WO2009113459A1 - Photosensitive polyorganosiloxane composition - Google Patents

Abstract

Disclosed is a photosensitive polyorganosiloxane composition comprising component (a): 100 parts by mass of a polyorganosiloxane wherein the polyorganosiloxane has been obtained by mixing a silanol compound represented by general formula (1): R2Si(OH)2, an alkoxysilane compound represented by general formula (2): R'Si(OR'')3, and an alkoxysilane compound represented by general formula (3): R'''Si(OR'''')3 in a specific molar ratio range with a catalyst selected from the group consisting of metal alkoxides represented by general formula (4): M(OR''''')4, metal alkoxides represented by general formula (5): M'(OR'''''')3, and Ba(OH)2 and polymerizing the mixture without the addition of water, and component (b): 0.1 to 20 parts by mass of a photopolymerization initiator. The groups in the general formulae (1) to (5) are as defined in the claims.

Description

Photosensitive polyorganosiloxane composition

The present invention relates to the formation of surface protection films, interlayer insulating films, α-ray shielding films, etc. in insulating materials for electronic components and semiconductor devices, and photosensitive devices used in semiconductor devices equipped with image sensors, micromachines, or microactuators. The present invention relates to a conductive polyorganosiloxane composition, a semiconductor device manufactured using the same, and the like.

Polyimide resins having excellent heat resistance, electrical properties, and mechanical properties are widely used for insulating materials for electronic parts, and surface protection films, interlayer insulation films, and α-ray shielding films for semiconductor devices.
This polyimide resin is usually provided in the form of a photosensitive polyimide precursor composition, which is applied to a substrate, soft baked, irradiated with actinic rays (exposure) through a desired patterning mask, and developed. And it has the characteristic that the hardening relief pattern which consists of a heat resistant polyimide resin can be formed easily by performing a thermosetting process. (For example, refer to Patent Document 1.)

In recent years, in the manufacturing process of semiconductor devices, a demand for a material capable of performing the above-described thermosetting treatment at a lower temperature is increasing mainly for the reasons of the material of the constituent elements and the structural design. However, in the case of the conventional polyimide resin precursor composition, if the curing treatment temperature is lowered, the thermal imidization cannot be completed, and various cured film properties are lowered. Therefore, the lower limit of the curing treatment temperature is about 300 ° C. at most. Met.
By the way, as a recent design philosophy of semiconductor devices, the wiring cross section of a necessary part has a large area for the purpose of reducing the electrical resistance and the accompanying resistance noise, resistance heat generation, etc. at the same time as the conventional multi-layer density increasing trend. Attempts have been made. In particular, when a “giant wiring” layer having a height of 10 microns or more is coated with a conventional polyimide precursor composition and thermally cured, the volume of the solvent is reduced by about 40% mainly due to volatilization of the remaining solvent component. Since a large level difference occurs between the top and the periphery thereof, there is a high demand for a material that can coat this more uniformly and flatly.

Patent Document 2 below discloses a photosensitive siloxane-based material that can be cured at a low temperature and has a small volume shrinkage during the heat curing process. However, in this disclosed technique, the surface of an electronic component or a semiconductor device is disclosed. Realizing performance that can stably form protective films, interlayer insulation films, α-ray shielding films, etc., such as applicability to various base materials, adhesion to underlying base materials, and mechanical properties at a practical level difficult.
Furthermore, the material disclosed in Patent Document 2 remains tacky and fluid even after being applied on a base material and then subjected to soft baking such as that performed with a conventional polyimide precursor composition. . Therefore, it is essential to keep the substrate level in order to prevent contamination of the device due to contact between the coated substrate and the device being transported, and to prevent the coating film from flowing on the substrate. It is undeniable that new constraints will be generated.

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 forming an element such as a transistor on a crystal substrate such as silicon using a conventionally known semiconductor process, an element (microstructure) having a function corresponding to the purpose of the semiconductor device is formed, It is manufactured by packaging these together.
As an example of such a packaging technique, for example, in Patent Document 3 below, a microstructure formed on a crystal substrate on which an integrated circuit is formed, a package material for covering the microstructure, A semiconductor device having a spacer for supporting the package material on the microstructure and an example thereof are disclosed in detail. The technique disclosed in Patent Document 3 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. For implementation, a spacer (also expressed as a dam or a partition) for supporting the packaging material on the microstructure plays an important role. The following three points can be considered as characteristics required for the spacer.

First, since this 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 the microstructure located under the spacer does not necessarily have high 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 containing a microstructure, and if the description of Patent Document 3 is cited, it forms a “cavity”, so that the volatile components 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 3 does not disclose a specific member suitably used for the spacer.

That is, a photosensitive film-forming material that has excellent low-temperature curability, has a small volume shrinkage during curing, is tack-free, and has practical performance that can replace conventional polyimide precursors has yet to be found. There is no current situation.
Japanese Patent No. 2826940 European Patent No. 1196478 Japanese Special Table 2003-516634

Problems to be solved by the present invention include the formation of surface protection films, interlayer insulation films, α-ray shielding films, etc. in recent electronic component insulation materials and semiconductor devices, and mounting image sensors, micromachines, or microactuators. Requirements for resin compositions used in semiconductor devices and the like, that is, excellent coating properties to various substrates and photosensitive properties, can be cured at a low temperature of 250 ° C. or less, and are volatile at 150 ° C. (Reduction rate) and volume shrinkage at 180 ° C. (remaining film ratio after curing) are small, and a soft bake film (hereinafter simply referred to as “soft bake film”) obtained by coating and soft baking the composition. It is to provide a photosensitive polyorganosiloxane composition that can reduce the tackiness of (ii).

As a result of intensive studies and experiments, the inventors of the present invention include a 5- or 6-membered nitrogen atom-containing heterocyclic group containing no photopolymerizable carbon-carbon double bond (including those having no aromaticity). Unexpectedly, it was found that the tackiness of the soft-baked film of the photosensitive polyorganosiloxane composition using the alkoxysilane compound having a) is dramatically reduced. Invented the invention.

｛式中、Ｒは、少なくとも芳香族基を１つ含む炭素数６～１８の一価の基であり、ともに同じであっても異なっていてもよい。｝で表される少なくとも１種のシラノール化合物、下記一般式（２）：

｛式中、Ｒ’は、光重合性の炭素－炭素二重結合を含まない５～６員の窒素原子含有複素環基（芳香族性を持たないものも含む）を有する炭素数２～１１の有機基であり、そしてＲ’’は、メチル基又はエチル基であり、ともに同じであっても異なっていてもよい。｝で表される少なくとも１種のアルコキシシラン化合物、及び下記一般式（３）：

｛式中、Ｒ’’’は、光重合性の炭素－炭素二重結合基を含む炭素数２～１７の有機基であり、そしてＲ’’’’は、メチル基又はエチル基であり、ともに同じであっても異なっていてもよい。｝で表される少なくとも１種のアルコキシシラン化合物を、下記一般式（４）：

｛式中、Ｍは、ケイ素、ゲルマニウム、チタニウム又はジルコニウムのいずれかであり、そしてＲ’’’’’は、炭素数１～４のアルキル基であり、ともに同じであっても異なっていてもよい。｝で表される金属アルコキシド、下記一般式（５）：

｛式中、Ｍ’は、ホウ素又はアルミニウムであり、そしてＲ’’’’’’は、炭素数１～４のアルキル基であり、ともに同じであっても異なっていてもよい。｝で表される金属アルコキシド、及びＢａ（ＯＨ）_２からなる群より選択される少なくとも１つの触媒と混合して、水を添加せずに、重合させることにより得られ、ここで、一般式（１）で表されるシラノール化合物対一般式（２）で表されるアルコキシシラン化合物及び一般式（３）で表されるアルコキシシラン化合物の合計のモル比は、５０：３０～５０：７０あり、かつ、一般式（２）で表されるアルコキシシラン化合物対一般式（３）で表されるアルコキシシラン化合物のモル比は、７０：３０～３０：７０である、
　（ｂ）光重合開始剤０．１～２０質量部。 That is, the present invention is the following [1] to [19]:
[1] Photosensitive polyorganosiloxane composition containing the following component (a) and component (b):
(A) 100 parts by mass of polyorganosiloxane, wherein the polyorganosiloxane has the following general formula (1):

{Wherein R is a monovalent group having 6 to 18 carbon atoms containing at least one aromatic group, and may be the same or different. } At least one silanol compound represented by the following general formula (2):

{In the formula, R ′ is a 5- to 6-membered nitrogen atom-containing heterocyclic group (including those having no aromaticity) that does not contain a photopolymerizable carbon-carbon double bond, and has 2 to 11 carbon atoms. And R ″ is a methyl group or an ethyl group, which may be the same or different. } At least one alkoxysilane compound represented by the following general formula (3):

{Wherein R ′ ″ is an organic group having 2 to 17 carbon atoms including a photopolymerizable carbon-carbon double bond group, and R ″ ″ is a methyl group or an ethyl group, Both may be the same or different. } At least one alkoxysilane compound represented by the following general formula (4):

{Wherein M is silicon, germanium, titanium or zirconium, and R ′ ″ ″ is an alkyl group having 1 to 4 carbon atoms, both of which may be the same or different. Good. } A metal alkoxide represented by the following general formula (5):

{Wherein M ′ is boron or aluminum, and R ″ ″ ″ is an alkyl group having 1 to 4 carbon atoms, which may be the same or different. Is obtained by mixing with at least one catalyst selected from the group consisting of Ba (OH) ₂ and polymerizing without adding water, wherein The total molar ratio of the silanol compound represented by 1) to the alkoxysilane compound represented by the general formula (2) and the alkoxysilane compound represented by the general formula (3) is 50:30 to 50:70, The molar ratio of the alkoxysilane compound represented by the general formula (2) to the alkoxysilane compound represented by the general formula (3) is 70:30 to 30:70.
(B) 0.1 to 20 parts by mass of a photopolymerization initiator.

