known semiconductor process, elements having a function corresponding to the purpose of the semiconductor device are formed, and these are integrated into a package. It is manufactured by doing.

  As an example of such packaging technology, for example, Patent Document 2 discloses a microstructure formed on a crystal substrate on which an integrated circuit is formed, a packaging material for covering the microstructure, and the packaging material. A semiconductor device having a spacer for supporting the microstructure and an example thereof are disclosed in detail. The technology disclosed in Patent Document 2 can be suitably used for various sensors such as microlens arrays and chemical sensors, or a wide range of semiconductor devices such as surface acoustic wave devices, but the invention described in Patent Document 2 is used. For implementation, a spacer for supporting the packaging material on the microstructure plays an important role. The following three points can be considered as the characteristics required for the spacer.

First, since the spacer should be formed only in a portion necessary as a support, it is advantageous that the spacer itself is formed of a photosensitive member. This is because, if the spacer itself has photosensitivity, the latter can be omitted from the lithography process and the etching process that are usually used to leave the spacer only in a necessary portion.
In addition, a member having low heat resistance, for example, an adhesive such as an epoxy resin is used around the spacer, and a microstructure located under the spacer is not necessarily high in heat resistance. Therefore, secondly, it can be said that the process of forming the spacer is more preferable as the temperature is lower.

Thirdly, since the spacer forms a closed space including a microstructure, and a “cavity” if the description of Patent Document 2 is cited, a volatile component contained therein after the package is completed, etc. Is not preferred. That is, this spacer is required to be a low volatile component.
Although it is considered that the above-described characteristics are required for the spacer, Patent Document 2 does not disclose a specific member suitably used for the spacer.

European Patent No. 1196478 Special table 2003-516634 gazette

  It is an object of the present invention to maintain good low-temperature curability, degassability, and volume shrinkage of a cured film when forming an insulating material for an electronic component or a surface protective film, an interlayer insulating film, a planarizing film, etc. in a semiconductor device. On the other hand, it is to realize a photosensitive polyorganosiloxane composition excellent in lithography characteristics by development on a base substrate and adhesiveness after heat curing.

The present invention is as follows.
(1) A polyorganosiloxane composition containing the following components (a) to (c).
(A) At least one silanol compound represented by the following general formula (1) and at least one alkoxysilane compound represented by the following general formula (2) are mixed, and water is actively added in the presence of a catalyst. 100 parts by mass of polyorganosiloxane obtained by polymerization without addition

（Ｒ_１は、少なくとも芳香族基を１つ含む炭素数６〜２０の基である。）

(R ₁ is a group having 6 to 20 carbon atoms including at least one aromatic group.)

（Ｒ_２はエポキシ基及び炭素−炭素二重結合を有する基からなる群より選ばれる少なくとも一種の基を含む炭素数２〜１７の有機基である。Ｒ_３はメチル基またはエチル基である。）
（ｂ）光重合開始剤０．２〜２０質量部
（ｃ）下記一般式（３）で示される有機ケイ素化合物を０．０５〜２０質量部

(R ₂ is an organic group having 2 to 17 carbon atoms including at least one group selected from the group consisting of an epoxy group and a group having a carbon-carbon double bond. R ₃ is a methyl group or an ethyl group. )
(B) 0.2-20 parts by mass of a photopolymerization initiator (c) 0.05-20 parts by mass of an organosilicon compound represented by the following general formula (3)

（ｎは１または２の整数であり、ｎが１の場合、X_１は２価の芳香族基であり、ｎが２の場合、X_１は４価の芳香族基である。X_２はケイ素原子に直接結合する炭素原子を含む２価の有機基であり、ｌは１の整数である。Ｒ₄及びＲ₅は同一でも異なっても良く、炭素原子数１〜４のアルキル基であり、mは０，１または２の整数である。Ｒ₆は水素原子または１価の炭化水素基である。）
（２）前記（a）ポリオルガノシロキサンの触媒が一般式（４）及び一般式（５）で示される金属アルコキシドからなる群より選択される少なくとも１つの金属アルコキシド並びにアルカリ金属水酸化物及びアルカリ土類金属水酸化物からなる群より選ばれる少なくとも一種の化合物である（１）のポリオルガノシロキサン組成物。

(N is an integer of 1 or 2, when n is 1, X ₁ is a divalent aromatic group, and when n is 2, X ₁ is a tetravalent aromatic group. X ₂ is It is a divalent organic group containing a carbon atom directly bonded to a silicon atom, and l is an integer of 1. R ₄ and R ₅ may be the same or different and are alkyl groups having 1 to 4 carbon atoms. M is an integer of 0, 1 or 2. R ₆ is a hydrogen atom or a monovalent hydrocarbon group.)
(2) At least one metal alkoxide selected from the group consisting of the metal alkoxides represented by the general formula (4) and the general formula (5), the alkali metal hydroxide and the alkaline earth (a) the polyorganosiloxane catalyst. The polyorganosiloxane composition according to (1), which is at least one compound selected from the group consisting of metal hydroxides.

(Ｍ_１はケイ素、ゲルマニウム、チタニウムまたはジルコニウムのいずれかを示し、Ｒ₇は炭素数１〜４のアルキル基である。)

(M ₁ represents any _one of silicon, germanium, titanium, or zirconium, and R ₇ is an alkyl group having 1 to 4 carbon atoms.)

（Ｍ_２はホウ素またはアルミニウムを示し、Ｒ₇は炭素数１〜４のアルキル基である。）

(M ₂ represents boron or aluminum, and R ₇ represents an alkyl group having 1 to 4 carbon atoms.)

(3) The poly according to claim 2, wherein at least one metal alkoxide selected from the group consisting of the metal alkoxides represented by the general formula (4) and the general formula (5) is used as the catalyst. Organosiloxane composition.
(4) The polyorganosiloxane composition according to claim 3, wherein the catalyst further comprises at least one compound selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides.
(5) A step of applying a polyorganosiloxane composition according to any one of (1) to (4) on a substrate to obtain a coating film, irradiating the coating film with actinic rays through a patterning mask A method for forming a polyorganosiloxane cured relief pattern comprising a step of photocuring an exposed portion, a step of removing an uncured portion of the film using a developer, and a step of heating the whole substrate.
(6) A polyorganosiloxane cured relief pattern obtained by the method according to (5).
(7) A semiconductor device comprising the polyorganosiloxane cured relief pattern according to (6).
(8) A microstructure formed on a crystal substrate on which an integrated circuit is formed, a package material for covering the microstructure, and a spacer material for supporting the package material on the microstructure And the spacer material is formed using the polyorganosiloxane cured relief pattern described in (6).
(9) The semiconductor device according to (8), wherein the integrated circuit includes a photodiode.
(10) The semiconductor device according to (8), wherein the microstructure is a microlens.
(11) A step of applying the polyorganosiloxane composition according to any one of (1) to (4) directly on the microstructure or via a thin film layer to form a coating film, via a patterning mask And a step of photocuring the exposed portion by irradiating the film with actinic rays, a step of removing an uncured portion of the film using a developer, and a step of heating the whole substrate. Production method.

  The composition of the present invention improves the low-temperature curing property, degassing property, and volume shrinkage rate of a cured film when forming an insulating material for electronic parts or a surface protective film, an interlayer insulating film, a planarizing film, etc. in a semiconductor device. It can be maintained, and is excellent in lithographic properties by development on the base substrate and adhesiveness after heat curing.

<Polyorganosiloxane composition>
Each component which comprises the polyorganosiloxane composition of this invention is demonstrated concretely below.
(A) Polyorganosiloxane The polyorganosiloxane used in the polyorganosiloxane composition of the present invention is at least one silanol compound represented by the following general formula (1) and at least 1 represented by the following general formula (2). It is obtained by a method in which a seed alkoxysilane compound is mixed and polymerized in the presence of a catalyst without actively adding water.

（Ｒ_１は、少なくとも芳香族基を１つ含む炭素数６〜２０の基である。）

(R ₁ is a group having 6 to 20 carbon atoms including at least one aromatic group.)

（Ｒ_２はエポキシ基及び炭素−炭素二重結合を有する基からなる群より選ばれる少なくとも一種の基を含む炭素数２〜１７の有機基である。Ｒ_３はメチル基またはエチル基である。）

(R ₂ is an organic group having 2 to 17 carbon atoms including at least one group selected from the group consisting of an epoxy group and a group having a carbon-carbon double bond. R ₃ is a methyl group or an ethyl group. )

  In this case, the catalyst is composed of at least one metal alkoxide selected from the group consisting of metal alkoxides represented by the following general formulas (4) and (5), an alkali metal hydroxide, and an alkaline earth metal hydroxide. At least one compound selected from the group is preferably used.

(Ｍ_１はケイ素、ゲルマニウム、チタニウムまたはジルコニウムのいずれかを示し、Ｒ₇は炭素数１〜４のアルキル基である。)

(M ₁ represents any _one of silicon, germanium, titanium, or zirconium, and R ₇ is an alkyl group having 1 to 4 carbon atoms.)

（Ｍ_２はホウ素またはアルミニウムを示し、Ｒ₇は炭素数１〜４のアルキル基である。）

(M ₂ represents boron or aluminum, and R ₇ represents an alkyl group having 1 to 4 carbon atoms.)

In the at least one silanol compound represented by the general formula (1) (hereinafter sometimes abbreviated as “silanol compound”), R ₁ is a group having 6 to 20 carbon atoms including at least one aromatic group. Specifically, it is preferably at least one group selected from the groups represented by the following structures.

（Ａは炭素原子数１〜４のアルキル基、−ＣＨ＝ＣＨ_２、−ＣＨ＝ＣＨ−ＣＨ_３または−ＣＨ_２−ＣＨ＝ＣＨ_２のいずれかであり、yは０、１または２の整数である。）

(A is an alkyl group having 1 to 4 carbon atoms, —CH═CH ₂ , —CH═CH—CH ₃ or —CH ₂ —CH═CH ₂ , and y is an integer of 0, 1 or 2 .)

Examples of suitable silanol compounds include diphenylsilane diol, di-p-toluylsilane diol, di-p-styrylsilane diol, and dinaphthylsilane diol. In view of price, availability, performance, etc., diphenylsilanediol is particularly suitable.
In the at least one alkoxysilane compound represented by the general formula (2) (hereinafter sometimes abbreviated as an alkoxysilane compound), R ₂ is a group consisting of an epoxy group and a group having a carbon-carbon double bond. an organic group of 2 to 17 carbon atoms containing at least one group more selected, R ₃ is methyl or ethyl. A specific example of R ₂ is preferably at least one group selected from the groups represented by the following structures.

（Ｂは炭素原子数１〜４のアルキル基であり、ｚは０、１または２の整数である。）

(B is an alkyl group having 1 to 4 carbon atoms, and z is an integer of 0, 1 or 2.)

  Suitable alkoxysilane compounds include, for example, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 1-propenyltrimethoxysilane, 1-propenyltriethoxysilane, 2-propenyltrimethoxysilane, 2-propenyltriethoxysilane, 3- Methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, p-styryl Limethoxysilane, p-styryltriethoxysilane, p- (1-propenylphenyl) trimethoxysilane, p- (1-propenylphenyl) triethoxysilane, p- (2-propenylphenyl) trimethoxysilane, p- ( 2-propenylphenyl) triethoxysilane and the like. In order to obtain excellent photosensitivity, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane having a photopolymerizable carbon-carbon double bond, 3-acryloyloxypropyltriethoxysilane is more preferable, and 3-methacryloyloxypropyltrimethoxysilane is particularly preferable in consideration of price, toxicity, performance, and the like.

  The catalyst in the present invention is a compound that accelerates the dealcoholization condensation reaction between the silanol group of the silanol compound represented by the general formula (1) and the alkoxysilyl group of the alkoxysilane compound represented by the general formula (2). The catalyst suitable for the present invention may be abbreviated as at least one metal alkoxide selected from the group consisting of the metal alkoxides represented by the above general formulas (4) and (5) (hereinafter referred to as metal alkoxides). And at least one compound selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides.

The metal alkoxide represented by the above general formula (4) and the above general formula (5) includes the silanol group of the silanol compound represented by the above general formula (1) and the alkoxysilyl of the alkoxysilane compound represented by the above general formula (2). While catalyzing the dealcoholization condensation reaction of the group, it itself behaves as an alkoxy group-containing compound, participates in the dealcoholization condensation reaction, and is incorporated into the polyorganosiloxane molecule.
The mixing ratio is basically that the silanol compound and the alkoxysilane compound are mixed at 1: 1, and when mixing the metal alkoxide of the present invention here, a part of the alkoxysilane compound is replaced (the alkoxysilane compound mixing amount is changed). It is preferable to adjust the overall mixing ratio in the form of a constant ratio.

  Specifically, when the tetravalent metal alkoxide represented by the above general formula (4) is used as the metal alkoxide, the tetravalent metal alkoxide and the alkoxysilane compound are respectively converted at a molar ratio of 1: 2. It is preferable to replace (every 1 mol of the mixed amount of tetravalent metal alkoxide is increased by 2 mol of the alkoxysilane compound). When the trivalent metal alkoxide represented by the general formula (5) is used, the trivalent metal alkoxide and the alkoxysilane compound are preferably converted at a molar ratio of 2: 3 and replaced.

  Suitable trivalent or tetravalent metal alkoxides include trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, tri-iso-propoxyaluminum, tri-n-butoxyaluminum, tri-iso-butoxyaluminum. , Tri-sec-butoxyaluminum, tri-tert-butoxyaluminum, trimethoxyboron, triethoxyboron, tri-n-propoxyboron, tri-iso-propoxyboron, tri-n-butoxyboron, tri-iso-butoxyboron , Tri-sec-butoxyboron, tri-tert-butoxyboron tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxy Lan, tetra-iso-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetramethoxygermanium, tetraethoxygermanium, tetra-n-propoxygermanium, tetra-iso-propoxygermanium, tetra-n-butoxy Germanium, tetra-iso-butoxygermanium, tetra-sec-butoxygermanium, tetra-tert-butoxygermanium, tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetra-iso-propoxytitanium, tetra-n-butoxy Titanium, tetra-iso-butoxy titanium, tetra-sec-butoxy titanium, tetra-tert-butoxy titanium, tetramethoxy zirconium, tetraethoxydi Koniumu, tetra -n- propoxy zirconium, tetra -iso- propoxy zirconium, tetra -n-butoxy zirconium, tetra -iso- butoxy zirconium, tetra -sec- butoxy zirconium, tetra--tert- butoxy zirconium, and the like. In order to achieve a rapid and uniform polymerization reaction, it is preferably liquid in the reaction temperature range, and tetra-iso-propoxytitanium is particularly suitable in view of high activity and availability as a catalyst.

The heating temperature at the time of polymerizing and producing the polyorganosiloxane of the present invention is an important parameter for controlling the degree of polymerization of the polyorganosiloxane to be produced. Although depending on the desired degree of polymerization, it is preferable to polymerize the raw material mixture by heating it to approximately 70 ° C to 150 ° C.
When the addition amount at the time of polymerization of the metal alkoxide is less than 2 mol% with respect to the silanol compound represented by the general formula (1), the degree of polymerization of the polyorganosiloxane is considered even when heated above the preferred temperature range. Can't be raised. In such a case, by adding an appropriate amount of alkali metal hydroxide or alkaline earth metal hydroxide as a catalyst, it is possible to compensate for the shortage of metal alkoxide and moderately control the degree of polymerization of the polyorganosiloxane produced. It becomes.