[2] The above [1], further comprising (c) a compound other than the component (a) having two or more photopolymerizable unsaturated bonding groups in an amount of 1 to 100 parts by mass with respect to the component (a). A photosensitive polyorganosiloxane composition.

[3] (d) A silicone resin other than the component (a) having a three-dimensional network structure obtained by cohydrolyzing and polymerizing an organosilane compound having 2 to 4 hydrolyzable groups; The photosensitive polyorganosiloxane composition according to [1] or [2], further comprising 50 to 200 parts by mass with respect to the component.

[4] The above [1], wherein the catalyst is at least one metal alkoxide selected from the group consisting of a metal alkoxide represented by the general formula (4) and a metal alkoxide represented by the general formula (5). The photosensitive polyorganosiloxane composition according to any one of [3] to [3].

[5] The catalyst is at least one catalyst selected from the group consisting of a metal alkoxide represented by the general formula (4), a metal alkoxide represented by the general formula (5), and Ba (OH) ₂ ; The photosensitive polyorganosiloxane composition according to any one of the above [1] to [3], which is a mixture with at least one catalyst selected from the group consisting of potassium hydroxide and sodium hydroxide.

[6] (e) (CH ₃ O) ₃ —Si— (CH ₂ ) ₃ —O—CO—C (CH ₃ ) ═CH ₂ , (CH ₃ O) ₃ —Si— (CH ₂ ) ₃ —O —CO—CH═CH ₂ and (CH ₃ O) ₃ —Si— (CH ₂ ) ₃ —O—CH ₂ —C ₂ H ₃ O {the C ₂ H ₃ O on the left is an epoxy group} The photosensitive polyorganosiloxane according to any one of the above [1] to [5], further comprising at least one organic silicon compound selected from 0.1 to 20 parts by mass with respect to component (a). Composition.

[7] The above [1] to [6], further comprising (f) a polyvalent thiol compound containing at least two thiol groups in an amount of 1 to 50 parts by mass with respect to the component (a). Photosensitive polyorganosiloxane composition.

｛式中、ｈは、１又は２の整数であり、ｈが１の場合、Ｘａは、２価の芳香族基であり、ｈが、２の場合、Ｘａは、４価の芳香族基であり、Ｘｃ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、ｄは、１～３の整数であり、Ｒｅ及びＲｆは、炭素数１～４のアルキル基であり、同一であっても異なっていてもよく、ｇは、０、１又は２であり、Ｒｂは、水素原子又は１価の炭化水素基である。｝で表されるカルボキシル基含有の有機ケイ素化合物を、（ａ）成分に対して０.０５～２０質量部でさらに含む、前記［１］～［７］のいずれかに記載の感光性ポリオルガノシロキサン組成物。 [8] (g) The following general formula (6):

{In the formula, h is an integer of 1 or 2, and when h is 1, Xa is a divalent aromatic group. When h is 2, Xa is a tetravalent aromatic group. Xc is a divalent organic group containing a carbon atom directly bonded to a silicon atom, d is an integer of 1 to 3, Re and Rf are alkyl groups of 1 to 4 carbon atoms, They may be the same or different, g is 0, 1 or 2, and Rb is a hydrogen atom or a monovalent hydrocarbon group. The photosensitive polyorgano according to any one of [1] to [7], further comprising 0.05 to 20 parts by mass of a carboxyl group-containing organosilicon compound represented by formula (a): Siloxane composition.

[9] The photosensitive polyorgano described in any one of [1] to [8], further including (h) a nonionic surfactant in an amount of 0.01 to 10 parts by mass with respect to the component (a). Siloxane composition.

[10] A method for forming a polyorganosiloxane film, comprising a step of applying the photosensitive polyorganosiloxane composition according to any one of [1] to [9] onto a substrate.

[11] A cured polyorganosiloxane film obtained by curing the polyorganosiloxane film obtained by the method described in [10] by irradiation with actinic rays or heating.

[12] A step of forming a polyorganosiloxane film on a substrate by the method described in [10] above, a step of irradiating the film with an actinic ray through a patterning mask and photocuring an exposed portion, and using a developer A method for forming a polyorganosiloxane cured relief pattern, comprising: removing an uncured portion of the film; and heating the whole substrate.

[13] A polyorganosiloxane cured relief pattern obtained by the method described in [12].

[14] A semiconductor device including the cured polyorganosiloxane film according to [11].

[15] A semiconductor device including the polyorganosiloxane cured relief pattern according to [12].

[16] 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 A semiconductor device in which the spacer material is the polyorganosiloxane cured relief pattern described in [12].

[17] The semiconductor device according to [16], wherein the integrated circuit includes a photodiode.

[18] The semiconductor device according to [16] or [17], wherein the microstructure is a microlens.

[19] A step of forming a polyorganosiloxane film directly on the microstructure or through a thin film layer, a step of irradiating the film with an actinic ray through a patterning mask to photocur the exposed portion, and a developer. The method for manufacturing a semiconductor device according to any one of [16] to [18], further including a step of removing an uncured portion of the film and a step of heating the whole substrate.

The photosensitive polyorganosiloxane composition of the present invention is excellent in applicability to various substrates, has a low soft bake film tackiness, has a volume shrinkage when cured at 180 ° C., and a soaking weight loss rate at 150 ° C. Is low, can be cured at a low temperature of 250 ° C. or less, and has excellent photosensitivity.

｛式中、Ｒは、少なくとも芳香族基を１つ含む炭素数６～１８の一価の基であり、ともに同じであっても異なっていてもよい。｝、

｛式中、Ｒ’は、光重合性の炭素－炭素二重結合を含まない５～６員の窒素原子含有複素環基（芳香族性を持たないものも含む。）を有する炭素数２～１１の有機基であり、Ｒ’’は、メチル基又はエチル基であり、ともに同じであっても異なっていてもよい。）、

｛式中、Ｒ’’’は、光重合性の炭素－炭素二重結合基を含む炭素数２～１７の有機基であり、Ｒ’’’’は、メチル基又はエチル基であり、ともに同じであっても異なっていてもよい。｝、

｛式中、Ｍは、ケイ素、ゲルマニウム、チタニウム又はジルコニウムであり、Ｒ’’’’’は、炭素数１～４のアルキル基であり、ともに同じであっても異なっていてもよい。｝、

｛式中、Ｍ’は、ホウ素又はアルミニウムであり、Ｒ’’’’’’は、炭素数１～４のアルキル基であり、ともに同じであっても異なっていてもよい。｝。 Hereinafter, each component which comprises a photosensitive polyorganosiloxane composition is demonstrated concretely below.
(A) Polyorganosiloxane The polyorganosiloxane is composed of at least one silanol compound represented by the following general formula (1), at least one alkoxysilane compound represented by the following general formula (2), and the following general formula. The at least one alkoxysilane compound represented by (3) comprises a metal alkoxide represented by the following general formula (4), a metal alkoxide represented by the following general formula (5), and Ba (OH) _2. It is obtained by a method of mixing with at least one catalyst selected from the group and polymerizing without adding water.
Here, “without adding water” means that the operation of adding water at the time of polymerization is not performed, and does not exclude water naturally contained in the raw material or moisture in the polymerization atmosphere. .

{Wherein R is a monovalent group having 6 to 18 carbon atoms containing at least one aromatic group, and may be the same or different. },

{In the formula, R ′ is a 5- to 6-membered nitrogen atom-containing heterocyclic group that does not contain a photopolymerizable carbon-carbon double bond (including those having no aromaticity) and has 2 to 11 organic groups, R ″ is a methyl group or an ethyl group, and both may be the same or different. ),

{Wherein R ′ ″ is a C 2-17 organic group including a photopolymerizable carbon-carbon double bond group, R ″ ″ is a methyl group or an ethyl group, They may be the same or different. },

{Wherein M is silicon, germanium, titanium or zirconium, and R ′ ″ ″ is an alkyl group having 1 to 4 carbon atoms, which may be the same or different. },

{Wherein M ′ is boron or aluminum, and R ″ ″ ″ is an alkyl group having 1 to 4 carbon atoms, which may be the same or different. }.

Especially, it is preferable that the said catalyst is at least 1 metal alkoxide selected from the group which consists of the said General formula (4) and the said General formula (5).
Further, in the process of polymerizing the polyorganosiloxane without adding water, at least one alkali metal hydroxide selected from the group consisting of potassium hydroxide and sodium hydroxide may be mixed as the catalyst.

で表される基の中から選ばれる少なくとも１つの基であることが好ましい。 In the silanol compound represented by the general formula (1), R is a group having 6 to 18 carbon atoms including at least one aromatic group. Specifically, the following structure:

It is preferable that it is at least 1 group chosen from the group represented by these.

で表される基の中から選ばれる少なくとも１つの基であることが好ましい。 In the alkoxysilane compound represented by the general formula (2), R ′ is a 5- to 6-membered nitrogen atom-containing heterocyclic group containing no photopolymerizable carbon-carbon double bond (having no aromaticity) And an organic group having 2 to 11 carbon atoms. Unlike the alkoxysilane compound represented by the general formula (3), the compound represented by the general formula (2) does not include a group having a photopolymerizable carbon-carbon double bond. R ″ is a methyl group or an ethyl group, and both may be the same or different. Specific examples of R ′ include the following structures:

It is preferable that it is at least 1 group chosen from the group represented by these.