Suitable alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like. Suitable alkaline earth metal hydroxides include alkaline earth metal hydroxides such as calcium hydroxide, strontium hydroxide and barium hydroxide, and hydrates thereof.
The upper limit of the polymerization addition amount of the metal alkoxide depends on the performance of the target polyorganosiloxane. In order to achieve excellent photosensitivity, the aforementioned alkoxysilane compound having a photopolymerizable carbon-carbon double bond is essential, and the upper limit of the polymerization addition amount of the metal alkoxide is calculated from the minimum required amount. (A) Preferably it is 40 mol% or less with respect to a silanol compound, More preferably, it is 30 mol% or less.

(B) Photopolymerization initiator It is important to add a photopolymerization initiator to the composition of the present invention for the purpose of imparting photosensitivity. Preferable compounds include the following compounds.
(1) Benzophenone derivatives: for example, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, fluorenone (2) acetophenone derivatives: for example, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] -phenyl} -2-methylpropan-1-one, phenylglyoxyl Methyl (3) thioxanthone derivatives: for example, thioxanthone, 2-methyl Ruthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone (4) benzyl derivatives: eg benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal (5) benzoin derivatives: eg benzoin, benzoin methyl ether, 2-hydroxy-2 -Methyl-1-phenylpropan-1-one

(6) Oxime compounds: for example, 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-benzoyl) oxime, 1,3-diphenylpropanetrione-2 -(O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O- Benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O Acetyl oxime)
(7) α-hydroxy ketone compounds: for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl -1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropane (8) α-aminoalkylphenone system Compound: For example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholine-4 -Yl-phenyl) butan-1-one (9) phosphine oxide compounds: for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxy Id, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl - pentyl phosphine oxide, 2,4,6-trimethylbenzoyl - diphenyl - phosphine oxide (10) titanocene compounds: such as bis (eta ⁵ -2,4-cyclopentadiene-1-yl) - bis (2,6-difluoro-3-(1H-pyrrol-1-yl) phenyl) titanium addition, when these used alone for two or more even It can be a mixture.

  Among the photopolymerization initiators described above, the α-aminoalkylphenone compound (8) is more preferable particularly from the viewpoint of photosensitivity. The addition amount is preferably 0.2 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of (a) polyorganosiloxane of the present invention. When the addition amount exceeds 0.2 parts by mass, radicals sufficient to allow radical photopolymerization to proceed sufficiently are supplied during exposure, so that curing of the exposed part proceeds and a practical relief pattern can be obtained. it can. On the other hand, when the addition amount is less than 20 parts by mass, the exposure light beam reaches the vicinity of the substrate surface in order to prevent the exposure absorption in the vicinity of the coating film surface from becoming too large. A uniform relief pattern and a practical relief pattern can be obtained.

(C) Organosilicon compound It is important to add an organosilicon compound represented by the following general formula (3) to the composition of the present invention for the purpose of improving adhesion to the base substrate.

(N is an integer of 1 or 2, and when n is 1, X ₁ is a divalent aromatic group, and when n is 2, X ₁ is a tetravalent aromatic group. X ₂ is A divalent organic group containing a carbon atom directly bonded to a silicon atom, and l is an integer of 0 or 1. R ₄ and R ₅ may be the same or different, and are an alkyl group having 1 to 4 carbon atoms. M is an integer of 0, 1 or 2. R ₆ is a hydrogen atom or a monovalent hydrocarbon group.)

The organosilicon compound can be obtained by reacting an organosilicon compound containing an amino group with a dicarboxylic anhydride or a tetracarboxylic dianhydride derivative.
Here, dicarboxylic anhydrides or tetracarboxylic dianhydride derivatives having various structures can be used, for example, maleic anhydride, phthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 4-methylcyclohexane- 1,2-dicarboxylic acid anhydride, 1-cyclohexene-1,2-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 1,2-naphthalic acid anhydride, 1,8-naphthalic acid Anhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 2,2 -Bis (3,4-dicarboxyphenyl) hexafluoropropylidenetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyltetracarboxylic acid 2 Anhydrides are mentioned.
In view of the effect of excellent adhesion to the base substrate and the price, phthalic anhydride and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride are particularly suitable.

Various structures can be used for the organosilicon compound containing an amino group, and examples thereof include the following (hereinafter, the notation of alkoxy indicates a methoxy group or an ethoxy group).
2-aminoethyltrialkoxysilane, 3-aminopropyltrialkoxysilane, 3-aminopropyl dialkoxymethylsilane, 2-aminoethylaminomethyltrialkoxysilane, 2-aminoethylaminomethyldialkoxymethylsilane, 3- (2 -Aminoethylaminopropyl) trialkoxysilane, 3- (2-aminoethylaminopropyl) dialkoxymethylsilane, 3-allylaminopropyltrialkoxysilane, 2- (2-aminoethylthioethyl) trialkoxysilane, 2- (2-Aminoethylthioethyl) dialkoxymethylsilane, 3-piperazinopropyltrialkoxysilane, 3-piperazinopropyl dialkoxymethylsilane, cyclohexylaminopropyltrialkoxysilane and the like.
In view of the effect of adhesiveness to the base substrate and the price, 3-aminopropyltriethoxysilane is particularly suitable.

  The addition amount of the organosilicon compound is preferably 0.05 to 20 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the component (a) of the present invention. When the addition amount exceeds 0.05 parts by mass, an effect of improving adhesion to the base substrate appears. When the addition amount is less than 20 parts by mass, it does not precipitate in the composition. Moreover, in using these, it may be individual or a mixture of 2 or more types.

  To the composition of the present invention, a compound having a photopolymerizable unsaturated bond group other than the component (a) can be added for the purpose of improving film forming characteristics, photosensitive characteristics, and mechanical characteristics after curing. As this, a polyfunctional (meth) acryl compound that can be polymerized by the action of a photopolymerization initiator is preferable. For example, polyethylene glycol diacrylate [number of ethylene glycol units 2 to 20], polyethylene glycol dimethacrylate [ethylene glycol unit] 2-20], poly (1,2-propylene glycol) diacrylate [1,2-propylene glycol unit number 2-20], poly (1,2-propylene glycol) dimethacrylate [1,2-propylene glycol Unit number 2-20], polytetramethylene glycol diacrylate [tetramethylene glycol unit number 2-10], polytetramethylene glycol dimethacrylate [tetramethylene glycol unit number 2-10], 1,4-cyclohexanediacrylene 1,4-cyclohexanedimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate [number of ethylene glycol units 2 to 20], trimethylolpropane trimethacrylate, Tri-2-hydroxyethyl isocyanurate triacrylate, tri-2-hydroxyethyl isocyanurate trimethacrylate, glycerol diacrylate, glycerol dimethacrylate, ditrimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipenta Erythritol hexaacrylate, methylene bisacryla Ethylene glycol diglycidyl ether-methacrylic acid adduct, glycerol diglycidyl ether-acrylic acid adduct, bisphenol A diglycidyl ether-acrylic acid adduct, bisphenol A diglycidyl ether-methacrylic acid adduct, ethoxylated bisphenol A di Examples include acrylate [number of ethylene glycol units 2 to 30], ethoxylated bisphenol A dimethacrylate [number of ethylene glycol units 2 to 30], and N, N′-bis (2-methacryloyloxyethyl) urea. Moreover, in using these, you may use individually or in mixture of 2 or more types as needed. When added, the addition amount is preferably 1 to 100 parts by mass and more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the component (a) of the present invention.