で表される基の中から選ばれる少なくとも１つの基であることが好ましい。 In the alkoxysilane compound represented by the general formula (3), R ′ ″ is an organic group having 2 to 17 carbon atoms including a group having a photopolymerizable carbon-carbon double bond, and R ″ ″ Are methyl groups or ethyl groups, which may be the same or different. Specific examples of R ′ ″ include the following structures:

It is preferable that it is at least 1 group chosen from the group represented by these.

The photosensitive polyorganosiloxane is represented by the general formula (3), at least one silanol compound represented by the general formula (1), at least one alkoxysilane compound represented by the general formula (2). And at least 1 selected from the group represented by the metal alkoxide represented by the general formula (4), the metal alkoxide represented by the general formula (5), and Ba (OH) _2. It is obtained by a method in which a seed catalyst (hereinafter sometimes simply referred to as “catalyst”) is mixed and polymerized without adding water.

The metal alkoxide represented by the general formula (4) and the metal alkoxide represented by the general formula (5) catalyze a dealcoholization condensation reaction of a silanol compound (silanol group) and an alkoxysilane compound (alkoxysilyl group). , Itself behaves as an alkoxy group-containing compound and participates in the dealcoholization condensation reaction, and a part forms a polysiloxane or polysilsesquioxane structure in a form incorporated into the molecule.

The mixing ratio is basically that the silanol compound and the alkoxysilane compound are mixed at 1: 1 (molar ratio), and the alkoxysilane compound can be mixed at a ratio of 30 to 70 mol with respect to 50 mol of the silanol compound. When mixing the metal alkoxide, it is preferable to adjust the overall mixing ratio in such a manner that a part of the alkoxysilane compound is replaced (the amount of the alkoxysilane compound mixed is reduced by a certain ratio).
Specifically, when the tetravalent metal alkoxide represented by the 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 (the amount of alkoxysilane compound is reduced by 2 mol for every 1 mol of the amount of tetravalent metal alkoxide mixed). 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 silanol compounds include diphenyl silane diol, di-p-toluyl silane diol, di-p-styryl silane diol, dinaphthyl silane diol, etc., but in terms of price, availability, copolymerization and heat resistance, etc. In view of the above, diphenylsilanediol is particularly suitable.

Further, as a compound suitable as an alkoxysilane compound having a 5- to 6-membered nitrogen atom-containing heterocyclic group (including those having no aromaticity) that does not contain a photopolymerizable carbon-carbon double bond, N-trialkoxysilyl-1,2,4-triazole, N-trialkoxysilylimidazole, N-trialkoxysilylpyrrole, N-trialkoxysilylpyridine, N-trialkoxysilylpyrrolidine, piperidinomethyltrialkoxysilane, 2-piperidinoethyltrialkoxysilane, 3-morpholinopropyltrialkoxysilane, 3-piperazinopropyltrialkoxysilane, 3-piperidinopropyltrialkoxysilane, 3- (4-methylpiperazinopropyl) tri Alkoxysilane, 3- (4-methylpiperidinopropyl) Trialkoxysilane, 4- (2-trialkoxysilylethyl) pyridine, N- (3-trialkoxysilylpropyl) -4,5-dihydroimidazole, 2- (2-trialkoxysilylethyl) pyridine, N- (3 -Trialkoxysilylpropyl) pyrrole (wherein the alkoxy moiety represents a methoxy group or an ethoxy group).

The present inventors have disclosed an alkoxysilane compound having a 5- to 6-membered nitrogen atom-containing heterocyclic group (including those having no aromaticity) that does not contain a photopolymerizable carbon-carbon double bond. It has been found that when used as a raw material for organosilane, the tackiness of the soft-baked film of the photosensitive polyorganosiloxane composition using the same is dramatically eliminated. Among them, 3-morpholinopropyltrimethoxysilane, 3-piperazinopropyltrimethoxysilane, 3-piperidinopropyltrimethoxysilane, 2- (2-trimethoxysilylethyl) pyridine, 4- (2-triethoxysilyl) Particular preference is given to using ethyl) pyridine.

Examples of suitable alkoxysilane compounds containing a photopolymerizable carbon-carbon double bond group include vinyltrimethoxysilane, vinyltriethoxysilane, 1-propenyltrimethoxysilane, 1-propenyltriethoxysilane, 2- Propenyltrimethoxysilane, 2-propenyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, p- Styryltrimethoxysilane, p-styryltriethoxysilane, p- (1-propenylphenyl) trimethoxysilane, p- (1-propenylphenyl) triethoxysilane, p- (2-propenyl) In order to obtain excellent UV-i photosensitivity, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxy and the like can be mentioned. Propyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, and 3-acryloyloxypropyltriethoxysilane are more preferable, and 3-methacryloyloxypropyltrimethoxy is considered in consideration of price, harmfulness, flexibility and high crosslinkability. Silane is particularly preferred.

As the metal alkoxide represented by the general formula (4) and the metal alkoxide represented by the general formula (5), trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, tri-iso- Propoxy aluminum, tri-n-butoxy aluminum, tri-iso-butoxy aluminum, tri-sec-butoxy aluminum, tri-tert-butoxy aluminum, trimethoxy boron, triethoxy boron, tri-n-propoxy boron, 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-butoxysilane, tetra-iso-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetramethoxygermanium, tetraethoxygermanium, tetra-n-propoxygermanium, Tetra-iso-propoxygermanium, tetra-n-butoxygermanium, tetra-iso-butoxygermanium, tetra-sec-butoxygermanium, tetra-tert-butoxygermanium, tetramethoxytitanium, tetraethoxytitanium, tetra-npropoxytitanium, Tetra-isopropoxytitanium, tetra-n-butoxytitanium, tetra-iso-butoxytitanium, tetra-sec-butoxytitanium, tetra-tert-butoxytita , Tetramethoxyzirconium, tetraethoxyzirconium, tetra-n-propoxyzirconium, tetra-iso-propoxyzirconium, tetra-n-butoxyzirconium, tetra-iso-butoxyzirconium, tetra-sec-butoxyzirconium, tetra-tert-butoxyzirconium Etc. 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 as a catalyst and availability.

A polyorganosiloxane can be polymerized by appropriately mixing and heating the above-mentioned silanol compound, the above-mentioned two types of alkoxysilane compounds, and a catalyst. The heating temperature and heating rate at this time are important parameters for controlling the degree of polymerization of the polyorganosiloxane to be produced. Although depending on the desired degree of polymerization, it is preferred that the raw material mixture is heated to about 70 ° C. to 150 ° C. for polymerization.
When the addition amount of the catalyst during the polymerization of the silanol compound is less than 2 mol%, the polymerization of the polyorganosiloxane may not sufficiently proceed when heated to the above preferable temperature range or more. In such a case, when an appropriate amount of potassium hydroxide or sodium hydroxide is added as a cocatalyst, the catalyst deficiency can be compensated and the degree of polymerization of the polyorganosiloxane produced can be controlled appropriately. In this case, potassium ions and sodium ions remain in the polyorganosiloxane after completion of the reaction, but these alkali metal ions can be easily removed and purified using an ion exchange resin or the like. It is preferable.
However, when the silanol compound and the alkoxysilane compound are polymerized only by the action of potassium hydroxide or sodium hydroxide without adding the catalyst at the time of polymerization, it is avoided that a part of the polymer component having high crystallinity is generated. This is not preferable because it crystallizes and precipitates, resulting in white turbidity and precipitation, and the system becomes disproportionate. From the viewpoint of avoiding this “crystallization”, it is important to add the catalyst at the time of polymerization.

The lower limit of the addition amount of the catalyst is 0.1 mol% or more, more preferably 0.5 mol% or more with respect to the silanol compound, for the above reason.
The upper limit of the amount of catalyst added 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. The amount is 30 mol% or less, more preferably 20 mol% or less, based on the silanol compound.

In addition, the ratio of the two alkoxysilane compounds used is important in achieving both the tack-removing effect of the soft bake film and the excellent photosensitive characteristics. As described above, the silanol compound and the alkoxysilane compound are basically mixed at a 1: 1 (molar ratio), but of these, they do not contain a photopolymerizable carbon-carbon double bond. The molar ratio of an alkoxysilane compound having a 6-membered nitrogen atom-containing heterocyclic group (including those having no aromaticity) and an alkoxysilane compound containing a photopolymerizable carbon-carbon double bond group is 70:30 to 30:70, and more preferably in the range of 60:40 to 40:60.
When the molar ratio of the alkoxysilane compound containing a photopolymerizable carbon-carbon double bond group exceeds 30% of the total alkoxysilane compound, the excellent photosensitive properties expected by the present invention are achieved. At the same time, the molar ratio of the alkoxysilane compound having a 5- to 6-membered nitrogen atom-containing heterocyclic group (including those having no aromaticity) that does not contain a photopolymerizable carbon-carbon double bond is If it exceeds 30% of the silane compound, the tackiness of the soft-baked film of the photosensitive polyorganosiloxane composition can be reduced.