  A silicone resin can be added to the composition of the present invention for the purpose of improving the tackiness and fluidity of the coating film after soft baking. The silicone resin as used herein refers to, for example, an organosilane compound having 2 to 4 hydrolyzable groups such as alkoxysilyl groups and chlorosilyl groups described in “Silicon Handbook” (1990) published by Nikkan Kogyo Shimbun. It refers to a polymer having a three-dimensional network structure obtained by cohydrolysis and polymerization.

  In the object of the present invention, it is preferable to add a so-called straight silicone resin such as methyl, phenyl, phenylmethyl, phenylethyl, or phenylpropyl. Examples of these include methyl silicone resins such as KR220L, KR242A, KC89, KR400, and KR500 (manufactured by Shin-Etsu Chemical Co., Ltd.), 217 flakes (manufactured by Dow Corning Toray), SR-20, SR-21 (manufactured by Konishi Chemical Industries, Ltd.). Phenyl silicone resins such as KR213, KR9218 (manufactured by Shin-Etsu Chemical Co., Ltd.), 220 flakes, 223 flakes, 249 flakes (manufactured by Dow Corning Toray), SR-23 (Konishi Chemical) And the like, and phenylpropyl silicone resins such as Z-6018 (manufactured by Dow Corning Toray). For the purpose of improving tackiness and fluidity, it is preferable to add a silicone resin that has a higher crosslink density and is solid in a normal temperature range. In that sense, among the above preferred examples, a phenyl-based or phenylpropyl-based silicone resin is preferably used. It is particularly preferred to select. Further, it is preferable to select those having a part of silanol residue in the structure, since the examination by the present inventors has revealed that the effect of improving tackiness and fluidity is further enhanced.

  It is preferable that the addition amount of these silicone resins suitable for this invention is 50-200 mass parts with respect to 100 mass parts of (a) component of this invention. In order to obtain an effect of improving tackiness and fluidity, at least 50 parts by mass is necessary, and if it is 200 parts by mass or less, it is possible to maintain lithography characteristics such as i-line sensitivity.

  A viscosity can be adjusted by adding a solvent to the composition of the present invention. Suitable solvents include N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, cyclopentanone , Γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl Examples include isobutyl ketone, anisole, ethyl acetate, ethyl lactate, and butyl lactate, and these can be used alone or in combination of two or more. Among these, N-methyl-2-pyrrolidone, γ-butyrolactone, and propylene glycol monomethyl ether acetate are particularly preferable. These solvents can be appropriately added to the composition of the present invention depending on the coating film thickness and viscosity, but should be used in the range of 5 to 100 parts by mass with respect to 100 parts by mass of the component (a) of the present invention. Is preferred.

  A sensitizer for improving photosensitivity can be added to the composition of the present invention as desired. Examples of such a sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzylidene) cyclopentanone, and 2,6-bis (4′-diethylamino). Benzylidene) cyclohexanone, 2,6-bis (4′-dimethylaminobenzylidene) -4-methylcyclohexanone, 2,6-bis (4′-diethylaminobenzylidene) -4-methylcyclohexanone, 4,4′-bis (dimethylamino) ) Chalcone, 4,4′-bis (diethylamino) chalcone, 2- (4′-dimethylaminocinnamylidene) indanone, 2- (4′-dimethylaminobenzylidene) indanone, 2- (p-4′-dimethylamino) Biphenyl) benzothiazole, 1,3-bis (4-dimethyla) Nobenzylidene) acetone, 1,3-bis (4-diethylaminobenzylidene) acetone, 3,3′-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7- Dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N-ethylethanolamine, N-phenyldiethanolamine , Np-tolyldiethanolamine, N-phenylethanolamine, N, N-bis (2-hydroxyethyl) aniline, 4-morpholinobenzophenone, isoamyl 4-dimethylaminobenzoate, 4-diethylamino Isoamyl benzoate, benztriazole, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, 1-cyclohexyl-5-mercapto-1,2,3,4-tetrazole, 1- (tert-butyl) -5-mercapto-1,2,3,4-tetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) Examples include benzthiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-p) thiazole, 2- (p-dimethylaminobenzoyl) styrene, and the like. In use, it may be used alone or as a mixture of two or more. The addition amount in the case of adding may have balance with other additive component amounts, but is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (a) of the present invention. More preferably, it is -5 mass parts.

  If desired, a polymerization inhibitor can be added to the composition of the present invention for the purpose of improving the viscosity during storage and the stability of photosensitivity. Examples of such polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid. 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N- Ethyl-N-sulfopropylamino) phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt ,Screw Or the like can be used 4-hydroxy-3,5-di-tert- butyl) phenyl methane. When added, the addition amount is preferably 0.01 to 5 parts by mass and more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the component (a) of the present invention.

A silane coupling agent can be added to the composition of the present invention for the purpose of further improving the adhesion. Examples of the silane coupling agent include the following. (Hereinafter, the notation of alkoxy refers to a methoxy group or an ethoxy group.) Vinyltrialkoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, 3-glycidoxypropyltrialkoxysilane, 3-glyci Doxypropylmethyl dialkoxysilane, p-styryltrialkoxysilane, 3-methacryloxypropyltrialkoxylane, 3-methacryloxypropylmethyl dialkoxylane, 3-acryloxypropyltrialkoxylane, 3-acryloxypropylmethyl dialkoxy Lan, N-2 (aminoethyl) -3-aminopropyltrialkoxysilane, N-2 (aminoethyl) -3-aminopropylmethyldialkoxysilane, 3-aminopropyltrialkoxysilane, 3-trialkoxysilane Ru-N- (1.3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrialkoxysilane, 3-ureidopropyltrialkoxysilane, 3-ureidopropylmethyldialkoxysilane, 3-mercaptopropyltri Alkoxysilane, 3-mercaptopropylmethyl dialkoxysilane, bis (trialkoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltrialkoxysilane and the like can be used. When added, the addition amount is preferably 0.1 to 50 parts by mass, more preferably 2 to 35 parts by mass with respect to 100 parts by mass of the component (a) of the present invention.
In addition to the above, the composition of the present invention includes various additives as necessary, as long as it does not inhibit various properties of the composition of the present invention, including an ultraviolet absorber, a coating film smoothness imparting agent, etc. An agent can be appropriately blended.

<Method for forming polyorganosiloxane cured relief pattern>
Next, the suitable example of the method of forming a hardening relief pattern using the composition of this invention is shown below.

[Process of obtaining a coating film by applying a polyorganosiloxane composition]
The composition is applied to various desired base materials in addition to a silicon wafer, a ceramic substrate, an aluminum substrate and the like, and a substrate on which an organic thin film is formed. As the coating apparatus or coating method, a spin coater, a die coater, a spray coater, dipping, printing, a blade coater, roll coating, or the like can be used.
You may soft-bake at 80-200 degreeC after application | coating.

[Step of irradiating the coating film with an actinic ray through a patterning mask to photocure the exposed portion]
An actinic ray is irradiated through a desired photomask using an exposure projection apparatus such as a contact aligner, a mirror projection, or a stepper.
X-rays, electron beams, ultraviolet rays, visible rays and the like can be used as the actinic rays, but in the present invention, those having a wavelength of 200 to 500 nm are preferably used. In light of pattern resolution and handleability, the light source wavelength is particularly preferably UV i-line (365 nm), and a stepper is particularly preferred as the exposure projection apparatus.
Post exposure bake (PEB) by any combination of temperature and time (preferably temperature 40 ° C. to 200 ° C., time 10 seconds to 360 seconds), if necessary, for the purpose of improving photosensitivity after exposure, Baking before development may be performed.