(B) Photopolymerization initiator It is important to add a photopolymerization initiator to the photosensitive polyorganosiloxane composition for the purpose of imparting photosensitivity.
Photopolymerization initiators include the following:
(1) Benzophenone derivatives such as benzophenone, 4,4′-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, fluorenone,
(2) 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} Acetophenone derivatives such as -2-methylpropan-1-one and methyl phenylglyoxylate,
(3) Thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone,
(4) benzyl derivatives such as benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal,
(5) benzoin derivatives such as benzoin, benzoin methyl ether, 2-hydroxy-2-methyl-1phenylpropan-1-one,
(6) 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-acetyloxime) Oxime compounds of,

(7) 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, Α-hydroxy ketone compounds such as 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropane,
(8) 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE369), 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholine Α-aminoalkylphenone compounds such as -4-yl-phenyl) butan-1-one,
(9) Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethyl Phosphine oxide compounds such as benzoyl-diphenyl-phosphine oxide,
(10) Titanocene compounds such as bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium,
(11) benzoate derivatives such as ethyl-p- (N, N-dimethylaminobenzoate),
(12) Acridine derivatives such as 9-phenylacridine.
When these photopolymerization initiators are used, they may be used alone or as a mixture of two or more.

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 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to the component (a). When the addition amount is 0.1 parts by mass or more, light sufficient to allow photopolymerization to proceed sufficiently is supplied during exposure, and curing of the exposed part sufficiently proceeds, so that a practical relief pattern can be obtained. On the contrary, if the addition amount is 20 parts by mass or less, the exposure absorption near the surface of the coating film does not become too large, the exposure light beam reaches near the substrate surface, and the photopolymerization becomes uniform in the film thickness direction. A practical relief pattern can be obtained.

(C) Compound other than component (a) having two or more photopolymerizable unsaturated bond groups Photopolymerization for the purpose of improving film forming characteristics, photosensitive characteristics, and mechanical properties after curing (elongation after curing) A compound other than the component (a) having two or more sex unsaturated bond groups can be added. As such a monomer, a polyfunctional (meth) acrylic acid ester 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 diester, Methacrylate [number of ethylene glycol units 2-20], poly (1,2-propylene glycol) diacrylate [1,2-propylene glycol units number 2-20], poly (1,2-propylene glycol) dimethacrylate [1 , 2-Propylene glycol unit number 2 to 20], polytetramethylene glycol diacrylate [tetramethylene glycol unit number 2 to 10], polytetramethylene glycol dimethacrylate [tetramethylene glycol unit number 2 to 1] ], 1,4-cyclohexanediacrylate, 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, dipentaerythritol Oxaacrylate, methylene bisacrylamide, 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 diacrylate [number of ethylene glycol units 2 to 30], ethoxylated bisphenol A dimethacrylate [number of ethylene glycol units 4 to 30], N, N′-bis (2-methacryloyloxyethyl) urea, etc. Can be mentioned.
Among these, one or more compounds selected from the group consisting of ethoxylated bisphenol A dimethacrylate [ethylene glycol unit number 4 to 30] and polytetramethylene glycol dimethacrylate [tetramethylene glycol unit number 2 to 10] are preferable.

｛式中、ｑ＋ｒ≒４～３０｝で表される日本油脂（株）製のブレンマーＰＤＢＥ－２００、２５０、４５０、１３００が例として挙げられる。 Ethoxylated bisphenol A dimethacrylate [number of ethylene glycol units 4 to 30] is represented by the following formula:

As an example, Blemmer PDBE-200, 250, 450, 1300 manufactured by Nippon Oil & Fats Co., Ltd. represented by {wherein q + r≈4 to 30} is given.

｛式中、ｓ≒８｝で表される日本油脂（株）製のブレンマーＰＤＴ－６５０が例として挙げられる。
　これらの中でも、ＰＤＢＥ－４５０やＰＤＢＥ－１３００、ＰＤＴ－６５０が特に好ましい。 As polytetramethylene glycol dimethacrylate [tetramethylene glycol unit number 2 to 10], those having a tetramethylene glycol unit number of 5 to 10 are preferable.

As an example, Bremer PDT-650 manufactured by Nippon Oil & Fats Co., Ltd. represented by {wherein s≈8} is given.
Among these, PDBE-450, PDBE-1300, and PDT-650 are particularly preferable.

Moreover, when using these, as needed, you may use individually or in mixture of 2 or more types. The addition amount is preferably 1 to 100 parts by mass, and more preferably 5 to 50 parts by mass with respect to the component (a). If the addition amount is 100 parts by mass or less, it is preferable because the stability of the resin liquid is high and quality variation is small.

(D) Silicone resin A silicone resin can be added to the photosensitive polyorganosiloxane composition for the purpose of further reducing tackiness and improving fluidity of the soft-baked film. Here, the silicone resin is, for example, “organosilane compound having 2 to 4 hydrolyzable groups such as alkoxysilyl group and chlorosilyl group” described in “Silicone Handbook” (1990) published by Nikkan Kogyo Shimbun. It is a “polymer having a three-dimensional network structure obtained by cohydrolyzing and polymerizing”. The component (a) does not correspond to the (c) silicone resin.

In order to achieve 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 are methylsilicone resins such as KR220L, KR242A, KC89, KR400, 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 reducing the tackiness and improving the fluidity of the soft bake film, it is preferable to add a silicone resin having a higher crosslinking density and a solid in a normal temperature range. More preferably, an ethyl or phenylpropyl silicone resin is selected. Specifically, among the above, 217 flakes, SR-20, SR-21, SR-23, Z-6018 and the like are particularly preferable. These may be used singly or may be used in combination as appropriate.
The amount of silicone resin added is preferably 50 to 200 parts by mass relative to the component (a). From the viewpoint of tackiness and fluidity, 50 parts by mass or more is preferable, and from the viewpoint of photosensitive characteristics such as i-line photosensitivity, 200 parts by mass or less is preferable.

(E) Organosilicon compound An organosilicon compound can be added to the photosensitive polyorganosiloxane composition for the purpose of improving adhesion to various substrates. (However, the following organic silicon compound containing a carboxyl group is excluded.) Examples of the organic silicon compound include the following. (Hereinafter, alkoxy represents a methoxy group or an ethoxy group.) Vinyltrialkoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, 3-glycidoxypropyltrialkoxysilane, 3-glycidyl 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-mercaptopropylmethyldialkoxysilane, bis (trialkoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltrialkoxysilane.

In particular, (CH ₃ O) ₃ —Si— (CH ₂ ) ₃ —O—CO—C (CH ₃ ) ═CH ₂ , (CH ₃ O) ₃ —Si— (CH ₂ ) ₃ —O—CO—CH ═CH ₂ and (CH ₃ O) ₃ —Si— (CH ₂ ) ₃ —O—CH ₂ —C ₂ H ₃ O (wherein C ₂ H ₃ O is an epoxy group) Compounds are preferred.
Among them, (CH ₃ O) ₃ —Si— (CH ₂ ) ₃ —O—CO—C (CH ₃ ) ═CH ₂ , that is, 3-methacryloyloxypropyltrimethoxysilane (hereinafter abbreviated as MEMO) However, it is preferable from the viewpoints of flexibility and adhesion improvement effect. In the case of adding an adhesion agent, the addition amount is preferably 0 to 20 parts by mass with respect to the component (a) of the present invention from the viewpoint of the stability of the composition. More preferably, it is 0.1 to 15% by mass, and further preferably 3 to 10% by mass.

(F) Polyvalent thiol compound The photosensitive polyorganosiloxane composition has a polyvalent thiol compound having two or more thiol groups for the purpose of improving applicability (wetability) on various substrates as desired. Can be added. Examples of the polyvalent thiol compound include the following:
(1) Divalent thiol compound 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, 2,3-dihydroxy-1,4-butanedithiol, 3,6-dioxa-1,8-octanedithiol, 3,7-dithia-1,9- Nonanedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 2,3-diamino-1,4-benzenedithiol, 4,5-dimethyl-O-xylenedithiol, toluene 3,4-dithiol, 4,4'-biphenyldithiol, 1,5-naphthalenedithiol, 6- (dibutylamino) 1,3,5-triazine-2,4-dithiol, 2-amino-1,3,5-triazine-4,6-dithiol, 6-anilino-1,3,5-triazine-2,4-dithiol, 6- (4′-anilinophenyliso-propylamino) -1,3,5-triazine-2,4-dithiol, 6- (3 ′, 5′-tert-butyl-4′-hydroxyanilino)- 1,3,5-triazine-2,4-dithiol, quinoxaline-2,3-dithiol, purine-2,6-dithiol, 1,3,4-thiadiazole-2,5-dithiol, 1,4-bis ( 3-mercaptobutyryloxy) butane (Karenz MT BD1 manufactured by Showa Denko KK),
(2) Trivalent thiol compound 1,3,5-benzenetrithiol, s-triazine-2,4,6-trithiol, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3 5-triazine-2,4,6 (1H, 3H, 5H) -trione) (Karenz MT NR1 manufactured by Showa Denko KK),
(3) Tetravalent thiol compound Pentaerythritol tetrakis (3-mercaptobutyrate) (Karenz MT PE1 manufactured by Showa Denko KK).

In using these, they may be used alone or as a mixture of two or more.
Among these polyvalent thiol compounds, trivalent thiol compounds are particularly preferable, and among the trivalent thiol compounds, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine is preferable. -2,4,6 (1H, 3H, 5H) -trione) (Karenz MT NR1 manufactured by Showa Denko KK) is particularly preferred.
(F) When the polyvalent thiol compound is added, the addition amount is preferably 1 to 50 parts by mass, and more preferably 10 to 30 parts by mass with respect to the component (a). The addition amount is preferably 1 part by mass or more from the viewpoint of applicability (wetability) on various substrates, and is preferably 50 parts by mass or less from the viewpoint of heat resistance.

｛式中、ｈは、１又は２の整数であり、ｈが１の場合、Ｘａは、２価の芳香族基であり、ｈが２の場合、Ｘａは、４価の芳香族基であり、Ｘｃ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、ｄは、１～３の整数であり、Ｒｅ及びＲｆは、炭素数１～４のアルキル基であり、同一であっても異なっていてもよく、ｇは、０、１又は２であり、そしてＲｂは、水素原子又は１価の炭化水素基である。｝で表されるカルボキシル基含有の有機ケイ素化合物を、添加することができる。 (G) Carboxyl group-containing organosilicon compound The photosensitive polyorganosiloxane composition may have the following general formula (6) for the purpose of improving applicability (wettability) on various substrates, if desired.

{Wherein h is an integer of 1 or 2, when h is 1, Xa is a divalent aromatic group, and when h is 2, Xa is a tetravalent aromatic group , Xc is a divalent organic group containing a carbon atom directly bonded to a silicon atom, d is an integer of 1 to 3, Re and Rf are alkyl groups of 1 to 4 carbon atoms, and the same Or may be different, g is 0, 1 or 2, and Rb is a hydrogen atom or a monovalent hydrocarbon group. }, An organosilicon compound containing a carboxyl group can be added.

The carboxyl group-containing organosilicon compound represented by the general formula (6) can be obtained by reacting a dicarboxylic anhydride or a tetracarboxylic dianhydride derivative with an organosilicon compound containing an amino group. it can. Various structures can be used as the dicarboxylic acid anhydride or tetracarboxylic dianhydride derivative. For example, maleic anhydride, phthalic anhydride, 1,2-cyclohexyl dicarboxylic acid anhydride, 4-methylcyclohexyl-1,2 -Dicarboxylic anhydride, 1-cyclohexene-1,2-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 1,2-naphthalic anhydride, 1,8-naphthalic anhydride, Pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, diphenyl hexafluoropropylidene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride Anhydride, cyclopexanetetracarboxylic dianhydride, terfe Le tetracarboxylic dianhydride, and the like.

In view of the effect of improving applicability (wetting property) and price, phthalic anhydride and benzophenone tetracarboxylic dianhydride are particularly suitable.
The organosilicon compound containing an amino group to be reacted with a dicarboxylic acid anhydride or a tetracarboxylic dianhydride derivative can be used in various structures, and examples thereof include the following (hereinafter referred to as alkoxy notation): Represents 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.
Considering the effect of improving the coating property (wetting property) and the price, 3-aminopropyltriethoxysilane is particularly preferable.
(G) When the carboxyl group-containing organosilicon compound is added, the addition amount is preferably 0.05 to 20 parts by mass, and preferably 1 to 10 parts by mass with respect to the component (a). More preferred. From the viewpoint of applicability (wettability) on various substrates, the amount added is preferably 0.05 parts by mass or more, and from the viewpoint of storage stability of the photosensitive polyorganosiloxane composition, it is preferably 20 parts by mass or less. In using these, it may be individual or a mixture of two or more.

｛式中、Ｒjは、トリフルオロメチル基又はペンタフルオロエチル基であり、そしてｋは、１～２５の整数である。｝で表される化合物。
　これらの使用にあたっては、単独でも２種以上の混合物でもかまわない。 (H) Nonionic surfactant A nonionic surfactant is added to the photosensitive polyorganosiloxane composition as desired for the purpose of improving applicability (wetability) on various substrates. be able to.
As the surfactant, it is preferable to add a nonionic surfactant as compared with an ionic surfactant from the viewpoint of preventing corrosion of the wiring metal.
Preferred nonionic surfactants include the following compounds:
(1) Ether type polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polycyclic phenyl ether, polyoxypropylene alkyl ether,
(2) Ester ether type polyoxyethylene glyceryl ether fatty acid ester, polyoxyethylene hydrogenated castor oil fatty acid ester,
(3) Ester type Polyethylene glycol fatty acid ester, polyoxyethylene trimethylolpropane fatty acid ester,
(4) Silicone surfactant dimethylsiloxane ethyleneoxy graft compound, dimethylsiloxane propyleneoxy graft compound, (hydroxyethyleneoxypropyl) methylsiloxane-dimethylsiloxane compound,
(5) Fluorosurfactant Perfluoroalkyl carboxylic acid, perfluoroalkyl sulfonic acid, perfluoroalkyl group-containing oligomer (manufactured by Dainippon Ink and Chemicals, trade name: Megafuck, product number R-08), the following general formula (7 ):

{Wherein Rj is a trifluoromethyl group or a pentafluoroethyl group, and k is an integer of 1 to 25. } The compound represented by this.
In using these, it may be individual or a mixture of two or more.

で表される化合物が挙げられる。 Among the nonionic surfactants described above, the fluorine-based surfactant (5) is more preferable in terms of the effect of coating properties on various substrates, and particularly in the case of the compound represented by the general formula (7), It is more preferable because it does not contain a perfluoroalkyl structure (C _n F _{2n + 1} , n = 6 to 12), which is considered harmful. Specifically, the following formula:

The compound represented by these is mentioned.

When the nonionic surfactant is added, the addition amount is preferably 0.01 to 10 parts by mass, and preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the component (a). Is more preferable.
The addition amount is preferably 0.01 parts by mass or more from the viewpoint of improving applicability to various base materials, and the addition amount is preferably 10 parts by mass or less from the viewpoint of suppressing development residue residue, pattern lifting and peeling in lithography.

(I) Other additives The photosensitive polyorganosiloxane composition can be adjusted by arbitrarily adding a solvent to adjust the viscosity. Suitable solvents include N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, tetrahydrofuran, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, cyclohexane Pentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethyl urea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone , Methyl isobutyl ketone, anisole, ethyl acetate, ethyl lactate, butyl lactate and the like, 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 photosensitive polyorganosiloxane composition according to the coating film thickness and viscosity, but are preferably used in the range of 5 to 120 parts by mass with respect to the component (a). .
A sensitizer for improving photosensitivity can be added to the photosensitive polyorganosiloxane composition as desired. Examples of such sensitizers 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-dimethylaminobenzylide) ) Acetone, 1,3-bis (4-diethylaminobenzylidene) acetone, 3,3′-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethyl Aminocoumarin, 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, isoamid 4-diethylaminobenzoate , 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) benzthiazole, 2 -(P-dimethylaminostyryl) naphtho (1,2-p) thiazole, 2- (p-dimethylaminobenzoyl) styrene and the like. Moreover, when using, it may be individual or a mixture of 2 or more types.
When the sensitizer is added, the addition amount is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to the component (a).

If desired, a polymerization inhibitor can be added to the photosensitive polyorganosiloxane composition 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 the polymerization inhibitor is added, the addition amount is preferably 0.001 to 5 parts by mass, and more preferably 0.01 to 1 part by mass with respect to the component (a).
In addition to the above, the photosensitive polyorganosiloxane composition includes an ultraviolet absorber, a coating film smoothness imparting agent, etc., as long as it does not inhibit various characteristics of the photosensitive polyorganosiloxane composition. Various additives can be appropriately blended.

<Method for forming cured relief pattern and polyorganosiloxane film>
Next, the suitable example of the method of forming a hardening relief pattern using the photosensitive polyorganosiloxane composition of this invention is shown below.
First, the composition is applied on various desired base materials in addition to a silicon wafer, a ceramic substrate, an aluminum substrate, and the like. 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. The coated substrate is soft baked at 80 to 200 ° C. for 1 to 15 minutes to obtain a soft baked film having a thickness of 10 to 100 microns, for example, using an exposure projection apparatus such as a contact aligner, mirror projection, or stepper. Actinic rays are irradiated through a desired photomask.

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. From the viewpoint of pattern resolution and handleability, the light source wavelength is particularly preferably UV-i ray (365 nm), and the aligner or stepper is particularly preferable as the exposure projection apparatus.
Thereafter, post-exposure baking (PEB) with 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, A pre-development bake may be applied.
Next, development is performed, and the development can be performed by selecting from methods such as an immersion method, a paddle method, and a rotary spray method. As a developing solution, the good solvent of the photosensitive polyorganosiloxane composition of this invention can be used individually or by mixing a good solvent and a poor solvent suitably. Good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, gamma butyrolactone, α-acetyl-gammabutyrolactone, cyclopenta Non, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone and the like are used as the poor solvent, and methanol, ethanol, isopropanol, isobutyl alcohol and water 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, isopropanol, isobutyl alcohol, propylene glycol monomethyl ether, or the like can be used alone or in an appropriate mixture, or can be used in a stepwise combination.
The relief pattern thus obtained is converted into a cured relief pattern at a curing temperature of 150 to 250 ° C., which is much lower than the conventional polyimide precursor composition. 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, and 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 above-mentioned cured relief pattern is applied between a micro structure such as a surface protective film, an interlayer insulating film, an α-ray shielding film, and 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 the coating film which consists of resin which hardened the photosensitive polyorganosiloxane 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 a semiconductor device, a semiconductor device can be formed using a cured relief pattern of the photosensitive polyorganosiloxane composition of the present invention as the spacer material.
Here, specific examples of the integrated circuit include an integrated circuit using a crystal substrate including silicon, lithium niobate, lithium tartrate, or quartz, and an integrated circuit including a photodiode. 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, the photosensitive polyorganosiloxane composition of the present invention is applied directly or via a thin film layer on a microstructure formed on a crystal substrate on which an integrated circuit is formed. A step of forming a film, a step of irradiating the coating film with an actinic ray through a patterning mask having an opening only in a portion where the spacer material is to be formed, and photocuring the exposed portion, and the coating film using a developer The manufacturing method which includes the process of removing the uncured part of this, and the process of heating a coating film with this base material is mentioned. Each process can be performed by the above-mentioned method.