[Step of removing uncured portion of coating film using developer]
The developing method can be selected from methods such as an immersion method, a paddle method, and a rotary spray method. Thereby, a post-development relief pattern is obtained. As the developer, the good solvent of the composition of the present invention can be used alone, or a good solvent and a poor solvent can be appropriately mixed and used. Good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, α-acetyl-gammabutyrolactone, cyclo Pentanone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, and the like are used as the poor solvent, and methanol, ethanol, iso-propanol, water, and the like are used.
After the development is completed, the film is washed with a rinse solution, and the developer solution is removed to obtain a coating film with a relief pattern. As the rinsing liquid, distilled water, methanol, ethanol, iso-propanol, propylene glycol monomethyl ether, iso-butyl alcohol, 4-methyl-pentanol, etc. are used alone or in combination as appropriate, or stepwise combined. It can also be used.

[Step of heating together with base material]
The obtained post-development relief pattern is converted into a polyorganosiloxane cured relief pattern (hereinafter sometimes abbreviated as a cured relief pattern) at a curing temperature of 150 to 250 ° C., which is much lower than conventional ones. . This heat curing can be performed using a hot plate, an inert oven, a temperature rising oven in which a temperature program can be set, or the like. Air may be used as the atmospheric gas for heat curing, and an inert gas such as nitrogen or argon may be used as necessary.
The cured relief pattern described above is applied between a micro structure such as a surface protective film, an interlayer insulating film, an α-ray shielding film, or a micro lens array of a semiconductor device formed on a substrate such as a silicon wafer and the package material. Various semiconductor devices including an optical element such as a CMOS image sensor are used as any one selected from the group consisting of the supports (partition walls) and other processes are applied to a known semiconductor device manufacturing method. Can be manufactured. Moreover, the electronic component and semiconductor device which have a coating film which consists of resin which hardened the composition mentioned above can be obtained.

  A microstructure formed on a crystal substrate on which an integrated circuit is formed; a package material for covering the microstructure; and a spacer material for supporting the package material on the microstructure. In the semiconductor device, the spacer material may be a semiconductor device using the polyorganosiloxane cured relief pattern of the present invention. Here, specific examples of the integrated circuit include a crystal substrate and a photodiode including silicon, lithium niobate, lithium tartrate, or quartz. A microstructure means a micron-sized mechanical, photomechanical, or electromechanical device. Specifically, a microlens is mentioned. The packaging material is preferably transparent and may be formed of glass.

  As a manufacturing method of the semiconductor device, a process for forming a coating film by applying the polyorganosiloxane composition of the present invention directly or through a thin film layer on a microstructure, an opening is formed only in a portion where a spacer material is to be formed. Including a step of irradiating the film with an actinic ray through a patterning mask, a step of photocuring the exposed portion, a step of removing an uncured portion of the film using a developer, and a step of heating the whole substrate A manufacturing method is mentioned. Each process can be performed by the above-mentioned method.

Next, the present invention will be described with reference to examples and comparative examples.
[Synthesis Example 1]
(Synthesis of polyorganosiloxane P-1)
In a 2-liter round bottom flask equipped with a water-cooled condenser and a stirring blade with a vacuum seal, 540.78 g (2.5 mol) of diphenylsilanediol (hereinafter referred to as DPD), 3-methacryloyloxypropyltrimethoxysilane (hereinafter referred to as MEMO) 577.41 g (2.325 mol) and 24.87 g (0.0875 mol) tetra-iso-propoxytitanium (hereinafter referred to as TIP) were charged, and stirring was started. This was immersed in an oil bath, the heating temperature was set to 120 ° C., and heating was started from room temperature. In the middle of the reaction, methanol generated with the progress of the polymerization reaction was refluxed with a water-cooled condenser while reacting until the temperature of the reaction solution became constant, and then heated and stirred for another 30 minutes.
After that, attach a hose connected to the cold trap and the vacuum pump, stir vigorously while heating at 80 ° C using an oil bath, and gradually raise the degree of methanol so that methanol does not bump up. Distilled off to obtain polyorganosiloxane P-1 (viscosity 100 poise at 23 ° C.).

[Synthesis Example 2]
(Synthesis of polyorganosiloxane P-2)
In a 2-liter round bottom flask equipped with a water-cooled condenser and a stirring blade with a vacuum seal, 43.62 g (2.0 mol) of DPD, 495.71 g (1.996 mol) of MEMO, and 0.568 g (0. 002 mol) and 0.16 g (0.004 mol) of sodium hydroxide were charged, and stirring was started. This was immersed in an oil bath, the heating temperature was set to 80 ° C., and heating was started from room temperature. In the middle of the reaction, methanol generated with the progress of the polymerization reaction was refluxed with a water-cooled condenser while reacting until the temperature of the reaction solution became constant, and then heated and stirred for another 30 minutes.
Thereafter, the reaction solution was cooled to room temperature and passed through a glass column filled with an ion exchange resin (Amberlyst 15 manufactured by Organo Corp., swollen and washed with 40 g of dry weight with methanol) to remove sodium ions. .
Transfer this to a round-bottomed flask equipped with a stirring blade with a vacuum seal and a hose connected to a cold trap and a vacuum pump, soak it in an oil bath heated to 80 ° C, and stir vigorously to prevent methanol from bumping. By gradually raising the degree of vacuum, methanol was distilled off to obtain polyorganosiloxane P-2 (viscosity 50 poise at 23 ° C.). As a result of inductively coupled plasma mass spectrometry, the sodium ion concentration in P-2 was less than 1 ppm.

[Synthesis Example 3]
(Synthesis of polyorganosiloxane P-3)
In a 2-liter round bottom flask equipped with a water-cooled condenser and a stirring blade with a vacuum seal, 43.62 g (2.0 mol) of DPD, 496.70 g (2.0 mol) of MEMO, and barium hydroxide monohydrate were added. 0.76 g (0.004 mol) was charged and stirring was started. This was immersed in an oil bath, the heating temperature was set to 80 ° C., and heating was started from room temperature. In the middle of the reaction, methanol generated with the progress of the polymerization reaction was refluxed with a water-cooled condenser while reacting until the temperature of the reaction solution became constant, and then heated and stirred for another 30 minutes.
Thereafter, the reaction solution was cooled to room temperature and passed through a glass column filled with an ion exchange resin (Amberlyst 15 manufactured by Organo Corporation, swollen and washed with 40 g of dry weight with methanol) to remove barium ions. .
Transfer this to a round-bottomed flask equipped with a stirring blade with a vacuum seal and a hose connected to a cold trap and a vacuum pump, soak it in an oil bath heated to 80 ° C, and stir vigorously to prevent methanol from bumping. By gradually raising the degree of vacuum, methanol was distilled off to obtain polyorganosiloxane P-3 (viscosity of 46 poise at 23 ° C.). As a result of inductively coupled plasma mass spectrometry, the barium ion concentration in P-3 was less than 1 ppm.

[Synthesis Example 4]
(Synthesis of organosilicon compound S-1)
A 1 L round bottom flask was charged with 29.6 g (0.2 mol) of phthalic anhydride and 195 g of N-methyl-2-pyrrolidone and agitated. The solution was cooled to 0 ° C., and a solution of 44.2 g (0.2 mol) of 3-aminopropyltriethoxysilane in 100 g of N-methyl-2-pyrrolidone was added. This was returned to room temperature and stirred for 4 hours to obtain an N-methyl-2-pyrrolidone solution containing 20% by mass of organosilicon compound S-1.

[Synthesis Example 5]
(Synthesis of organosilicon compound S-2)
In the same manner as in Synthesis Example 4, maleic anhydride (0.2 mol) and 3-aminopropyldiethoxymethylsilane (0.2 mol) were reacted to obtain an N-methyl-2-pyrrolidone solution containing 20% by mass of organosilicon compound S-2. It was.

[Synthesis Example 6]
(Synthesis of organosilicon compound S-3)
In the same manner as in Synthesis Example 4, 0.2 mol of 4-methylcyclohexane-1,2-dicarboxylic anhydride and 0.2 mol of 3- (2-aminoethylaminopropyl) triethoxysilane are reacted to form an organosilicon compound S-3. An N-methyl-2-pyrrolidone solution containing 20% by mass was obtained.

[Synthesis Example 7]
(Synthesis of organosilicon compound S-4)
In a 1 L round bottom flask, 32.2 g (0.1 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and 206 g of N-methyl-2-pyrrolidone were charged and stirring was started. The solution was cooled to 0 ° C., and a solution of 44.2 g (0.2 mol) of 3-aminopropyltriethoxysilane in 100 g of N-methyl-2-pyrrolidone was added. This was returned to room temperature and stirred for 4 hours to obtain an N-methyl-2-pyrrolidone solution containing 20% by mass of organosilicon compound S-4.

[Synthesis Example 8]
(Synthesis of organosilicon compound S-5)
In the same manner as in Synthesis Example 7, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride 0.1 mol was reacted with 0.2 mol of 3-aminopropyltrimethoxysilane to give 20 organosilicon compound S-5. An N-methyl-2-pyrrolidone solution containing mass% was obtained.

[Synthesis Example 9]
(Synthesis of organosilicon compound S-6)
In the same manner as in Synthesis Example 7, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride 0.1 mol and 3- (2-aminoethylaminopropyl) triethoxysilane 0.2 mol were reacted. An N-methyl-2-pyrrolidone solution containing 20% by mass of silicon compound S-6 was obtained.

[Example 1]
(Preparation of polyorganosiloxane composition C-1)
100 parts by mass of polyorganosiloxane P-1 obtained in Synthesis Example 1 and 20 parts by mass of N-methyl-2-pyrrolidone solution containing 20% by mass of organosilicon compound S-1 obtained in Synthesis Example 4 (S -1 pure 4 parts by mass), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE369 manufactured by Ciba Specialty Chemicals), 4 parts by mass, 4,4′-bis ( 0.5 parts by weight of diethylamino) benzophenone, 30 parts by weight of polytetramethylene glycol dimethacrylate (tetramethylene glycol unit number 8 PDT-650 manufactured by NOF Corporation), and 150 parts by weight of silicone resin (217 flakes manufactured by Toray Dow Corning) , N-methyl-2-pyrrolidone, 24 parts by weight, respectively, and mixed to obtain a pore size of 0.2 microns Teflon filtered (registered trademark) filter to obtain a varnish-like polyorganosiloxane composition C-1.

(Lithography characteristics evaluation)
The varnish-like polyorganosiloxane composition C-1 obtained in Example 1 above was applied onto a 5-inch silicon wafer using a spin coater (model name Clean Track Mark 7 manufactured by Tokyo Electron), and 12 ° C. at 12 ° C. Soft baking was performed for a minute to obtain a coating film having an initial film thickness of 45 microns. This coating film was exposed to an exposure dose of 100 to 900 mJ / through an evaluation photomask that designed a lattice pattern imitating a lens array protection spacer structure of a CMOS image sensor using an i-line stepper exposure machine (Nikon model name NSR2005i8A). The exposure was performed in steps of 100 mJ / cm ² in the lateral direction in the range of cm ^{2 and} in steps of 2 microns in the longitudinal direction in the range of 16 to 32 microns. 30 minutes after exposure, propylene glycol monomethyl ether acetate was used as a developer, and the time until the unexposed area completely dissolved and disappeared was multiplied by 1.4, followed by iso-butyl alcohol. Then, a rotary spray rinsing treatment was performed for 10 seconds to obtain a grid-like relief pattern.
The obtained relief pattern was visually observed under an optical microscope, and the presence or absence of residue in the developed portion (○: no residue, Δ: slightly residual residue, ×: excessive residue), presence or absence of pattern swelling (○ : Sharp without swelling, △: Slightly swelled locally, ×: Clearly swollen), presence or absence of lifting or peeling from the substrate (○: No lifting or peeling, △: Slightly lifting or peeling locally , X: evaluation was made on the entire surface or with clear lifting or peeling. The results are shown in Table 1.

(Low-temperature curing characteristics; evaluation of tensile elongation of cured film)
The composition was applied onto a substrate obtained by vacuum-depositing aluminum on a 5-inch silicon wafer and soft-baked in the same manner as in the above-described lithography property evaluation, and then a vertical curing furnace (manufactured by Koyo Thermo Systems, model name VF). -2000B), a heat curing treatment was performed for 2 hours at 180 ° C. in air, and a resin film having a film thickness of 15 μm after curing was produced. This resin film is cut to a width of 3.0 mm using a dicing saw (manufactured by DISCO, model name DAD-2H / 6T), immersed in a 10% hydrochloric acid aqueous solution and peeled off from the silicon wafer, and a strip-shaped film sample. It was.
This film sample was allowed to stand in an atmosphere of 23 ° C. and 55% RH for 24 hours, and then subjected to a tensile test using Tensilon in accordance with ASTM D-882-88 to evaluate the elongation. The results are shown in Table 2.

(Degassing 5% weight loss temperature and 150 ° C soaking weight loss rate evaluation)
Degassability was evaluated by two methods using a strip-shaped film sample prepared for evaluation of the tensile elongation. The results are shown in Table 2.
1) 5% weight reduction temperature Using a thermogravimetry measurement apparatus (manufactured by Shimadzu, model name TGA-50), a temperature indicating a 5% weight reduction was measured. The measurement conditions are a measurement temperature range of 25 ° C. to 450 ° C., a temperature increase rate of 10 ° C./min, and a nitrogen atmosphere.
2) 150 ° C. Soaking Weight Reduction Rate Similarly, using TGA-50, the weight reduction rate (unit%) at 150 ° C. soaking was measured. The measurement conditions were a heating rate of 10 ° C./min up to 150 ° C., a soaking time of 22 hours at 150 ° C., and a nitrogen atmosphere.

(Evaluation of volume shrinkage during heat curing)
The thickness of the coating film before and after the heat curing treatment (curing) at 180 ° C. for 2 hours using a vertical curing furnace performed when preparing the sample for tensile elongation evaluation was measured with a stylus step meter (KLA Tencor). Product, model name P-15), and the rate of change (remaining film rate, unit%) was calculated and used as an index of volume shrinkage. The results are shown in Table 2.

(Adhesion after heat curing: peeling test)
The composition was applied onto a 5-inch silicon wafer and soft baked in the same manner as the above-described lithography property evaluation, and then in the air using a vertical curing furnace (manufactured by Koyo Thermo Systems, model name VF-2000B). A heat curing treatment was performed at 180 ° C. for 2 hours to produce a resin film having a film thickness of 15 μm after curing.
This resin film was cleaved with a cutter knife so that 100 squares of 1 mm were aligned, and then a cellophane tape was adhered thereto and peeled off. The peel test was evaluated by the number remaining on the substrate without adhering to the cellophane tape (JIS K5400). Next, it processed for 100 hours at 133 degreeC and 3 atmospheres using the pressure cooker apparatus (model name TPC-211 by ESPEC). After the pressure cooker treatment, a peeling test was performed in the same manner as described above. If the number remaining on the substrate is 90 or more, it can be said that the adhesiveness is good. If the number remaining on the substrate is 100, there is no peeling in this test, and the adhesiveness is the best. These results are shown in Table 3.