The present invention will be described in detail by the following synthesis examples, examples and comparative examples.
[Synthesis Example 1]
(Synthesis of polyorganosiloxane POS-1)
To a 500 ml three-necked round bottom flask equipped with a water-cooled condenser and a stirring blade with a vacuum seal, 86.52 g (0.4 mol) of diphenylsilanediol (hereinafter referred to as DPD), 3-methacryloyloxypropyltrimethoxysilane (hereinafter referred to as MEMO) 52.45 g (0.211 mol), 3-morpholinopropyltrimethoxysilane (hereinafter MOPS) 35.12 g (0.141 mol), tetra-isopropoxytitanium (hereinafter TIP) 6.82 g (0.024 mol) were charged and stirred. Started. (Memo: MOPS = mixing ratio of 60:40 mol%) This was immersed in an oil bath, the temperature was set to 120 ° C., and heating was started from room temperature. On the way, methanol generated with the progress of the polymerization reaction was allowed to react 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.
Then, attach a hose connected to a cold trap and a vacuum pump, stir vigorously while heating at 80 ° C. using an oil bath, and gradually increase the degree of vacuum so that the methanol does not bump. Distilled off to obtain polyorganosiloxane POS-1 (viscosity 220 poise at 40 ° C.).

[Synthesis Example 2]
(Synthesis of polyorganosiloxane POS-2)
A polyorganosiloxane POS-2 was prepared in the same manner as in Synthesis Example 1 except that MOPS in Synthesis Example 1 was changed to 32.05 g (0.141 mol) of 2- (2-trimethoxysilylethyl) pyridine (hereinafter referred to as PES). (Viscosity 191 poise at 40 ° C.) was obtained.

[Synthesis Example 3]
(Synthesis of polyorganosiloxane POS-3)
In a 500 ml three-necked round bottom flask equipped with a water-cooled condenser and a stirring blade with a vacuum seal, 86.52 g (0.4 mol) of DPD, 58.36 g (0.235 mol) of MEMO, and 39.16 g of MOPS ( 0.157 mol), 1.14 g (0.004 mol) of TIP and 3.79 g (0.02 mol) of barium hydroxide monohydrate 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. On the way, methanol generated with the progress of the polymerization reaction was returned with a water-cooled condenser and reacted until the temperature of the reaction solution became constant, and then heated and stirred for another 30 minutes.
Then, attach a hose connected to a cold trap and a vacuum pump, stir vigorously while heating at 80 ° C. using an oil bath, and gradually increase the degree of vacuum so that the methanol does not bump. Distilled off to obtain polyorganosiloxane POS-3 (viscosity 181 poise at 40 ° C.).

[Synthesis Example 4]
(Synthesis of polyorganosiloxane POS-4)
The same operation as in Synthesis Example 1 was performed, except that the barium hydroxide monohydrate in Synthesis Example 3 was changed to 0.80 g (0.02 mol) of sodium hydroxide, and the operation before methanol distillation was performed. 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 bottom 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 while methanol does not bump The methanol was distilled off by gradually raising the degree of vacuum to obtain polyorganosiloxane POS-4 (viscosity 298 poise at 40 ° C.). As a result of ICP-MS ion analysis, the sodium ion concentration in POS-4 was less than 1.0 ppm.

[Synthesis Example 5]
(Synthesis of polyorganosiloxane POS-5)
Synthesis Example 1 except that MEMO in Synthesis Example 1 was 54.14 g (0.218 mol), MOPS was 36.41 g (0.146 mol), and TIP was 9.30 g (0.024 mol) of tetra-isopropoxyzirconium isopropanol adduct. In the same manner as in Example 1, polyorganosiloxane POS-6 (viscosity 242 poise at 23 ° C.) was obtained.

[Synthesis Example 6]
(Synthesis of polyorganosiloxane POS-6)
Synthetic Example 1 except that MEMO in Synthesis Example 1 was 54.14 g (0.218 mol), MOPS was 36.41 g (0.146 mol), and TIP was 4.90 g (0.024 mol) of tri-iso-propoxyaluminum. Similarly, polyorganosiloxane POS-6 (viscosity 198 poise at 23 ° C.) was obtained.

[Synthesis Example 7]
(Synthesis of polyorganosiloxane POS-7)
In a 500-ml three-necked round bottom flask equipped with a water-cooled condenser and a stirring blade with a vacuum seal, 86.52 g (0.4 mol) of DPD, 59.60 g (0.24 mol) of MEMO, and 39.90 g of MOPS ( 0.16 mol) and 0.8 g (0.02 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. On the way, methanol generated with the progress of the polymerization reaction was allowed to react 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 bottom 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 while methanol does not bump The methanol was distilled off by gradually raising the degree of vacuum to obtain polyorganosiloxane POS-7 (viscosity 262 poise at 40 ° C.). As a result of ICP-MS ion analysis, the sodium ion concentration in POS-7 was less than 1 ppm.
This product gradually began to become cloudy in the process of methanol distillation, and the clouding progressed during storage at room temperature.

[Synthesis Example 8]
(Synthesis of polyorganosiloxane POS-8)
In a 500 ml three-necked round bottom flask equipped with a water-cooled condenser and a stirring blade with a vacuum seal, 86.52 g (0.4 mol) of DPD, 87.42 g (0.352 mol) of MEMO, and 6.82 g of TIP ( 0.024 mol) was charged and stirring was started. This was immersed in an oil bath, the temperature was set to 120 ° C., and heating was started from room temperature. On the way, methanol generated with the progress of the polymerization reaction was allowed to react 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.
Then, attach a hose connected to a cold trap and a vacuum pump, stir vigorously while heating at 80 ° C. using an oil bath, and gradually increase the degree of vacuum so that the methanol does not bump. Distilled off to obtain polyorganosiloxane POS-8 (viscosity 209 poise at 40 ° C.).

[Synthesis Example 9]
(Synthesis of polyorganosiloxane POS-9)
The same as Synthesis Example 1 except that MEMO in Synthesis Example 1 was 70.03 g (0.282 mol) and MOPS was 17.46 g (0.07 mol) (MEMO: MOPS = 80: 20 mol% mixing ratio). The operation was carried out to obtain polyorganosiloxane POS-9 (viscosity 249 poise at 40 ° C.).

[Synthesis Example 10]
(Synthesis of polyorganosiloxane POS-10)
The same as Synthesis Example 1 except that MEMO in Synthesis Example 1 was 17.39 g (0.070 mol) and MOPS was 70.33 g (0.282 mol) (MEMO: MOPS = 20: 80 mol% mixing ratio). Operation was performed to obtain polyorganosiloxane POS-10 (viscosity 216 poise at 40 ° C.).

[Synthesis Example 11]
(Synthesis of polyorganosiloxane POS-11)
The same as Synthesis Example 1 except that MEMO in Synthesis Example 1 was changed to 61.19 g (0.246 mol) and MOPS was changed to 26.34 g (0.106 mol) (mixing ratio of MEMO: MOPS = 70: 30 mol%). Operation was performed to obtain polyorganosiloxane POS-11 (viscosity 230 poise at 40 ° C.).

[Synthesis Example 12]
(Synthesis of polyorganosiloxane POS-12)
The same as Synthesis Example 1 except that MEMO in Synthesis Example 1 was changed to 26.23 g (0.106 mol) and MOPS was changed to 61.45 g (0.246 mol) (mixing ratio of MEMO: MOPS = 30: 70 mol%). Operation was performed to obtain polyorganosiloxane POS-12 (viscosity 226 poise at 40 ° C.).

[Example 1]
(Preparation of photosensitive polyorganosiloxane composition C-1)
100 parts by mass of polyorganosiloxane POS-1 obtained in Synthesis Example 1, 4 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 4,4′- 0.4 parts by mass of bis (diethylamino) benzophenone, 30 parts by mass of ethoxylated bisphenol A dimethacrylate [number of ethylene glycol units 30; PDBE-1300 manufactured by NOF Corporation], 15 parts by mass of 3-methacryloxypropyltrimethoxysilane 150 parts by mass of silicone resin (Toray Dow Corning 217 flakes) and 40 parts by mass of N-methyl-2-pyrrolidone were weighed and mixed, and filtered through a Teflon (registered trademark) filter having a pore size of 0.2 microns. A varnish-like photosensitive polyorganosiloxane composition C-1 was obtained.

[Example 2]
(Preparation of photosensitive polyorganosiloxane composition C-2)
A varnish-like photosensitive polyorganosiloxane composition C-2 was obtained in the same manner as in Example 1 except that 150 parts by mass of SR-20 manufactured by Konishi Chemical was used as the silicone resin.

[Example 3]
(Preparation of photosensitive polyorganosiloxane composition C-3)
100 parts by mass of polyorganosiloxane POS-2 obtained in Synthesis Example 2, 4 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 4,4′- 0.4 parts by mass of bis (diethylamino) benzophenone, 30 parts by mass of polytetramethylene glycol dimethacrylate (tetramethylene glycol unit number 8 PDT-650 manufactured by NOF Corporation), 15 parts by mass of 3-methacryloxypropyltrimethoxysilane, 150 parts by mass of silicone resin (Toray Dow Corning 217 flakes) and 40 parts by mass of N-methyl-2-pyrrolidone were weighed and mixed, and filtered through a Teflon (registered trademark) filter having a pore size of 0.2 microns. A varnish-like photosensitive polyorganosiloxane composition C-3 was obtained.