[Example 2]
(Preparation of polyorganosiloxane composition C-2)
100 parts by mass of polyorganosiloxane P-1 obtained in Synthesis Example 1 and 20 parts by mass of N-methyl-2-pyrrolidone solution containing 20% by mass of organosilicon compound S-2 obtained in Synthesis Example 5 (S -2 pure 4 parts by mass), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE 369 manufactured by Ciba Specialty Chemicals), 4 parts by mass, 4,4′-bis ( 0.5 parts by weight of diethylamino) benzophenone, 30 parts by weight of polytetramethylene glycol dimethacrylate (tetramethylene glycol unit number 8 PDT-650 manufactured by NOF Corporation), and 150 parts by weight of silicone resin (217 flakes manufactured by Toray Dow Corning) , N-methyl-2-pyrrolidone, 24 parts by weight, respectively, and mixed to obtain a pore size of 0.2 microns Teflon was filtered (registered trademark) filter to obtain a varnish-like polyorganosiloxane composition C-2.
The polyorganosiloxane composition C-1 in Example 1 described above was changed to the polyorganosiloxane composition C-2, and lithography characteristics, low-temperature curability, degassability, volume shrinkage during heat curing, and adhesiveness after heat curing Was similarly evaluated. The results are shown in Table 1, Table 2 and Table 3.

[Example 3]
(Preparation of polyorganosiloxane composition C-3)
100 parts by mass of polyorganosiloxane P-1 obtained in Synthesis Example 1 and 20 parts by mass of N-methyl-2-pyrrolidone solution containing 20% by mass of organosilicon compound S-3 obtained in Synthesis Example 6 (S -3 pure component 4 parts by mass), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE369 manufactured by Ciba Specialty Chemicals), 4 parts by mass, 4,4′-bis ( 0.5 parts by weight of diethylamino) benzophenone, 30 parts by weight of polytetramethylene glycol dimethacrylate (tetramethylene glycol unit number 8 PDT-650 manufactured by NOF Corporation), and 150 parts by weight of silicone resin (217 flakes manufactured by Toray Dow Corning) , N-methyl-2-pyrrolidone, 24 parts by weight, respectively, and mixed to obtain a pore size of 0.2 microns Teflon was filtered (registered trademark) filter to obtain a varnish-like polyorganosiloxane composition C-3.
The polyorganosiloxane composition C-1 in Example 1 described above was changed to the polyorganosiloxane composition C-3, and lithography characteristics, low-temperature curability, degassability, volume shrinkage during heat curing, and adhesiveness after heat curing Was similarly evaluated. The results are shown in Table 1, Table 2 and Table 3.

[Example 4]
(Preparation of polyorganosiloxane composition C-4)
100 parts by mass of polyorganosiloxane P-1 obtained in Synthesis Example 1 and 10 parts by mass of N-methyl-2-pyrrolidone solution containing 20% by mass of organosilicon compound S-4 obtained in Synthesis Example 7 (S -4 pure 2 parts by mass), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE 369 manufactured by Ciba Specialty Chemicals), 4 parts by mass, 4,4′-bis ( 0.5 parts by weight of diethylamino) benzophenone, 30 parts by weight of polytetramethylene glycol dimethacrylate (tetramethylene glycol unit number 8 PDT-650 manufactured by NOF Corporation), and 150 parts by weight of silicone resin (217 flakes manufactured by Toray Dow Corning) , N-methyl-2-pyrrolidone, 32 parts by mass, each mixed with a pore size of 0.2 microns Teflon was filtered (registered trademark) filter to obtain a varnish-like polyorganosiloxane composition C-4.
The polyorganosiloxane composition C-1 in Example 1 described above was changed to the polyorganosiloxane composition C-4, and lithography characteristics, low-temperature curability, degassability, volume shrinkage during heat curing, and adhesiveness after heat curing Was similarly evaluated. The results are shown in Table 1, Table 2 and Table 3.

[Example 5]
(Preparation of polyorganosiloxane composition C-5)
100 parts by mass of polyorganosiloxane P-1 obtained in Synthesis Example 1 and 10 parts by mass of N-methyl-2-pyrrolidone solution containing 20% by mass of organosilicon compound S-5 obtained in Synthesis Example 8 (S -5 pure 2 parts by mass), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE 369 manufactured by Ciba Specialty Chemicals), 4 parts by mass, 4,4′-bis ( 0.5 parts by weight of diethylamino) benzophenone, 30 parts by weight of polytetramethylene glycol dimethacrylate (tetramethylene glycol unit number 8 PDT-650 manufactured by NOF Corporation), and 150 parts by weight of silicone resin (217 flakes manufactured by Toray Dow Corning) , N-methyl-2-pyrrolidone, 32 parts by mass, each mixed with a pore size of 0.2 microns Teflon was filtered (registered trademark) filter to obtain a C-5 varnish-like polyorganosiloxane composition.
The polyorganosiloxane composition C-1 in Example 1 described above was changed to the polyorganosiloxane composition C-5, and lithography properties, low-temperature curability, degassability, volume shrinkage during heat curing, and adhesiveness after heat curing Was similarly evaluated. The results are shown in Table 1, Table 2 and Table 3.

[Example 6]
(Preparation of polyorganosiloxane composition C-6)
100 parts by mass of polyorganosiloxane P-1 obtained in Synthesis Example 1 and 10 parts by mass of N-methyl-2-pyrrolidone solution containing 20% by mass of organosilicon compound S-6 obtained in Synthesis Example 8 (S -6 pure 2 parts by mass), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE 369 manufactured by Ciba Specialty Chemicals), 4 parts by mass, 4,4′-bis ( 0.5 parts by weight of diethylamino) benzophenone, 30 parts by weight of polytetramethylene glycol dimethacrylate (tetramethylene glycol unit number 8 PDT-650 manufactured by NOF Corporation), and 150 parts by weight of silicone resin (217 flakes manufactured by Toray Dow Corning) , N-methyl-2-pyrrolidone, 32 parts by mass, each mixed with a pore size of 0.2 microns Teflon was filtered (registered trademark) filter to obtain a varnish-like polyorganosiloxane composition C-6.
The polyorganosiloxane composition C-1 in Example 1 described above was changed to the polyorganosiloxane composition C-6, and lithography characteristics, low-temperature curability, degassability, volume shrinkage during heat curing, and adhesiveness after heat curing Was similarly evaluated. The results are shown in Table 1, Table 2 and Table 3.

[Example 7]
(Preparation of polyorganosiloxane composition C-7)
100 parts by mass of polyorganosiloxane P-1 obtained in Synthesis Example 1 and 10 parts by mass of N-methyl-2-pyrrolidone solution containing 20% by mass of organosilicon compound S-1 obtained in Synthesis Example 4 (S -1 pure part 2 parts by mass), 5 parts by mass of N-methyl-2-pyrrolidone solution containing 20% by mass of the organosilicon compound S-4 obtained in Synthesis Example 7 (S-4 pure part 1 part by mass), 4 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE 369 manufactured by Ciba Specialty Chemicals) and 0.5 parts by mass of 4,4′-bis (diethylamino) benzophenone , 30 parts by mass of polytetramethylene glycol dimethacrylate (tetramethylene glycol unit number 8: PDT-650 manufactured by NOF Corporation), silicone resin (Toray Dowco 217 flakes) and 38 parts by mass of N-methyl-2-pyrrolidone were weighed and mixed, filtered through a Teflon (registered trademark) filter having a pore size of 0.2 microns, and varnished polyorganosiloxane. Composition C-7 was obtained.
The polyorganosiloxane composition C-1 in Example 1 described above was changed to the polyorganosiloxane composition C-7, and lithography characteristics, low-temperature curability, degassability, volume shrinkage during heat curing, and adhesion after heat curing Was similarly evaluated. The results are shown in Table 1, Table 2 and Table 3.