[Example 4]
(Preparation of photosensitive polyorganosiloxane composition C-4)
A varnish-like photosensitive polyorganosiloxane composition C-4 was obtained in the same manner as in Example 1 except that POS-3 of Synthesis Example 3 was used as the polyorganosiloxane.

[Example 5]
(Preparation of photosensitive polyorganosiloxane composition C-5)
A varnish-like photosensitive polyorganosiloxane composition C-5 was obtained in the same manner as in Example 1 except that POS-4 of Synthesis Example 4 was used as the polyorganosiloxane.

[Example 6]
(Preparation of photosensitive polyorganosiloxane composition C-6)
A varnish-like photosensitive polyorganosiloxane composition C-6 was obtained in the same manner as in Example 1 except that POS-5 of Synthesis Example 5 was used as the polyorganosiloxane.

[Example 7]
(Preparation of photosensitive polyorganosiloxane composition C-7)
A varnish-like photosensitive polyorganosiloxane composition C-7 was obtained in the same manner as in Example 1 except that POS-6 of Synthesis Example 6 was used as the polyorganosiloxane.

[Example 8]
(Preparation of photosensitive polyorganosiloxane composition C-8)
A varnish-like photosensitive polyorganosiloxane composition C-8 was obtained in the same manner as in Example 1 except that POS-9 of Synthesis Example 9 was used as the polyorganosiloxane.

[Example 9]
(Preparation of photosensitive polyorganosiloxane composition C-9)
A varnish-like photosensitive polyorganosiloxane composition C-9 was obtained in the same manner as in Example 1 except that POS-11 of Synthesis Example 11 was used as the polyorganosiloxane.

[Example 10]
(Preparation of photosensitive polyorganosiloxane composition C-10)
A varnish-like photosensitive polyorganosiloxane composition C-10 was obtained in the same manner as in Example 1 except that POS-12 of Synthesis Example 12 was used as the polyorganosiloxane.

[Example 11]
(Preparation of photosensitive polyorganosiloxane composition C-11)
A varnish-like photosensitive polyorganosiloxane composition C-11 was obtained in the same manner as in Example 1 except that POS-10 of Synthesis Example 10 was used as the polyorganosiloxane.

[Example 12]
(Preparation of photosensitive polyorganosiloxane composition C-12)
100 parts by mass of polyorganosiloxane POS-1 obtained in Synthesis Example 1, 4 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 4,4′- 0.4 parts by mass of bis (diethylamino) benzophenone and 40 parts by mass of N-methyl-2-pyrrolidone are weighed and mixed, filtered through a Teflon (registered trademark) filter with a pore size of 0.2 microns, and varnish-like photosensitive. Polyorganosiloxane composition C-12 was obtained.

[Comparative Example 1]
(Preparation of photosensitive polyorganosiloxane composition C-13)
The mixture was measured and mixed in the same manner as in Example 1 except that POS-7 of Synthesis Example 7 was used as the polyorganosiloxane. After that, I tried to filter with a Teflon (registered trademark) filter with a pore size of 0.2 microns, but it became clogged due to white turbidity component derived from polyorganosiloxane POS-7, and it became impossible to filter. Abandoned.

[Comparative Example 2]
(Preparation of photosensitive polyorganosiloxane composition C-14)
A varnish-like photosensitive polyorganosiloxane composition C-14 was obtained in the same manner as in Example 1 except that POS-8 of Synthesis Example 8 was used as the polyorganosiloxane.

[Comparative Example 3]
(Preparation of photosensitive polyorganosiloxane composition C-15)
A varnish-like photosensitive polyorganosiloxane composition C-15 was obtained in the same manner as in Example 1 except that POS-8 of Synthesis Example 8 was used as the polyorganosiloxane and no silicone resin was added.

[Comparative Example 4]
(Preparation of photosensitive polyorganosiloxane composition C-16)
100 parts by mass of polyorganosiloxane POS-8 obtained in Synthesis Example 8, 4 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 4,4′- 0.4 parts by mass of bis (diethylamino) benzophenone and 40 parts by mass of N-methyl-2-pyrrolidone are weighed and mixed, filtered through a Teflon (registered trademark) filter with a pore size of 0.2 microns, and varnish-like photosensitive. Polyorganosiloxane composition C-16 was obtained.

[Evaluation of tackiness]
The varnish-like photosensitive polyorganosiloxane compositions obtained in Examples and Comparative Examples of the present invention were applied onto a 6-inch silicon wafer using a spin coater (model name Clean Track Mark 8 manufactured by Tokyo Electron). Soft baking was performed at a temperature of 12 minutes to obtain a coating film having an initial film thickness of 45 microns.
The coating film was touched with a fingertip, and the degree of tackiness (stickiness) was evaluated. Evaluation criteria are rank “A” when no contact marks remain, rank “B” when slight contact marks remain, and rank “C” when contact marks remain sticky when touched. ”, The case of stickiness at the same level as before soft baking was evaluated in four grades with a rank“ D ”. The results are shown in Table 1 below.

[Photosensitive evaluation]
The coating film obtained in the same manner as described above was passed through an evaluation photomask designed with a lattice pattern imitating a spacer structure for protecting a lens array of a CMOS image sensor by an i-line stepper exposure machine (Nikon model name: NSR2005i8A). by 100 mJ / cm ² in the transverse direction the exposure amount in the range of 100 ~ 900 mJ / cm ^2, by 2 microns focus from 16 microns 32 micron range in the longitudinal direction, were exposed stepwise changed respectively. 30 minutes after exposure, propylene glycol monomethyl ether acetate was used as a developing solution, and the time until the unexposed area completely dissolved and disappeared was multiplied by 1.4, followed by 10 times with isopropanol. Rotating spray rinse for 2 seconds to obtain a lattice-like relief pattern.
The obtained relief pattern was visually observed under an optical microscope, and the presence or absence of residues in the developed portion (rank “A”: no residue, rank “B”: a slight residue locally, rank “C”: a large amount of residue. ), Degree of pattern swelling in shots with an exposure amount of 200 mJ / cm ² (rank “A”: sharp without swelling, rank “B”: slightly swollen, rank “C”: severely swollen), lift from substrate The presence or absence of peeling (rank “A”: no lifting or peeling, rank “B”: slightly lifting or peeling locally, rank “C”: whole surface or clear lifting or peeling) was evaluated. The results are shown in Table 1 below.

[Low-temperature curing characteristics; evaluation of tensile elongation of cured film]
Each composition of the above-mentioned examples and comparative examples was applied onto a substrate obtained by vacuum-depositing aluminum on a 6-inch silicon wafer using the same method as in the above-described photosensitivity evaluation, and soft baking (initial film after soft baking) The thickness is adjusted so that the film thickness after curing is 10 μm), and then heated and cured at 180 ° C. for 2 hours in an air atmosphere using a vertical curing furnace (manufactured by Koyo Thermo Systems, model name VF-2000B). The resin film having a thickness of 10 μm was prepared after the treatment. 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 a Tensilon tensile tester based on ASTM D-882-88 to evaluate the elongation. The results are shown in Table 2 below.

[Low volatility: Evaluation of 150 ° C soaking weight reduction rate]
Using a strip-shaped film prepared for the above tensile elongation evaluation as a sample, the weight loss rate (unit%) at 150 ° C soaking is measured using a thermogravimetry device (Shimadzu, model name TGA-50). The degassing index was used. 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. The results are shown in Table 2 below.

[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 below.

The embodiment of the present invention greatly improves the tackiness of the soft bake film, and at the same time exhibits excellent photosensitive characteristics and low temperature curing characteristics, has extremely small volume shrinkage during heat curing, and the cured film has low volatility.
Comparative Example 1 is a case where only sodium hydroxide is used as a catalyst during the polymerization of polyorganosiloxane, but the system becomes cloudy during the polymerization, whereby the varnish composition cannot be filtered and is not practical.
In Comparative Example 2, a 5- to 6-membered nitrogen atom-containing heterocyclic group containing no photopolymerizable carbon-carbon double bond in the polyorganosiloxane structure (including those having no aromaticity) is used. Although not included, the tackiness of the soft bake film is difficult compared to the embodiment of the present invention.
Comparative Example 3 and Comparative Example 4 include a 5- to 6-membered nitrogen atom-containing heterocyclic group containing no photopolymerizable carbon-carbon double bond in the structure of the polyorganosiloxane (including those having no aromaticity). .) And is not a case where the silicone resin, which is one of the requirements of the present invention, is added to the photosensitive polyorganosiloxane composition. As a matter of course, the examples of the present invention Also, it is inferior to Comparative Example 2.

[Example 13]
(Preparation of photosensitive polyorganosiloxane composition C-17)
In addition to the composition of Example 1, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H)- Trion) (Karenz MT NR1 manufactured by Showa Denko KK) was weighed and mixed with 25 parts by mass, filtered through a Teflon (registered trademark) filter having a pore size of 0.2 microns, and a varnish-like photosensitive polyorganosiloxane composition. C-15 was obtained.

[Example 14]
(Preparation of carboxyl group-containing organosilicon compound S-1 solution)
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 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 wt% of carboxyl group-containing organosilicon compound S-1. The structure of S-1 is shown below.

(Preparation of carboxyl group-containing organosilicon compound S-2 solution)
A round bottom flask with a volume of 1 L was charged with 32.2 g (0.1 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and 206 g of N-methyl-2-pyrrolidone, 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 weight of carboxyl group-containing organosilicon compound S-2. The structure of S-2 is shown below.

(Preparation of photosensitive polyorganosiloxane composition C-18)
In addition to the composition of Example 1, 10 parts by mass of the 20% NMP solution of carboxyl group-containing organosilicon compound S-1 prepared above (2 parts by mass as pure S-1), carboxyl group-containing organosilicon compound solution S -2 20% NMP solution (1 part by mass as pure S-2), each weighed and mixed, filtered through a Teflon (registered trademark) filter with a pore size of 0.2 microns, varnish-like photosensitive A polyorganosiloxane composition C-18 was obtained.

で示される非イオン性界面活性剤（ＯＭＮＯＶＡ　Ｓｏｌｕｔｉｏｎｓ製　商標名ＰｏｌｙＦｏｘ　品番ＰＦ－６５６）を０．４質量部、計量混合し、孔径０．２ミクロンのテフロン（登録商標）製フィルターでろ過し、ワニス状のポリオルガノシロキサン組成物Ｃ－１９を得た。 [Example 15]
(Preparation of photosensitive polyorganosiloxane composition C-19)
In addition to the composition of Example 1, the following formula:

0.4 parts by mass of a nonionic surfactant (trade name: PolyFox product number PF-656, manufactured by OMNOVA Solutions, Inc.) represented by formula (1) is filtered through a Teflon (registered trademark) filter having a pore size of 0.2 microns, and then varnished. A polyorganosiloxane composition C-19 was obtained.

(Evaluation of applicability (wetting))
A 10% methyl ethyl ketone solution (manufactured by Wako Pure Chemical Industries, Ltd.) of poly (glycidyl methacrylate) was applied onto a 6-inch silicon wafer using a spin coater (model name Clean Track Mark 7 manufactured by Tokyo Electron) at 160 ° C. Soft baking was performed for 10 minutes to obtain a 6-inch silicon wafer on which an organic thin film made of poly (glycidyl methacrylate) having a thickness of 0.8 microns was formed.
The photosensitive polyorganosiloxane compositions C-1, C-17, C-18, and C-19 obtained in Examples 13 to 15 of the present invention and Comparative Example 1 were compared with a spin coater (Tokyo Electron). Application (spin coating) using model name Clean Track Mark 7) and edge cutting (edge rinsing) of 3 mm width from the wafer edge using cyclopentanone and soft baking at 125 ° C. for 12 minutes, initial film thickness A 45 micron coating was obtained.
The outer periphery of the wafer on which this coating film was formed was observed, the distance from the wafer edge to the outermost periphery of the coating film was measured, and the coating property (wetting property) was evaluated. (Rank “A”: 3 mm from wafer edge, no film retreat. Rank “B”: 3 mm or more and 5 mm or less, slightly retract from wafer edge. Rank “C”: Retreat 5 mm or more from wafer edge. Table 3 shows.

In Examples 13 to 15 of the present invention, it is possible to obtain a photosensitive polyorganosiloxane composition that is more excellent in coatability (wetting property) on the substrate than in Comparative Example 1 of the present invention.
Incidentally, the evaluation of tack property, photosensitive property, low temperature curing property, low volatility, and volume shrinkage of the pre-baked films of Examples 13 to 15 was the same as that of Example 1.

The photosensitive polyorganosiloxane composition of the present invention is equipped with an image sensor, a micromachine, or a microactuator for forming an insulating material for an electronic component, a surface protective film, an interlayer insulating film, an α-ray shielding film, etc. in a semiconductor device. It can be suitably used as a semiconductor device or the like and a resin composition used for forming the semiconductor device.

Claims (19)

Photosensitive polyorganosiloxane composition containing the following component (a) and component (b):
(A) 100 parts by mass of polyorganosiloxane, wherein the polyorganosiloxane has the following general formula (1):

{Wherein R is a monovalent group having 6 to 18 carbon atoms containing at least one aromatic group, and may be the same or different. } At least one silanol compound represented by the following general formula (2):

{In the formula, R ′ is a 5- to 6-membered nitrogen atom-containing heterocyclic group (including those having no aromaticity) that does not contain a photopolymerizable carbon-carbon double bond, and has 2 to 11 carbon atoms. And R ″ is a methyl group or an ethyl group, which may be the same or different. } At least one alkoxysilane compound represented by the following general formula (3):

{Wherein R ′ ″ is an organic group having 2 to 17 carbon atoms including a photopolymerizable carbon-carbon double bond group, and R ″ ″ is a methyl group or an ethyl group, Both may be the same or different. } At least one alkoxysilane compound represented by the following general formula (4):

{Wherein M is silicon, germanium, titanium or zirconium, and R ′ ″ ″ is an alkyl group having 1 to 4 carbon atoms, both of which may be the same or different. Good. } A metal alkoxide represented by the following general formula (5):

{Wherein M ′ is boron or aluminum, and R ″ ″ ″ is an alkyl group having 1 to 4 carbon atoms, which may be the same or different. Is obtained by mixing with at least one catalyst selected from the group consisting of Ba (OH) ₂ and polymerizing without adding water, wherein The total molar ratio of the silanol compound represented by 1) to the alkoxysilane compound represented by the general formula (2) and the alkoxysilane compound represented by the general formula (3) is 50:30 to 50:70, The molar ratio of the alkoxysilane compound represented by the general formula (2) to the alkoxysilane compound represented by the general formula (3) is 70:30 to 30:70.
(B) 0.1 to 20 parts by mass of a photopolymerization initiator. The photosensitive poly (ethylene) according to claim 1, further comprising (c) a compound other than the component (a) having two or more photopolymerizable unsaturated bonding groups in an amount of 1 to 100 parts by mass with respect to the component (a). Organosiloxane composition. (D) A silicone resin other than the component (a) exhibiting a three-dimensional network structure obtained by cohydrolyzing and polymerizing an organosilane compound having 2 to 4 hydrolyzable groups, The photosensitive polyorganosiloxane composition according to claim 1, further comprising 50 to 200 parts by mass. The catalyst according to any one of claims 1 to 3, wherein the catalyst is at least one metal alkoxide selected from the group consisting of a metal alkoxide represented by the general formula (4) and a metal alkoxide represented by the general formula (5). The photosensitive polyorganosiloxane composition according to claim 1. The catalyst is at least one catalyst selected from the group consisting of a metal alkoxide represented by the general formula (4), a metal alkoxide represented by the general formula (5), and Ba (OH) ₂ ; and potassium hydroxide. The photosensitive polyorganosiloxane composition according to any one of claims 1 to 3, which is a mixture with at least one catalyst selected from the group consisting of sodium hydroxide. (E) (CH ₃ O) ₃ —Si— (CH ₂ ) ₃ —O—CO—C (CH ₃ ) ═CH ₂ , (CH ₃ O) ₃ —Si— (CH ₂ ) ₃ —O—CO— CH═CH ₂ , and (CH ₃ O) ₃ —Si— (CH ₂ ) ₃ —O—CH ₂ —C ₂ H ₃ O {the C ₂ H ₃ O on the left is an epoxy group} is selected from the group consisting of The photosensitive polyorganosiloxane composition according to any one of claims 1 to 3, further comprising 0.1 to 20 parts by mass of at least one organosilicon compound with respect to component (a). The photosensitive property according to any one of claims 1 to 3, further comprising (f) a polyvalent thiol compound containing at least two thiol groups in an amount of 1 to 50 parts by mass relative to the component (a). Polyorganosiloxane composition. (G) The following general formula (6):

{In the formula, h is an integer of 1 or 2, and when h is 1, Xa is a divalent aromatic group. When h is 2, Xa is a tetravalent aromatic group. Xc is a divalent organic group containing a carbon atom directly bonded to a silicon atom, d is an integer of 1 to 3, Re and Rf are alkyl groups of 1 to 4 carbon atoms, They may be the same or different, g is 0, 1 or 2, and Rb is a hydrogen atom or a monovalent hydrocarbon group. The photosensitive polyorganosiloxane composition according to claim 1 or 2, further comprising 0.05 to 20 parts by mass of a carboxyl group-containing organosilicon compound represented by the formula (a): The photosensitive polyorganosiloxane composition according to any one of claims 1 to 3, further comprising (h) a nonionic surfactant in an amount of 0.01 to 10 parts by mass relative to the component (a). object. A method for forming a polyorganosiloxane film, comprising a step of applying the photosensitive polyorganosiloxane composition according to any one of claims 1 to 3 on a substrate. A cured polyorganosiloxane film obtained by curing the polyorganosiloxane film obtained by the method according to claim 10 by irradiation with actinic light or heating. A step of forming a polyorganosiloxane film on a substrate by the method according to claim 10, a step of irradiating the film with an actinic ray through a patterning mask and photocuring an exposed portion, and using a developer A method for forming a polyorganosiloxane cured relief pattern, comprising a step of removing an uncured portion and a step of heating the whole substrate. A polyorganosiloxane cured relief pattern obtained by the method according to claim 12. A semiconductor device comprising the cured polyorganosiloxane film according to claim 11. A semiconductor device comprising the polyorganosiloxane cured relief pattern according to claim 12. 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. The semiconductor device according to claim 12, wherein the spacer material is the polyorganosiloxane cured relief pattern according to claim 12. The semiconductor device according to claim 16, wherein the integrated circuit includes a photodiode. The semiconductor device according to claim 16, wherein the microstructure is a microlens. A step of forming a polyorganosiloxane film directly on the microstructure or through a thin film layer, a step of irradiating the film with an actinic ray through a patterning mask and photocuring an exposed portion, and a film using a developer The method for manufacturing a semiconductor device according to claim 16, comprising: removing the uncured portion of the substrate; and heating the whole substrate.