[Example 8]
(Preparation of polyorganosiloxane composition C-8)
100 parts by mass of polyorganosiloxane P-2 obtained in Synthesis Example 2 and 10 parts by mass of N-methyl-2-pyrrolidone solution containing 20% by mass of organosilicon compound S-4 obtained in Synthesis Example 7 (S -4 pure 2 parts by mass), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE 369 manufactured by Ciba Specialty Chemicals), 4 parts by mass, 4,4′-bis ( 0.5 parts by weight of diethylamino) benzophenone, 30 parts by weight of polytetramethylene glycol dimethacrylate (tetramethylene glycol unit number 8 PDT-650 manufactured by NOF Corporation), and 150 parts by weight of silicone resin (217 flakes manufactured by Toray Dow Corning) , N-methyl-2-pyrrolidone, 24 parts by weight, respectively, and mixed to obtain a pore size of 0.2 microns Teflon was filtered (registered trademark) filter to obtain a varnish-like polyorganosiloxane composition C-8.
The polyorganosiloxane composition C-1 in Example 1 described above was changed to the polyorganosiloxane composition C-8, and lithography characteristics, low-temperature curability, degassability, volume shrinkage during heat curing, and adhesion after heat curing Was similarly evaluated. The results are shown in Table 1, Table 2 and Table 3.

[Example 9]
(Preparation of polyorganosiloxane composition C-9)
100 parts by mass of polyorganosiloxane P-3 obtained in Synthesis Example 3 and 10 parts by mass of N-methyl-2-pyrrolidone solution containing 20% by mass of organosilicon compound S-4 obtained in Synthesis Example 7 (S -4 pure 2 parts by mass), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE 369 manufactured by Ciba Specialty Chemicals), 4 parts by mass, 4,4′-bis (diethylamino) ) 0.5 parts by mass of benzophenone, 30 parts by mass of polytetramethylene glycol dimethacrylate (8 tetramethylene glycol units, PDT-650 manufactured by NOF Corporation), 150 parts by mass of silicone resin (217 flakes manufactured by Toray Dow Corning) 24 parts by mass of N-methyl-2-pyrrolidone was mixed and weighed to a pore size of 0.2 microns. Teflon was filtered (registered trademark) filter to obtain a varnish-like polyorganosiloxane composition C-9.
The polyorganosiloxane composition C-1 in Example 1 described above was changed to the polyorganosiloxane composition C-9, and lithography properties, low-temperature curability, degassability, volume shrinkage during heat curing, and adhesion after heat curing Was similarly evaluated. The results are shown in Table 1, Table 2 and Table 3.

[Comparative Example 1]
(Preparation of polyorganosiloxane composition C-10)
In Example 1 described above, the N-methyl-2-pyrrolidone solution containing 20% by mass of the organosilicon compound S-1 obtained in Synthesis Example 4 was not added, and the N-methyl-2-pyrrolidone was adjusted to 40 parts by mass. The others were prepared in the same manner to obtain a varnish-like polyorganosiloxane composition C-10.
The polyorganosiloxane composition C-1 in Example 1 described above was changed to the polyorganosiloxane composition C-10, and lithography characteristics, low-temperature curability, degassability, volume shrinkage during heat curing, and adhesiveness after heat curing Was similarly evaluated. The results are shown in Table 1, Table 2 and Table 3.

[Comparative Example 2]
(Preparation of polyorganosiloxane composition C-11)
In Example 1 described above, the organosilicon compound S-4 obtained in Synthesis Example 7 was replaced with the N-methyl-2-pyrrolidone solution containing 20% by mass of the organosilicon compound S-1 obtained in Synthesis Example 4. Preparation was carried out in the same manner except that 120 parts by mass of N-methyl-2-pyrrolidone solution containing 20% by mass (25 parts by mass of pure S-4) was added and N-methyl-2-pyrrolidone was not added. The organosilicon compound S-4 was precipitated therein, and the polyorganosiloxane composition C-11 could not be obtained, and the subsequent evaluation was impossible.

The examples of the present invention exhibit excellent lithography properties and low temperature curing properties, have extremely small volume shrinkage during heat curing, and achieve excellent low degassing properties and adhesion even after heat curing.
Comparative Example 1 is a case in which the organosilicon compound represented by the general formula (3), which is an essential component of the present invention, is not applied. Protrusion occurred.
Comparative Example 2 is a case where 25 parts by mass of the organosilicon compound represented by the general formula (3), which is an essential component of the present invention, is added, but the organosilicon compound is precipitated in the composition and cannot be used. It was.

  The polyorganosiloxane composition of the present invention is an insulating material for electronic parts, formation of surface protective films, interlayer insulating films, α-ray shielding films, etc. in semiconductor devices, and semiconductor devices equipped with image sensors, micromachines, or microactuators, etc. And it can utilize suitably as a resin composition used for the formation.

Claims (11)

A polyorganosiloxane composition comprising the following components (a) to (c):
(A) At least one silanol compound represented by the following general formula (1) and at least one alkoxysilane compound represented by the following general formula (2) are mixed, and water is actively added in the presence of a catalyst. 100 parts by mass of polyorganosiloxane obtained by polymerization without addition

(R ₁ is a group having 6 to 20 carbon atoms including at least one aromatic group.)

(R ₂ is an organic group having 2 to 17 carbon atoms including at least one group selected from the group consisting of an epoxy group and a group having a carbon-carbon double bond. R ₃ is a methyl group or an ethyl group. )
(B) 0.2-20 parts by mass of a photopolymerization initiator (c) 0.05-20 parts by mass of an organosilicon compound represented by the following general formula (3)

(N is an integer of 1 or 2, when n is 1, X ₁ is a divalent aromatic group, and when n is 2, X ₁ is a tetravalent aromatic group. X ₂ is It is a divalent organic group containing a carbon atom directly bonded to a silicon atom, and l is an integer of 1. R ₄ and R ₅ may be the same or different and are alkyl groups having 1 to 4 carbon atoms. M is an integer of 0, 1 or 2. R ₆ is a hydrogen atom or a monovalent hydrocarbon group.) The (a) polyorganosiloxane catalyst is at least one metal alkoxide selected from the group consisting of metal alkoxides represented by the following general formula (4) and the following general formula (5), an alkali metal hydroxide, and an alkaline earth. The polyorganosiloxane composition according to claim 1, which is at least one compound selected from the group consisting of metal hydroxides.

(M ₁ represents any _one of silicon, germanium, titanium, or zirconium, and R ₇ is an alkyl group having 1 to 4 carbon atoms.)

(M ₂ represents boron or aluminum, and R ₇ represents an alkyl group having 1 to 4 carbon atoms.)   The polyorganosiloxane composition according to claim 2, wherein at least one metal alkoxide selected from the group consisting of the metal alkoxides represented by the general formula (4) and the general formula (5) is used as the catalyst. object.   The polyorganosiloxane composition according to claim 3, wherein the catalyst further comprises at least one compound selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides.   The process of apply | coating the polyorganosiloxane composition as described in any one of Claims 1-4 on a base material, and obtaining a coating film, Actinic rays are irradiated to this coating film through a patterning mask, and an exposure part is lightened. A method for forming a polyorganosiloxane cured relief pattern, comprising: a step of curing; a step of removing an uncured portion of the coating film using a developer; and a step of heating the substrate together.   A polyorganosiloxane cured relief pattern obtained by the method according to claim 5.   A semiconductor device comprising the polyorganosiloxane cured relief pattern according to claim 6.   A microstructure formed on a crystal substrate on which an integrated circuit is formed; a package material for covering the microstructure; and a spacer material for supporting the package material on the microstructure. 6. The semiconductor device according to claim 1, wherein the spacer material is formed using the polyorganosiloxane cured relief pattern according to claim 5.   The semiconductor device according to claim 8, wherein the integrated circuit includes a photodiode.   The semiconductor device according to claim 8, wherein the microstructure is a microlens.   The polyorganosiloxane composition according to any one of claims 1 to 4 is applied directly or via a thin film layer on a microstructure formed on a crystal substrate on which an integrated circuit is formed, thereby forming a coating film. A step of forming, a step of irradiating the coating film with an actinic ray through a patterning mask and photocuring the exposed portion, a step of removing an uncured portion of the coating film using a developer, and a step of heating the whole substrate A method for manufacturing a semiconductor device, comprising: