KR20100099317A - Photosensitive polyorganosiloxane composition - Google Patents

Abstract

component (a): a polyorganosiloxane to 100 parts by weight, wherein the polyorganosiloxane has a molar ratio of a specific range of the formula (1): a silanol compound represented by the formula R ₂ Si (OH) _2, formula (2 ): Alkoxysilane compound represented by R'Si (OR '') ₃ , and General formula (3): Alkoxysilane compound represented by R '''Si(OR'''') ₃ is represented by General Formula (4): Selected from the group consisting of a metal alkoxide represented by M (OR ''''') ₄ , a metal alkoxide represented by general formula (5): M' (OR '''''') ₃ , and Ba (OH) ₂ . It is obtained by mixing with a catalyst and polymerizing without adding water, and (b) component: The photosensitive polyorganosiloxane composition containing 0.1-20 mass parts of photoinitiators. Groups in the general formulas (1) to (5) are defined in the claims.

Description

Photosensitive polyorganosiloxane composition {PHOTOSENSITIVE POLYORGANOSILOXANE COMPOSITION}

선 차폐막 등의 형성에, 및 이미지 센서나 마이크로 머신, 또는 마이크로 액추에이터를 탑재한 반도체 장치 등에 사용되는 감광성 폴리오르가노실록산 조성물, 및 그것을 사용하여 제조되는 반도체 장치 등에 관한 것이다.The present invention provides an insulating material for an electronic component, a surface protective film, an interlayer insulating film in a semiconductor device,

The photosensitive polyorganosiloxane composition used for formation of a line shield film | membrane, etc., and a semiconductor device with an image sensor, a micromachine, or a micro actuator, etc., the semiconductor device manufactured using the same, etc. are provided.

선 차폐막 등의 용도에는, 우수한 내열성과 전기 특성, 기계 특성을 겸비하는 폴리이미드 수지가 널리 사용되고 있다.Insulating materials for electronic components, and surface protective films of semiconductor devices, interlayer insulating films, and

BACKGROUND ART Polyimide resins having excellent heat resistance, electrical characteristics, and mechanical characteristics are widely used for applications such as line shielding films.

This polyimide resin is normally provided in the form of the photosensitive polyimide precursor composition, apply | coated this to a base material, soft-bakes, irradiates (exposures) an active light ray through a desired patterning mask, develops it, and heats it. It has the characteristic that the hardening relief pattern which consists of heat-resistant polyimide resin can be easily formed by performing hardening process (for example, refer patent document 1).

In recent years, in the manufacturing process of a semiconductor device, the demand for the material which can perform the said thermosetting process at lower temperature is increasing mainly because of the material of a component, or structural design. However, in the case of the conventional polyimide resin precursor composition, when the curing treatment temperature is lowered, thermal imidization cannot be completed, and various cured film physical properties are lowered, the lower limit of the curing treatment temperature is at most 300 ° C.

By the way, as a design concept of the recent semiconductor device, a large area of wiring cross section at a necessary point is made to reduce the electric resistance, resistance noise, resistance heat generation, and the like accompanying the conventional multi-layer high density flow. Attempts are being made. In particular, when the "coarse wiring" layer having a height of 10 microns or more is coated with a conventional polyimide precursor composition and thermally cured, a volume shrinkage of about 40% or more is caused by volatilization of the remaining solvent component, and thus the "giant wiring" phase and its Since a large step occurs in the periphery, there is a high demand for a material that can cover it more uniformly and evenly.

선 차폐막 등을 안정적으로 형성시킬 만한 성능, 예를 들어 각종 기재에 대한 도포성이나 하지 (下地) 기재와의 밀착성이나 실용 레벨의 역학 특성 등을 실현하기는 어렵다.Patent Document 2 below discloses a photosensitive siloxane material which can be cured at a low temperature and has a low volume shrinkage during the thermosetting process. The disclosed technology includes surface protection films, interlayer insulating films,

It is difficult to realize the performance which can stably form a line shielding film etc., for example, the applicability | paintability with respect to various base materials, adhesiveness with a base base material, the dynamics characteristic of a practical level, etc.

In addition, after apply | coating the material disclosed in patent document 2 on a base material, even if it performs the soft bake performed with the conventional polyimide precursor composition, a coating film remains a state with tackiness and fluidity | liquidity. Therefore, it is necessary to generate new constraints in the process, such as worrying about device contamination due to contact between the substrate after application and the apparatus during transportation, or to keep the substrate horizontal at all times to prevent the flow of the coating film on the substrate. It cannot be denied.

On the other hand, semiconductor devices in which an element having an optical function and a mechanical function are mounted in or in an integrated circuit are put to practical use. Most of these are formed by forming a device such as a transistor on a crystal substrate such as silicon using a conventionally known semiconductor process, and then forming a device (microstructure) having a function corresponding to the purpose of the semiconductor device, and packaging them integrally. Are manufactured.

As an example of such a packaging technique, for example, Patent Document 3 below describes a microstructure formed on a crystal substrate on which an integrated circuit is formed, a package material for covering the microstructure, and the package material as the microstructure. Disclosed are a semiconductor device having a spacer for supporting an image and an example thereof. Although the technique disclosed in patent document 3 can be used suitably for various sensors, such as a microlens array and a chemical sensor, or a wide range of semiconductor devices, such as a surface acoustic wave device, in order to implement invention of patent document 3, a package material is used as a microstructure. Spacers (also referred to as dams, bulkheads) for supporting the image play an important role. The following three things can be considered as a characteristic calculated | required by a spacer.

First, since this spacer should be formed only in the part which is needed as a support body, it is advantageous if it is formed by the member which has photosensitive itself. This is because, if the spacer itself has photosensitivity, the latter can be omitted during the lithography process and the etching process which are usually used to leave the spacer only in necessary portions.

In addition, a member having a low heat resistance, for example, an epoxy resin or the like, is used in the periphery of the spacer, and a microstructure or the like located below the spacer is not necessarily high in heat resistance. Therefore, secondly, it can be said that the process of forming this spacer is preferable at a lower temperature.

Third, since the spacer forms a "cavity" in the closed space including the microstructure, and the description of Patent Document 3, it is not preferable that the volatile components and the like contained in the package remain after the package is completed. That is, this spacer is required to be a low volatile component.

The above characteristics are considered to be required for the spacer, but Patent Document 3 does not disclose the specific members used for the spacer.

That is, it is the present situation that the photosensitive film-forming material which is excellent in low temperature hardenability, has small volume shrinkage at the time of hardening, is tack-free, and has the practical performance which can replace the conventional polyimide precursor is not found yet.

Japanese Patent Publication No. 2826940 European Patent Publication No. 1196478 Japanese Patent Publication No. 2003-516634

선 차폐막 등의 형성에, 및 이미지 센서나 마이크로 머신, 또는 마이크로 액추에이터를 탑재한 반도체 장치 등에 사용되는 수지 조성물에 대한 요구, 즉 각종 기재에 대한 도포성, 감광 특성이 우수하고, 250 ℃ 이하에서의 저온 경화가 가능하고, 150 ℃ 에서의 휘발성 (균열 (均熱) 중량 감소율), 및 180 ℃ 큐어시에서의 체적 수축률 (큐어 후 잔막률) 이 작고, 조성물을 코팅하고 소프트 베이크하여 얻어지는 소프트 베이크막 (이하, 간단히 「소프트 베이크막」이라고도 한다) 의 택성을 저감시킬 수 있는 감광성 폴리오르가노실록산 조성물을 제공하는 것이다.The problem to be solved by the present invention is a surface protective film, an interlayer insulating film in an insulating material of a recent electronic component or a semiconductor device,

It is excellent in the requirements for resin compositions used in the formation of line shielding films and the like, and in semiconductor devices equipped with image sensors, micro machines, or micro actuators, that is, coating properties and photosensitive properties to various substrates. Soft baking film which can be cured at low temperature, has low volatility (crack weight loss rate) at 150 ° C., and volume shrinkage rate (cure after film residual rate) at 180 ° C., and coats the composition and soft bakes. It is providing the photosensitive polyorganosiloxane composition which can reduce the tackiness of (it is also only hereafter called a "soft bake film | membrane").

The present inventors earnestly examined and experimented, and the result showed that the alkoxysilane compound which has the 5-6 membered nitrogen atom containing heterocyclic group (including the thing which does not have aromaticity) which does not contain a photopolymerizable carbon-carbon double bond is included. When used as a raw material of polyorganosilane, it discovered unexpectedly that the tackiness of the soft bake film of the photosensitive polyorganosiloxane composition using this unexpectedly fell, and came to this invention.

That is, this invention is the following [1]-[19]:

[1] A photosensitive polyorganosiloxane composition comprising the following (a) component and (b) component:

(a) 100 parts by mass of polyorganosiloxane, wherein the polyorganosiloxane is represented by the following general formula (1):

[Formula 1]

At least 1 type of silanol compound represented by {in formula, R is a C6-C18 monovalent group containing one aromatic group at least, and may all be same or different}, General formula (2) below:

[Formula 2]

{In formula, R 'is a C2-C11 organic group which has the 5-6-membered nitrogen atom containing heterocyclic group which does not contain a photopolymerizable carbon-carbon double bond, including the thing which does not have aromaticity, And R '' is a methyl group or an ethyl group, all of which may be the same or different} and at least one alkoxysilane compound represented by the following general formula (3):

(3)

(Wherein R '' 'is a C2-C17 organic group containing a photopolymerizable carbon-carbon double bond group, and R' '' 'is a methyl group or an ethyl group, all of which may be the same or different} At least one alkoxysilane compound is represented by the following general formula (4):

[Formula 4]

A metal alkoxide represented by {wherein M is any one of silicon, germanium, titanium or zirconium, and R '' '' 'is an alkyl group having 1 to 4 carbon atoms and may be the same or different} (5):

[Chemical Formula 5]

Consisting of a metal alkoxide represented by {wherein M 'is boron or aluminum, and R''''''is an alkyl group having 1 to 4 carbon atoms and may be the same or different} and Ba (OH) ₂ It is obtained by mixing with at least one catalyst selected from the group and polymerizing without adding water, wherein the silanol compound represented by the general formula (1) versus the alkoxysilane compound represented by the general formula (2) and the general formula (3) The molar ratio of the sum total of the alkoxysilane compound represented by) is 50: 30-50: 70, and the molar ratio of the alkoxysilane compound represented by General formula (2) to the alkoxysilane compound represented by General formula (3) is 70: 30-30 Is 70,

(b) 0.1-20 mass parts of photoinitiators.

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

[3] (d) Silicone resins other than (a) component which show the three-dimensional network structure obtained by co-hydrolyzing and polymerizing the organosilane compound which has 2-4 hydrolyzable groups to (a) component The photosensitive polyorganosiloxane composition as described in said [1] or [2] which is contained in 50-200 mass parts with respect to the above.

[4] any one of the above [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 of description.

[5] 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 , potassium hydroxide, and hydroxide; The photosensitive polyorganosiloxane composition in any one of said [1]-[3] which is a mixture of at least 1 catalyst chosen from the group which consists of sodium.

[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 in the left is an epoxy group} The photosensitive polyorganosiloxane composition in any one of said [1]-[5] which further contains at least 1 or more types of organosilicon compounds chosen with respect to (a) component at 0.1-20 mass parts.

[7] The photosensitive polyol according to any one of the above [1] to [6], wherein the polyvalent thiol compound containing at least two or more thiol groups is further contained in an amount of 1 to 50 parts by mass based on the component (a). Ganosiloxane composition.

[8] (g) The following general formula (6):

[Formula 6]

{Wherein h is an integer of 1 or 2, when h is 1, Xa is a divalent aromatic group, when h is 2, Xa is a tetravalent aromatic group and Xc is a carbon directly bonded to a silicon atom A divalent organic group containing an atom, d is an integer of 1-3, Re and Rf are a C1-C4 alkyl group, may be same or different, g is 0, 1 or 2, Rb is hydrogen The photosensitive polyorgano in any one of said [1]-[7] which further contains the carboxyl group-containing organosilicon compound represented by the atom or monovalent hydrocarbon group} by 0.05-20 mass parts with respect to (a) component. Siloxane composition.

[9] The photosensitive polyorganosiloxane composition according to any one of the above [1] to [8], which further contains (h) a nonionic surfactant at 0.01 to 10 parts by mass with respect to the component (a).

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

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

[12] A step of forming a polyorganosiloxane film on a substrate by the method described in [10] above, irradiating active film to the film via a patterning mask to photocuring the exposed portion, and using a developer to A method of forming a polyorganosiloxane cured relief pattern comprising a step of removing a cured portion and a step of heating each substrate.

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

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

[15] A semiconductor device comprising the polyorganosiloxane curing relief pattern according to the above [12].

[16] A semiconductor device having 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 whose ash is the polyorganosiloxane hardening relief pattern of the said [12].

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

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

[19] A process of forming a polyorganosiloxane film directly on a microstructure or through a thin film layer, irradiating active film to the film through a patterning mask to photocuring the exposed portion, and using the developer to uncur the portion of the film. The method of manufacturing the semiconductor device according to any one of the above [16] to [18], including a step of removing the step and a step of heating each substrate.

The photosensitive polyorganosiloxane composition of this invention is excellent in the applicability | paintability to various base materials, the soft baking film has low tackiness, the volume shrinkage rate at 180 degreeC cure, and the crack weight reduction rate at 150 degreeC are small, and it is 250 degrees C or less. It is possible to cure at low temperature and to be excellent in photosensitivity.

Hereinafter, each component which comprises the photosensitive polyorganosiloxane composition is demonstrated concretely below.

(a) polyorganosiloxane

The polyorganosiloxane is 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 at least one kind represented by the following general formula (3). Of the alkoxysilane compound is mixed with at least one catalyst selected from the group consisting of a metal alkoxide represented by the following general formula (4), a metal alkoxide represented by the following general formula (5), and Ba (OH) ₂ , and water It is obtained by a method of polymerization without addition.

Here, "without adding water" means that the operation of adding water at the time of polymerization is not carried out, and it does not exclude water which is naturally contained in a raw material or even water in a polymerization atmosphere.

[Formula 7]

{In formula, R is a C6-C18 monovalent group containing one aromatic group at least, all may be same or different.},

[Formula 8]

{In formula, R 'is a C2-C11 organic group which has the 5-6-membered nitrogen atom containing heterocyclic group which does not contain a photopolymerizable carbon-carbon double bond, including the thing which does not have aromaticity, R '' is a methyl group or an ethyl group, all may be the same or different),

[Formula 9]

{In formula, R '' 'is a C2-C17 organic group containing a photopolymerizable carbon-carbon double bond group, R' '' is a methyl group or an ethyl group, all may be same or different},

[Formula 10]

{In formula, M is silicon, germanium, titanium, or zirconium, R '' '' 'is a C1-C4 alkyl group, all may be same or different},

[Formula 11]

{In formula, M 'is boron or aluminum, R' '' '' is a C1-C4 alkyl group, and all may be 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).

In addition, in the process of superposing | polymerizing a polyorganosiloxane without adding water, you may mix at least 1 alkali metal hydroxide selected from the group which consists of potassium hydroxide and sodium hydroxide as the catalyst.

In the silanol compound represented by General formula (1), R is a C6-C18 group which contains at least one aromatic group, Specifically, the following structures:

[Formula 12]

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

In the alkoxysilane compound represented by General formula (2), R 'has a 5-6 membered nitrogen atom containing heterocyclic group (including the thing which does not have aromaticity) which does not contain a photopolymerizable carbon-carbon double bond. It is a C2-C11 organic group. Unlike the alkoxysilane compound represented by General formula (3), the compound represented by General formula (2) does not contain the group which has a photopolymerizable carbon-carbon double bond. R '' is a methyl group or an ethyl group, and both may be same or different. As a specific example of R ', the following structure:

[Formula 13]

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

In the alkoxysilane compound represented by General formula (3), R '' 'is a C2-C17 organic group containing group which has photopolymerizable carbon-carbon double bond, R "' is a methyl group or an ethyl group, All may be same or different. As a specific example of R '' ', the following structure:

[Formula 14]

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

The photosensitive polyorganosiloxane is 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 one kind represented by the general formula (3). An alkoxysilane compound and at least one catalyst 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 (hereinafter simply referred to as "catalyst"). It is obtained by the method of mixing and superposing | polymerizing without adding water.

The metal alkoxide represented by General formula (4) and the metal alkoxide represented by General formula (5) catalyze the de-alcohol condensation reaction of a silanol compound (silanol group) and an alkoxysilane compound (alkoxysilyl group), and it is alkoxy itself. It acts as a group-containing compound and participates in the dealcoholization condensation reaction, with some forming a polysiloxane or polysilsesquioxane structure in the form introduced into the molecule.

As a mixing ratio, it is based on mixing a silanol compound and an alkoxysilane compound in 1: 1 (molar ratio), and an alkoxysilane compound can be mixed in the ratio of 30-70 mol with respect to 50 mol of silanol compounds. . When mixing a metal alkoxide, it is preferable to adjust a whole mixing ratio in the form which replaces a part of alkoxysilane compound (reduces the amount of alkoxysilane compound mixture in fixed ratio).

Specifically, when using the tetravalent metal alkoxide represented by General formula (4) as a metal alkoxide, the tetravalent metal alkoxide and an alkoxysilane compound are converted into the molar ratio of 1: 2, respectively (quavalent metal) For every 1 mole increase in the amount of alkoxide mixture, 2 moles of the alkoxysilane compound are reduced. Moreover, when using the trivalent metal alkoxide represented by General formula (5), it is preferable to substitute and convert the trivalent metal alkoxide and the alkoxysilane compound in the molar ratio of 2: 3, respectively.

Preferred silanol compounds include diphenylsilanediol, di-p-toluylsilanediol, di-p-styrylsilanediol, dinaphthylsilanediol, and the like. Price, availability, copolymerization and heat resistance In view of viewpoints and the like, diphenylsilanediol is particularly preferable.

Moreover, as a compound preferable as an alkoxysilane compound which has the nitrogen atom containing heterocyclic group of 5-6 atoms (including the thing which does not have aromaticity) which does not contain a photopolymerizable carbon-carbon double bond, N-trialkoxy silyl -1,2,4-triazole, N-trialkoxysilylimidazole, N-trialkoxysilylpyrrole, N-trialkoxysilylpyridine, N-trialkoxysilylpyrrolidine, piperidinomethyltrialkoxysilane, 2-piperidinoethyltrialkoxysilane, 3-morpholinopropyltrialkoxysilane, 3-piperazinopropyltrialkoxysilane, 3-piperidinopropyltrialkoxysilane, 3- (4-methylpiperazinopropyl ) Trialkoxysilane, 3- (4-methylpiperidinopropyl) trialkoxysilane, 4- (2-trialkoxysilylethyl) pyridine, N- (3-trialkoxysilylpropyl) -4,5-dihydroimi Dazole, 2- (2-trialkoxysilylethyl) pyridine, N- (3-trialkoxysilylpropyl) pyrrole (above, The alkoxy part represents a methoxy group or an ethoxy group), etc. are mentioned.

MEANS TO SOLVE THE PROBLEM The present inventors used the alkoxysilane compound which has the 5-6 membered nitrogen atom containing heterocyclic group (including the thing which does not have aromaticity) which does not contain these photopolymerizable carbon-carbon double bonds as a raw material of polyorganosilane. When used, it was found that the tackiness of the soft bake film of the photosensitive polyorganosiloxane composition using this was resolved dramatically. Among them, 3-morpholinopropyltrimethoxysilane, 3-piperazinopropyltrimethoxysilane, 3-piperidinopropyltrimethoxysilane, 2- (2-trimethoxysilylethyl) pyridine, 4 Particular preference is given to using-(2-triethoxysilylethyl) pyridine.

Moreover, as an alkoxysilane compound containing a photopolymerizable carbon-carbon double bond group, vinyltrimethoxysilane, vinyltriethoxysilane, 1-propenyl trimethoxysilane, 1-propenyl triethoxysilane, 2 -Propenyltrimethoxysilane, 2-propenyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyl Trimethoxysilane, 3-acryloyloxypropyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, p- (1-propenylphenyl) trimethoxysilane, p -(1-propenylphenyl) triethoxysilane, p- (2-propenylphenyl) trimethoxysilane, p- (2-propenylphenyl) triethoxysilane and the like, but excellent UV-i In order to obtain line | wire photosensitivity characteristic, 3-methacryloyl oxypropyl trimethoxysilane and 3-methacryloyl oxypropyl tri Cysilane, 3-acryloyloxypropyltrimethoxysilane, and 3-acryloyloxypropyltriethoxysilane are more preferable, and in consideration of price and harmfulness, flexibility and performance of high crosslinking, 3-methacryloyl Especially preferred is oxypropyltrimethoxysilane.

Preferable examples of the metal alkoxide represented by the general formula (4) and the metal alkoxide represented by the general formula (5) include trimethoxy aluminum, triethoxy aluminum, tri-n-propoxy aluminum and tri-iso-propoxy aluminum. , Tri-n-butoxyaluminum, tri-iso-butoxyaluminum, tri-sec-butoxyaluminum, tri-tert-butoxyaluminum, trimethoxyboron, triethoxyboron, tri-n-propoxyboron , Tri-iso-propoxyboron, tri-n-butoxyboron, tri-iso-butoxyboron, tri-sec-butoxyboron, tri-tert-butoxyboron, tetramethoxysilane, tetraethoxysilane , Tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-iso-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetra Methoxy germanium, tetraethoxy germanium, tetra-n-propoxygernium, tetra-iso-propoxyge Germanium, tetra-n-butoxy germanium, tetra-iso-butoxy germanium, tetra-sec-butoxy germanium, tetra-tert-butoxy germanium, tetramethoxytitanium, tetraethoxytitanium, tetra-n propoxy Titanium, tetra-iso-propoxytitanium, tetra-n-butoxytitanium, tetra-iso-butoxytitanium, tetra-sec-butoxytitanium, tetra-tert-butoxytitanium, tetramethoxyzirconium, tetraethoxy Zirconium, tetra-n-propoxy zirconium, tetra-iso-propoxy zirconium, tetra-n-butoxy zirconium, tetra-iso-butoxy zirconium, tetra-sec-butoxy zirconium, tetra-tert-butoxy zirconium, etc. Can be mentioned. In order to achieve a rapid and uniform polymerization reaction, it is preferable to be liquid in the reaction temperature range, and tetra-iso-propoxycitane is particularly preferable in consideration of the activity height, availability, and the like as a catalyst.

The polyorganosiloxane can be polymerized by mixing the above-mentioned silanol compound, the above-mentioned two alkoxysilane compounds, and a catalyst suitably and heating. The heating temperature and the temperature increase rate at this time are important parameters in controlling the degree of polymerization of the polyorganosiloxane to be produced. Although depending on the degree of polymerization desired, it is preferable to heat and polymerize the said raw material mixture to about 70 degreeC-150 degreeC.

When the addition amount at the time of superposition | polymerization of a catalyst is less than 2 mol% with respect to a silanol compound, when heating to the said suitable temperature range or more, the polymerization of polyorganosiloxane may not fully advance. In such a case, when potassium hydroxide and sodium hydroxide are added in an appropriate amount as an auxiliary catalyst, the deficiency of the catalyst can be compensated for, and the degree of polymerization of the resulting polyorganosiloxane can be controlled appropriately. In this case, potassium ions and sodium ions remain in the polyorganosiloxane after the completion of the reaction, and since these alkali metal ions can be easily removed and purified using an ion exchange resin or the like, they are not particularly problematic in practical use. Do.

However, when the silanol compound and the alkoxysilane compound are to be polymerized only by the action of potassium hydroxide or sodium hydroxide without adding the catalyst at the time of polymerization, partial formation of a high crystalline polymer component cannot be avoided. It is unpreferable since it precipitates, becomes cloudy, precipitates, and disgenerates a system. It is important to add the said catalyst at the time of superposition | polymerization also in the meaning which avoids this "crystallization."

The minimum of the addition amount of a catalyst is 0.1 mol% or more, More preferably, it is 0.5 mol% or more with respect to a silanol compound for the said reason.

The upper limit of the addition amount of a catalyst depends on the performance of the target polyorganosiloxane. In order to achieve the excellent photosensitivity property, the alkoxysilane compound which has the photopolymerizable carbon-carbon double bond mentioned above is essential, and the upper limit of the polymerization addition amount of a metal alkoxide is 30 mol% or less with respect to a silanol compound, calculated from the minimum required amount, More preferably, it is 20 mol% or less.

In addition, the use ratio of 2 types of alkoxysilane compounds is important in making both the tackiness elimination effect of a soft bake film | membrane, and the outstanding photosensitive characteristic compatible. As described above, the silanol compound and the alkoxysilane compound are basically mixed at a ratio of 1: 1 (molar ratio), but among these, 5 to 6 membered nitrogen atoms containing no photopolymerizable carbon-carbon double bonds are contained. It is preferable that the molar ratio of the alkoxysilane compound which has a heterocyclic group (including the thing which does not have aromaticity), and the alkoxysilane compound containing a photopolymerizable carbon-carbon double bond group shall be 70: 30-30: 70, More preferably, it is the range of 60: 40-40: 60.

When the use molar ratio of the alkoxysilane compound containing a photopolymerizable carbon-carbon double bond group exceeds 30% of all the alkoxysilane compounds, the outstanding photosensitive characteristic anticipated by this invention is achieved. At the same time, the use molar ratio of the alkoxysilane compound having a 5 to 6-membered nitrogen atom-containing heterocyclic group (including not having aromaticity) that does not contain a photopolymerizable carbon-carbon double bond is 30% of the total alkoxysilane compound. When it exceeds%, the tackiness of the soft bake film of the photosensitive polyorganosiloxane composition can be reduced.

(b) photopolymerization initiator

It is important to add a photoinitiator to the photosensitive polyorganosiloxane composition for the purpose of providing photosensitivity.

As a photoinitiator, the following are mentioned:

(1) benzophenone derivatives such as benzophenone, 4,4'-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylketone, dibenzyl ketone, fluorenone,

(2) 2,2'- diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl Phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2 Acetophenone derivatives such as -methylpropionyl) -benzyl] -phenyl} -2-methylpropane-1-one and methyl phenylglyoxylate;

(3) thioxanthone derivatives such as thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone and diethyl thioxanthone;

(4) benzyl derivatives such as benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal,

(5) benzoin derivatives such as benzoin, benzoin methyl ether, 2-hydroxy-2-methyl-1-phenylpropan-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-diphenylpropanetri On-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) and the like Oxime compounds,

-하이드록시케톤계 화합물,(7) 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane- 1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropane, etc.

-Hydroxyketone compounds,

-아미노알킬페논계 화합물,(8) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE369), 2-dimethylamino-2- (4-methylbenzyl) -1- (4- Such as morpholin-4-yl-phenyl) butan-1-one

Aminoalkylphenone compounds,

(9) bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6- Phosphine oxide compounds such as trimethylbenzoyl-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.

In the case of using these photoinitiators, you may be individual or 2 or more types of mixtures.

-아미노알킬페논계 화합물이 보다 바람직하다. 그 첨가량은, 상기 (a) 성분에 대하여, 0.1 ∼ 20 질량부로 하는 것이 바람직하고, 1 ∼ 10 질량부로 하는 것이 보다 바람직하다. 첨가량이 0.1 질량부 이상에서, 노광시에 광중합이 충분히 진행될 만큼의 광이 공급되고, 노광부의 경화가 충분히 진행되어, 실용적인 릴리프 패턴을 얻을 수 있다. 반대로 첨가량이 20 질량부 이하이면, 도포막 표면 부근에서의 노광 흡수가 지나치게 커지지 않고, 기판면 부근까지 노광 광선이 도달하여, 광중합이 막두께 방향에서 균일해지기 때문에, 실용적인 릴리프 패턴을 얻을 수 있다.Among the photoinitiators described above, in particular in terms of photosensitivity,

More preferred are aminoalkyl phenone compounds. It is preferable to set it as 0.1-20 mass parts with respect to the said (a) component, and, as for the addition amount, it is more preferable to set it as 1-10 mass parts. At 0.1 mass part or more of addition amount, the light enough to fully advance photopolymerization at the time of exposure is supplied, hardening of an exposure part advances sufficiently, and a practical relief pattern can be obtained. On the contrary, when the addition amount is 20 parts by mass or less, the exposure absorption in the vicinity of the coating film surface does not become too large, and the exposure light beam reaches the vicinity of the substrate surface and the photopolymerization becomes uniform in the film thickness direction, whereby a practical relief pattern can be obtained. .

(c) compounds other than the component (a) having two or more photopolymerizable unsaturated bond groups

In order to improve the film-forming characteristic, the photosensitive characteristic, and the mechanical characteristic (elongation after hardening) after hardening, compounds other than (a) component which have two or more photopolymerizable unsaturated bond groups can be added. As such a monomer, the polyfunctional (meth) acrylic acid ester type compound which can superpose | polymerize by the action of a photoinitiator is preferable, For example, polyethyleneglycol diacrylate [number of ethylene glycol units 2-20], polyethylene Glycol dimethacrylate [number of ethylene glycol units 2-20], poly (1,2-propylene glycol) diacrylate [number of 1,2-propylene glycol units 2-20], poly (1,2-propylene glycol ) Dimethacrylate [number of 1,2-propylene glycol units 2-20], polytetramethylene glycol diacrylate [number of tetramethylene glycol units 2-10], polytetramethylene glycol dimethacrylate [tetramethylene glycol unit 2-10], 1,4-cyclohexanediacrylate, 1,4-cyclohexanedimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolprop Triacrylate, ethoxylated trimethylolpropane triacrylate [number of ethylene glycol units 2-20], trimethylolpropane trimethacrylate, tri-2-hydroxyethyl isocyanurate triacrylate, tri-2- Hydroxyethyl isocyanurate trimethacrylate, glycerol diacrylate, glycerol dimethacrylate, ditrimethylol propane triacrylate, ditrimethylol propane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythrate Lithol hexaacrylate, methylenebisacrylamide, ethylene glycol diglycidyl ether-methacrylic acid adduct, glycerol diglycidyl ether-acrylic acid adduct, bisphenol A diglycidyl ether-acrylic acid adduct, bisphenol A di Glycidyl ether-methacrylic acid adduct, ethoxylated bisphenol A diacrylate [ethyleneglycol oil Number 2-30 of nits, ethoxylated bisphenol A dimethacrylate [number 4-30 of ethylene glycol units], N, N'-bis (2-methacryloyloxyethyl) urea, etc. are mentioned.

Especially, 1 or more types of compounds chosen from the group which consists of ethoxylated bisphenol A dimethacrylate [number of ethylene glycol units 4-30], polytetramethylene glycol dimethacrylate [number of tetramethylene glycol units 2-10] This is preferred.

As ethoxylated bisphenol A dimethacrylate [number 4-30 of an ethylene glycol unit], it is a following formula:

[Formula 15]

In the formula, Bremmer PDBE-200, 250, 450, 1300 by Nihon Oils and Chemicals Co., Ltd. shown by q + r <4> -30 is mentioned as an example.

As polytetramethylene glycol dimethacrylate [number of tetramethylene glycol units 2-10], it is preferable that the number of tetramethylene glycol units is 5-10, and a following formula:

[Formula 16]

The Bremmer PDT-650 by Nihon Oils and Chemicals Co., Ltd. shown by {s <8> is mentioned as an example.

Among these, PDBE-450, PDBE-1300, and PDT-650 are especially preferable.

In addition, at the time of use, you may mix and use 2 or more types individually as needed. It is preferable that it is 1-100 mass parts with respect to the said (a) component, and, as for the addition amount, it is more preferable that it is 5-50 mass parts. If the amount is 100 parts by mass or less, the stability of the resin liquid is high and the quality variation is small, which is preferable.

(d) silicone resin

Silicone resin can be added to the photosensitive polyorganosiloxane composition for the purpose of further reducing the tackiness and fluidity of the soft bake film. Here, the silicone resin is, for example, a covalently numbered organosilane compound having 2 to 4 hydrolyzable groups such as an alkoxysilyl group and a chlorosilyl group, which is recorded in, for example, a "Silicone Handbook" published in the daily industrial newspaper. Polymer having a three-dimensional network structure obtained by decomposition and polymerization ''. In addition, the said (a) component shall not correspond to (c) silicone resin.

In order to achieve the objective of this invention, it is preferable to add especially what is called straight silicone resin, such as a methyl type, a phenyl type, a phenylmethyl type, a phenylethyl type, and a phenylpropyl type. Examples of these include methyl silicone resins such as KR220L, KR242A, KC89, KR400, KR500 (above Shin-Etsu Chemical Co., Ltd.), 217 flakes (manufactured by Toray Dow Corning), SR-20, SR-21 (above Konishi Chemical Co., Ltd.) Phenyl-based silicone resins such as phenyl-based silicone resins such as Manufacture), KR213, KR9218 (manufactured by Shin-Etsu Chemical Co., Ltd.), 220 flakes, 223 flakes, and 249 flakes (manufactured by Toray Dow Corning), SR-23 (Konish) Phenyl ethyl-type silicone resins, such as the chemical industry make, Z-6018 (made by Toray Dow Corning), etc. are mentioned.

For the purpose of reducing the tackiness of the soft bake film and improving the fluidity, the addition of a silicone resin having a higher crosslinking density and a solid at a commercial temperature range is preferable, and in that sense, phenyl-based or phenylethyl or phenylpropyl-based It is more preferable to select silicone resin. Specifically, 217 flakes, SR-20, SR-21, SR-23, Z-6018 and the like are particularly preferable. These may be used independently and may be mixed and used suitably.

It is preferable that the addition amount at the time of adding these silicone resin is 50-200 mass parts with respect to the said (a) component. 50 mass parts or more are preferable from a viewpoint of tackiness and fluidity, and 200 mass parts or less are preferable from a viewpoint of photosensitive characteristics, such as i line | wire photosensitivity.

(e) organosilicon compounds

An organosilicon compound can be added to the photosensitive polyorganosiloxane composition for the purpose of improving adhesiveness with various base materials (however, the organosilicon compound containing a carboxyl group mentioned later is excluded). Examples of the organosilicon compound include the following (hereinafter, alkoxy notation refers to a methoxy group or an ethoxy group). Vinyltrialkoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropylmethyl dialkoxysilane, p-styryltrialkoxysilane, 3-methacryloxypropyltrialkoxysilane, 3-methacryloxypropylmethyl dialkoxysilane, 3-acryloxypropyltrialkoxysilane, 3-acryloxypropylmethyl dialkoxysilane, N-2 (aminoethyl) -3- Aminopropyltrialkoxysilane, N-2 (aminoethyl) -3-aminopropylmethyldiakoxysilane, 3-aminopropyltrialkoxysilane, 3-trialkoxysilyl-N- (1,3-dimethyl-butylidene) Propylamine, N-phenyl-3-aminopropyltrialkoxysilane, 3-ureidopropyltrialkoxysilane, 3-ureidopropylmethyl dialkoxysilane, 3-mercaptopropyltrialkoxysilane, 3-mercaptopropylmethyldi Alkoxysilane, Bis (trialkoxysilylpropyl) tetrasulfide, 3-isocyane Agent profile trialkoxysilane.

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 (left C ₂ H ₃ O is an epoxy group) at least one member selected from the group consisting of Compounds are preferred.

In particular, (CH ₃ O) ₃ -Si- (CH ₂ ) ₃ -O-CO-C (CH ₃ ) = CH ₂ , that is, 3-methacryloyloxypropyltrimethoxysilane (hereinafter, MEMO) May be abbreviated as), which is preferable from the viewpoint of flexibility and adhesiveness improving effect. As for the addition amount in the case of adding an adhesive agent, 0-20 mass parts is preferable with respect to the component (a) of this invention from a stability viewpoint of a composition. More preferably, it is 0.1-15 mass%, More preferably, it is 3-10 mass%.

(f) polyvalent thiol compounds

As desired, a polyvalent thiol compound having two or more thiol groups can be added to the photosensitive polyorganosiloxane composition for the purpose of improving the applicability (wetting property) on various substrates. As a polyvalent thiol compound, the following are mentioned, for example:

(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-di Thia-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'-anilinophenyl-iso-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-thia Diazol-2,5-dithiol, 1,4-bis (3-mercaptobutyryloxy) butane (Carens manufactured by Showa Denko Co., Ltd.) MT BD1),

(2) trivalent thiol compounds

1,3,5-benzenetritriol, s-triazine-2,4,6-tritriol, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine- 2,4,6 (1H, 3H, 5H) -trion) (Carens MT NR1 manufactured by Showa Electric Co., Ltd.),

(3) tetravalent thiol compounds

Pentaerythritol tetrakis (3-mercaptobutylate) (Carens MT PE1 manufactured by Showa Electric Co., Ltd.).

In the case of using these, individual may be sufficient and 2 or more types of mixtures may be sufficient as them.

Among these polyvalent thiol compounds, trivalent thiol compounds are particularly preferred, and among trivalent thiol compounds, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2, 4,6 (1H, 3H, 5H) -trione) (Carens MT NR1 manufactured by Showa Electric Co., Ltd.) is particularly preferable.

(f) As addition amount when adding a polyvalent thiol compound, it is preferable that it is 1-50 mass parts with respect to the said (a) component, and it is more preferable that it is 10-30 mass parts. As addition amount, 1 mass part or more is preferable from a viewpoint of the coating property (wetting property) on various base materials, and 50 mass parts or less are preferable from a heat resistant viewpoint.

(g) Carboxyl group-containing organosilicon compounds

The photosensitive polyorganosiloxane composition has the following general formula (6) for the purpose of improving the applicability (wetability) on various substrates as desired.

[Formula 17]

{Wherein h is an integer of 1 or 2, when h is 1, Xa is a divalent aromatic group, when h is 2, Xa is a tetravalent aromatic group and Xc is a carbon directly bonded to a silicon atom A divalent organic group containing an atom, d is an integer of 1-3, Re and Rf are a C1-C4 alkyl group, may be same or different, g is 0, 1 or 2, and Rb is The carboxyl group-containing organosilicon compound shown by the hydrogen atom or the monovalent hydrocarbon group} can be added.

The carboxyl group-containing organosilicon compound represented by the general formula (6) can be obtained by reacting an organosilicon compound containing an amino group with a derivative of dicarboxylic anhydride or tetracarboxylic dianhydride. Various structures can be used as the dicarboxylic acid anhydride or tetracarboxylic dianhydride derivative, for example, maleic anhydride, phthalic anhydride, 1,2-cyclohexyldicarboxylic acid anhydride, 4-methylcyclohexyl -1,2-dicarboxylic acid anhydride, 1-cyclohexene-1,2-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 1,2-naphthalic anhydride, 1,8-naphthalic anhydride, pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, diphenylsulfontetracarboxylic dianhydride, diphenylhexafluoropropylidene tetracarboxylic dianhydride, diphenyl ether Tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, terphenyl tetracarboxylic dianhydride, etc. are mentioned.

In consideration of the improvement effect of coating property (wetting property) and price, phthalic anhydride and benzophenone tetracarboxylic dianhydride are especially preferable.

An organosilicon compound containing an amino group reacted with a dicarboxylic acid anhydride or a tetracarboxylic dianhydride derivative can also be used in various structures, and examples thereof include the following (hereinafter, alkoxy denotes a methoxy group or Ethoxy group).

2-aminoethyltrialkoxysilane, 3-aminopropyltrialkoxysilane, 3-aminopropyldialkoxymethylsilane, 2-aminoethylaminomethyltrialkoxysilane, 2-aminoethylaminomethyldiakoxymethylsilane, 3- (2 -Aminoethylaminopropyl) trialkoxysilane, 3- (2-aminoethylaminopropyl) dialkoxymethylsilane, 3-allylaminopropyltrialkoxysilane, 2- (2-aminoethylthioethyl) trialkoxysilane, 2- (2-aminoethylthioethyl) dialkoxy methylsilane, 3-piperazinopropyl trialkoxysilane, 3-piperazinopropyl dialkoxy methylsilane, cyclohexylaminopropyl trialkoxysilane, etc. are mentioned.

In consideration of the improvement effect of coating property (wetting property) and a price, 3-aminopropyl triethoxysilane is especially preferable.

(g) It is preferable that it is 0.05-20 mass parts with respect to the said (a) component, and, as for the addition amount when adding the organosilicon compound containing a carboxyl group, it is more preferable that it is 1-10 mass parts. From the standpoint of applicability (wetting) on various substrates, the addition amount is preferably 0.05 parts by mass or more, and 20 parts by mass or less is preferable from the viewpoint of storage stability of the photosensitive polyorganosiloxane composition. In the case of using these, independent or 2 or more types of mixtures may be sufficient.

(h) nonionic surfactants

A nonionic surfactant can be added to the photosensitive polyorganosiloxane composition for the purpose of improving the coating property (wetting property) on various base materials as desired.

As surfactant, it is preferable to add a nonionic surfactant compared with an ionic surfactant from a corrosion prevention of 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 cured castor oil fatty acid ester,

(3) ester type

Polyethylene glycol fatty acid esters, polyoxyethylenetrimethylolpropane fatty acid esters,

(4) silicone surfactant

Dimethylsiloxane ethyleneoxy graft compound, dimethylsiloxane propyleneoxy graft compound, (hydroxyethyleneoxypropyl) methylsiloxane-dimethylsiloxane compound,

(5) fluorine-based surfactants

Perfluoroalkylcarboxylic acid, perfluoroalkylsulfonic acid, perfluoroalkyl group-containing oligomer (Dainippon Ink Chemical Industries, trade name Megapak, product number R-08), the following general formula (7):

[Formula 18]

(Wherein Rj is a trifluoromethyl group or a pentafluoroethyl group, and k is an integer of 1 to 25).

In the case of using these, independent or 2 or more types of mixtures may be sufficient.

Among the nonionic surfactants described above, the fluorine-based surfactant of (5) is more preferable in view of the effect of applicability to various substrates, and particularly in the case of the compound represented by the general formula (7), purple is considered to be harmful to the environment. It is more preferable because it does not contain a fluoroalkyl structure (C _n F _{2n + 1} , n = 6 to 12). Specifically, the following formula:

[Formula 19]

[Formula 20]

The compound represented by this is mentioned.

It is preferable to set it as 0.01-10 mass parts with respect to 100 mass parts of said (a) component, and, as for the addition amount at the time of adding a nonionic surfactant, it is more preferable to set it as 0.1-5 mass parts.

In view of improving the applicability to various substrates, the amount of addition is preferably 0.01 parts by mass or more, and the amount of addition is 10 parts by mass in view of suppression of developing part residue, pattern floating and peeling in lithography. Part or less is preferable.

(i) other additives

-아세틸-γ-부티로락톤, 테트라메틸우레아, 1,3-디메틸-2-이미다졸리논, N-시클로헥실-2-피롤리돈, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노메틸에테르아세테이트, 메틸에틸케톤, 메틸이소부틸케톤, 아니솔, 아세트산에틸, 락트산에틸, 락트산부틸 등을 들 수 있고, 이들은 단독으로 또는 2 종 이상의 조합으로 사용할 수 있다. 이들 중에서도, N-메틸-2-피롤리돈이나 γ-부티로락톤, 프로필렌글리콜모노메틸에테르아세테이트가 특히 바람직하다.A viscosity can be adjusted by adding a solvent arbitrarily to the photosensitive polyorganosiloxane composition. Preferred solvents include N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, tetrahydrofuran, N, N-dimethylacetamide, dimethyl sulfoxide, hexa Methylphosphoramide, pyridine, cyclopentanone, γ-butyrolactone,

-Acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Methyl ethyl ketone, methyl isobutyl ketone, anisole, ethyl acetate, ethyl lactate, butyl lactate, etc. are mentioned, These can be used individually or in combination of 2 or more types. Among these, N-methyl-2-pyrrolidone, (gamma) -butyrolactone, and propylene glycol monomethyl ether acetate are especially preferable.

Although these solvent can be added to the photosensitive polyorganosiloxane composition suitably according to a coating film thickness and a viscosity, it is preferable to use in the range of 5-120 mass parts with respect to the said (a) component.

A sensitizer for improving photosensitivity can be added to the photosensitive polyorganosiloxane composition as desired. As such a sensitizer, For example, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2, 5-bis (4'- diethylamino benzylidene) cyclopentanone, 2, 6 -Bis (4'-diethylaminobenzylidene) cyclohexanone, 2,6-bis (4'-dimethylaminobenzylidene) -4-methylcyclohexanone, 2,6-bis (4'-diethylamino Benzylidene) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, 2- (4'-dimethylaminocinnamylidene) indanon , 2- (4'-dimethylaminobenzylidene) indanon, 2- (p-4'-dimethylaminobiphenyl) benzothiazole, 1,3-bis (4-dimethylaminobenzylidene) acetone, 1,3 -Bis (4-diethylaminobenzylidene) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7- Dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-e Cycarbonyl-7-diethylaminocoumarin, N-phenyl-N-ethylethanolamine, N-phenyldiethanolamine, Np-tolyl diethanolamine, N-phenylethanolamine, N, N-bis (2-hydr Oxyethyl) aniline, 4-morpholinobenzophenone, 4-dimethylaminobenzoic acid isoamyl, 4-diethylaminobenzoic acid isoamyl, 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. In addition, at the time of use, you may be individual or 2 or more types of mixtures.

It is preferable that it is 0.1-10 mass parts with respect to the said (a) component, and, as for the addition amount when adding the said sensitizer, it is more preferable that it is 1-5 mass parts.

As desired, a polymerization inhibitor can be added to the photosensitive polyorganosiloxane composition for the purpose of improving the viscosity at the time of storage, and stability of photosensitivity. As such a polymerization inhibitor, for example, hydroquinone, N-nitrosodiphenylamine, p-tert- butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclo Hexanediamine tetraacetic acid, glycol etherdiamine tetraacetic 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-phenylhydroxyamineammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt , N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt, bis (4-hydroxy-3,5-ditert-butyl) phenylmethane and the like can be used. It is preferable that it is 0.001-5 mass parts with respect to said (a) component, and, as for the addition amount when adding a polymerization inhibitor, it is more preferable that it is 0.01-1 mass part.

In addition to the above, various additives may be appropriately added to the photosensitive polyorganosiloxane composition, as necessary, as long as it does not impair various properties of the photosensitive polyorganosiloxane composition, including a UV absorber, a coating film smoothing agent, and the like. Can be.

<Formation of Curing Relief Pattern and Polyorganosiloxane Film>

Next, the preferable 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 onto various desired substrates in addition to a silicon wafer, a ceramic substrate, an aluminum substrate, and the like. As a coating apparatus or a coating method, a spin coater, a die coater, a spray coater, immersion, printing, a blade coater, roll coating, etc. can be used. Soft-baking the apply | coated base material at 80-200 degreeC for 1 to 15 minutes, for example, obtaining the soft-baking film of a film thickness of 10-100 micrometers, and using exposure projection apparatuses, such as a contact aligner, a mirror projection, and a stepper, Active rays are irradiated through a desired photo mask.

X-rays, electron beams, ultraviolet rays, visible rays and the like can be used as the actinic rays. In the present invention, those having a wavelength of 200 to 500 nm are preferably used. In view of the resolution and handleability of the pattern, the wavelength of the light source is particularly preferably UV-i ray (365 nm), and an aligner or stepper is particularly preferable as the exposure projection apparatus.

Thereafter, for the purpose of improving the photosensitivity, a post-exposure bake (PEB) with an arbitrary temperature and time combination (preferably a temperature of 40 ° C to 200 ° C and a time of 10 seconds to 360 seconds), You may bake before image development.

-아세틸-감마부티로락톤, 시클로펜타논, 시클로헥사논, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노메틸에테르아세테이트, 메틸에틸케톤, 메틸이소부틸케톤, 메틸아밀케톤 등이, 빈용매로는 메탄올, 에탄올, 이소프로판올, 이소부틸알코올 및 물 등이 사용된다.Next, the development is carried out, which can be carried out by selecting from methods such as dipping method, puddle method and rotary spray method. As a developing solution, the good solvent of the photosensitive polyorganosiloxane composition of this invention can be used individually, or a good solvent and a poor solvent can be mixed and used suitably. Examples of good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, gamma butyrolactone,

Acetyl-gamma butyrolactone, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, and the like as methanol, Ethanol, isopropanol, isobutyl alcohol, water and the like are used.

After completion of the development, the coating film having a relief pattern is obtained by washing with a rinse solution and removing the developer. As a rinse liquid, distilled water, methanol, ethanol, isopropanol, isobutyl alcohol, propylene glycol monomethyl ether, etc. can be used individually or in mixture suitably, and can be used combining it step by step.

The relief pattern obtained in this way is converted into a cure relief pattern at the curing temperature much lower than the conventional polyimide precursor composition of 150-250 degreeC. This heat-hardening can be performed using a hotplate, an inner oven, the temperature rising oven which can set a temperature program, etc. As an atmosphere gas at the time of heat-hardening, air may be used and inert gas, such as nitrogen and argon, may be used as needed.

선 차폐막, 및 마이크로 렌즈 어레이 등의 미크로 구조체와 그 패키지재 사이의 지지체 (격벽) 로 이루어지는 군에서 선택되는 어느 것으로서 사용하고, 다른 공정은 주지의 반도체 장치의 제조 방법을 적용함으로써, CMOS 이미지 센서 등의 광학 소자를 포함하는 각종 반도체 장치를 제조할 수 있다. 또, 상기 서술한 감광성 폴리오르가노실록산 조성물을 경화시킨 수지로 이루어지는 도포막을 갖는 전자 부품이나 반도체 장치를 얻을 수 있다.The surface protective film, the interlayer insulating film of the semiconductor device formed on the base material, such as a silicon wafer, the hardening relief pattern mentioned above,

It is used as any selected from the group which consists of a microstructure, such as a line shielding film and a microlens array, and the support body (b partition) between the package materials, and another process applies a manufacturing method of a well-known semiconductor device, Various semiconductor devices including the optical element of can be manufactured. Moreover, the electronic component and semiconductor device which have a coating film which consists of resin which hardened the photosensitive polyorganosiloxane composition mentioned above can be obtained.

A semiconductor device having 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, which is referred to as the spacer material. It can also be set as a semiconductor device using the hardening relief pattern of the photosensitive polyorganosiloxane composition of this invention.

Here, as an example of an integrated circuit, the integrated circuit containing an integrated circuit using a crystal substrate containing a silicon, lithium niobate, lithium tartarate, or a crystal | crystallization, or a photodiode is mentioned. Microstructures refer to micron-sized mechanical, photomechanical, and electromechanical devices. Specifically, a micro lens is mentioned. The package material is preferably transparent and may be formed of glass.

As a method for manufacturing the semiconductor device, a step of forming a coating film by applying the photosensitive polyorganosiloxane composition of the present invention directly or through a thin film layer on a microstructure formed on a crystal substrate on which an integrated circuit is formed, and forming a spacer material Irradiating actinic rays to the coating film through a patterning mask having only an opening to be photosensitive, and photocuring the exposed portion, removing the uncured portion of the coating film using a developer, and heating the coating film for each substrate. The manufacturing method containing a process is mentioned. Each process can be performed by the method mentioned above.

Example

The present invention will be specifically described by the following synthesis examples, examples and comparative examples.

Synthesis Example 1

(Synthesis of polyorganosiloxane POS-1)

In a 500 mL three-necked round bottom flask equipped with a water-cooled condenser and a stirring blade with a vacuum seal, diphenylsilanediol (hereinafter referred to as DPD) 86.52 g (0.4 mol), 3-methacryloyloxypropyltrimethoxysilane ( MEMO) 52.45 g (0.211 mol), 35.12 g (0.141 mol) of 3-morpholinopropyltrimethoxysilane (hereinafter referred to as MOPS) and 6.82 g (0.024 mol) of tetra-iso propoxycitane (hereinafter referred to as TIP) were injected thereto. And stirring were started (mixing ratio of MEMO: MOPS = 60: 40 mol%). It was immersed in an oil bath, the temperature was set to 120 degreeC, and heating was started from room temperature. Reaction was carried out until the reaction solution temperature became constant while refluxing methanol generated with the progress of the polymerization reaction in the water cooling condenser, and heating and stirring were further continued for 30 minutes thereafter.

Thereafter, a hose connected to a cold trap and a vacuum pump was attached, stirred vigorously while heating at 80 ° C. using an oil bath, and methanol was distilled off by gradually increasing the vacuum degree so that methanol did not dolby, Ganosiloxane POS-1 (viscosity 220 poise at 40 degreeC) was obtained.

Synthesis Example 2

(Synthesis of Polyorganosiloxane POS-2)

Polyorganosiloxane POS was performed by the same operation 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 PES). -2 (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, 39.16 g (0.157 mol) of MOPS, TIP 1.14 g (0.004 mol) and 3.79 g (0.02 mol) of barium hydroxide monohydrate were injected, and stirring was started. This was immersed in an oil bath, heating temperature was set to 80 degreeC, and heating was started from room temperature. Reaction was carried out until the reaction solution temperature became constant while refluxing methanol generated with the progress of the polymerization reaction in the water cooling condenser, and heating and stirring were further continued for 30 minutes thereafter.

Thereafter, a hose connected to a cold trap and a vacuum pump was attached, stirred vigorously while heating at 80 ° C. using an oil bath, and methanol was distilled off by gradually increasing the vacuum degree so that methanol did not dolby, Kanosiloxane POS-3 (viscosity 181 poise in 40 degreeC) was obtained.

Synthesis Example 4

(Synthesis of Polyorganosiloxane POS-4)

The same operation as in Synthesis Example 1 was carried out except that 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 (Amberite 15, manufactured by Organo Co., Ltd., swelled and washed with dry weight of 40 g), and sodium ions. Was removed.

This is transferred to a round bottom flask equipped with a stirring vane with a vacuum seal and a hose connected to a cold trap and a vacuum pump, soaked in an oil bath heated at 80 ° C. and vigorously stirred, while gradually increasing the vacuum degree so that methanol does not dolby. Methanol was distilled off by winding and polyorganosiloxane POS-4 (viscosity 298 poise at 40 degreeC) was obtained. 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 and Synthesis Example 1 except that 54.14 g (0.218 mol) of MEMO, 36.41 g (0.146 mol) of MOPS, and 9.30 g (0.024 mol) of TIP of tetra-iso propoxyzirconium isopropanol adduct In the same manner, polyorganosiloxane POS-5 (viscosity 242 poise at 23 ° C.) was obtained.

[Synthesis Example 6]

(Synthesis of polyorganosiloxane POS-6)

In the same manner as in 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 4.90 g (0.024 mol) tri-iso-propoxy aluminum. And polyorganosiloxane POS-6 (viscosity 198 poise at 23 ° C) were 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, 39.90 g (0.16 mol) of MOPS, hydroxide 0.8 g (0.02 mol) of sodium was injected and stirring was started. This was immersed in an oil bath, heating temperature was set to 80 degreeC, and heating was started from room temperature. Reaction was carried out until the reaction solution temperature became constant while refluxing methanol generated with the progress of the polymerization reaction in the water cooling condenser, and heating and stirring were further continued for 30 minutes thereafter.

Thereafter, the reaction solution was cooled to room temperature, and passed through a glass column filled with an ion exchange resin (Amberite 15, manufactured by Organo Co., Ltd., swelled and washed with dry weight of 40 g), and sodium ions. Was removed.

This is transferred to a round bottom flask equipped with a stirring vane with a vacuum seal and a hose connected to a cold trap and a vacuum pump, soaked in an oil bath heated at 80 ° C. and vigorously stirred, while gradually increasing the vacuum degree so that methanol does not dolby. Methanol was distilled off by winding and polyorganosiloxane POS-7 (viscosity 262 poise at 40 degreeC) was obtained. As a result of ICP-MS ion analysis, the sodium ion concentration in POS-7 was less than 1 ppm.

This gradually began to become cloudy in the process of methanol distillation, and also clouded during storage at room temperature.

[Synthesis Example 8]

(Synthesis of Polyorganosiloxane POS-8)

Into 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 (0.024 mol) of TIP were injected. , Stirring was started. It was immersed in an oil bath, the temperature was set to 120 degreeC, and heating was started from room temperature. Reaction was carried out until the reaction solution temperature became constant while refluxing methanol generated with the progress of the polymerization reaction in the water cooling condenser, and heating and stirring were further continued for 30 minutes thereafter.

Thereafter, a hose connected to a cold trap and a vacuum pump was attached, stirred vigorously while heating at 80 ° C. using an oil bath, and methanol was distilled off by gradually increasing the vacuum degree so that methanol did not dolby, Kanosiloxane POS-8 (viscosity 209 poise at 40 degreeC) was obtained.

Synthesis Example 9

(Synthesis of Polyorganosiloxane POS-9)

The same procedure as in Synthesis Example 1 was carried out except that 70.03 g (0.282 mol) of MEMO and 17.46 g (0.07 mol) of MOPS were used (MEMO: MOPS = 80:20 mol%). And polyorganosiloxane POS-9 (viscosity 249 poise at 40 ° C) were obtained.

Synthesis Example 10

(Synthesis of polyorganosiloxane POS-10)

The same procedure as in Synthesis Example 1 was conducted except that 17.39 g (0.070 mol) of MEMO in Synthesis Example 1 and 70.33 g (0.282 mol) of MOPS were used (MEMO: MOPS = 20:80 mol% of a mixing ratio). And polyorganosiloxane POS-10 (viscosity 216 poise at 40 degreeC) were obtained.

Synthesis Example 11

(Synthesis of polyorganosiloxane POS-11)

The same procedure as in Synthesis Example 1 was carried out except that 61.19 g (0.246 mol) of MEMO and 26.34 g (0.106 mol) of MOPS (MEMO: MOPS = 70: 30 mol% of mixing ratio) were used. And polyorganosiloxane POS-11 (viscosity 230 poise at 40 degreeC) were obtained.

Synthesis Example 12

(Synthesis of polyorganosiloxane POS-12)

The same procedure as in Synthesis Example 1 was carried out except that 26.23 g (0.106 mol) of MEMO and 61.45 g (0.246 mol) of MOPS were used (MEMO: MOPS = 30:70 mol% of a mixing ratio). And polyorganosiloxane POS-12 (viscosity 226 poise at 40 degreeC) were obtained.

Example 1

(Preparation of the 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 mass part of -bis (diethylamino) benzophenone and the ethoxylated bisphenol A dimethacrylate [the number of ethylene glycol units 30; 30 parts by mass of PDBE-1300 manufactured by Nihon Oil and Fat, 15 parts by mass of 3-methacryloxypropyltrimethoxysilane, 150 parts by mass of silicone resin (217 flakes manufactured by Toray Dow Corning), and N-methyl-2 -40 mass parts of pyrrolidone was metered-mixed, respectively, and it filtered with the filter made from Teflon (trademark) of the pore diameter of 0.2 micron, and obtained the varnish-shaped photosensitive polyorganosiloxane composition C-1.

[Example 2]

(Preparation of the photosensitive polyorganosiloxane composition C-2)

A varnish-shaped photosensitive polyorganosiloxane composition C-2 was obtained in the same manner as in Example 1 except that 150 parts by mass of Cornish Chemical Co., Ltd. SR-20 was used as the silicone resin.

Example 3

(Preparation of the 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 and 30 parts by mass of polytetramethylene glycol dimethacrylate (PDT-650 manufactured by Tetramethylene Glycol Unit Number 8 Nippon Oil Fat and Oil) and 3-methacryloxypropyltrime Weigh 15 parts by mass of oxysilane, 150 parts by mass of silicone resin (217 flakes manufactured by Toray Dow Corning) and 40 parts by mass of N-methyl-2-pyrrolidone, respectively, and a teflon of 0.2 micron pore diameter. It filtered by the filter (trademark) and the varnish-shaped photosensitive polyorganosiloxane composition C-3 was obtained.

Example 4

(Preparation of the photosensitive polyorganosiloxane composition C-4)

A varnish-shaped photosensitive polyorganosiloxane composition C-4 was obtained like Example 1 except having used POS-3 of the synthesis example 3 as polyorganosiloxane.

Example 5

(Preparation of the photosensitive polyorganosiloxane composition C-5)

Varnish-shaped photosensitive polyorganosiloxane composition C-5 was obtained like Example 1 except having used POS-4 of the synthesis example 4 as polyorganosiloxane.

Example 6

(Preparation of the photosensitive polyorganosiloxane composition C-6)

A varnish-shaped photosensitive polyorganosiloxane composition C-6 was obtained like Example 1 except having used POS-5 of the synthesis example 5 as polyorganosiloxane.

Example 7

(Preparation of the photosensitive polyorganosiloxane composition C-7)

Varnish-shaped photosensitive polyorganosiloxane composition C-7 was obtained like Example 1 except having used POS-6 of the synthesis example 6 as polyorganosiloxane.

Example 8

(Preparation of the photosensitive polyorganosiloxane composition C-8)

A varnish-shaped photosensitive polyorganosiloxane composition C-8 was obtained like Example 1 except having used POS-9 of the synthesis example 9 as polyorganosiloxane.

Example 9

(Preparation of the photosensitive polyorganosiloxane composition C-9)

Varnish-shaped photosensitive polyorganosiloxane composition C-9 was obtained like Example 1 except having used POS-11 of the synthesis example 11 as polyorganosiloxane.

Example 10

(Preparation of the photosensitive polyorganosiloxane composition C-10)

Varnish-shaped photosensitive polyorganosiloxane composition C-10 was obtained like Example 1 except having used POS-12 of the synthesis example 12 as polyorganosiloxane.

Example 11

(Preparation of photosensitive polyorganosiloxane composition C-11)

Varnish-shaped photosensitive polyorganosiloxane composition C-11 was obtained like Example 1 except having used POS-10 of the synthesis example 10 as polyorganosiloxane.

Example 12

(Preparation of the 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 mass parts of -bis (diethylamino) benzophenone and 40 mass parts of N-methyl- 2-pyrrolidone were metered-mixed, respectively, and it filtered with the filter made from Teflon (trademark) of pore diameter of 0.2 micron, and varnish The photosensitive polyorganosiloxane composition C-12 of the shape was obtained.

Comparative Example 1

(Preparation of photosensitive polyorganosiloxane composition C-13)

The measurement was carried out 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 filter made of Teflon (registered trademark) having a pore diameter of 0.2 micron, but it caused clogging, which is thought to be caused by a turbidity component derived from polyorganosiloxane POS-7, on the way. Gave up.

Comparative Example 2

(Preparation of the photosensitive polyorganosiloxane composition C-14)

Varnish-shaped photosensitive polyorganosiloxane composition C-14 was obtained like Example 1 except having used POS-8 of the synthesis example 8 as polyorganosiloxane.

Comparative Example 3

(Preparation of the photosensitive polyorganosiloxane composition C-15)

A varnish-shaped 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 the 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 mass parts of -bis (diethylamino) benzophenone and 40 mass parts of N-methyl- 2-pyrrolidone were metered-mixed, respectively, and it filtered with the filter made from Teflon (trademark) of pore diameter of 0.2 micron, and varnish The photosensitive polyorganosiloxane composition C-16 of the shape was obtained.

[Evaluation of taste]

The varnish-shaped photosensitive polyorganosiloxane composition obtained by the Example of this invention and a comparative example is apply | coated on a 6 inch silicon wafer using a spin coater (form name Clean Track Mark 8 by Tokyo Electron make), and it is 125 degreeC. It soft-baked for 12 minutes and obtained the coating film of 45 microns of initial film thicknesses.

This coating film was contacted with a fingertip to evaluate the degree of tackiness (stickiness). As a criterion of the evaluation, the case where no contact marks remain is ranked "A", the case where minor contact marks remain is rank "B", and when the contact is adhesive, when the contact marks remain clearly, the rank "C", soft The case where stickiness of the level equivalent to before baking was evaluated by four steps which made rank "D". The results are shown in Table 1 below.

[Photosensitive characteristic evaluation]

The i-line stepper exposure machine (model name NSR2005i8A manufactured by Nikon) was made to pass through the photomask for evaluation which designed the grid | lattice-shaped pattern which imitated the spacer structure for lens array protection of a CMOS image sensor through the coating film obtained by carrying out similarly to the above, The exposure amount was changed in steps of 100 mJ / cm 2 in the transverse direction in the range of 100 to 900 mJ / cm 2, and the focus was changed in steps of 2 microns in the longitudinal direction in the range of 16 microns to 32 microns, respectively. After 30 minutes from the exposure, using a propylene glycol monomethyl ether acetate as the developer, a rotary spray development was performed by multiplying 1.4 by the time until the unexposed portion was completely dissolved and disappeared, followed by a rotary spray for 10 seconds with isopropanol. It rinsed and the lattice-shaped relief pattern was obtained.

The obtained relief pattern was visually observed under an optical microscope, and the presence or absence of the residual part of a developing part (rank "A": no residue, rank "B": local residue a little, rank "C": many residue), exposure amount 200mJ / Swelling degree of the pattern in the short of cm 2 (rank "A": sharp without swelling, rank "B": slightly swelling, rank "C": severe swelling), presence or absence of injury or peeling from the substrate (rank "A": No injury or peeling, rank "B": locally wound or peeled off slightly, rank "C": whole surface or clear injury or peeling)) were evaluated. The results are shown in Table 1 below.

[Low Temperature Curing Characteristics; Evaluation of Tensile Elongation of Cured Film]

Each composition of the said Example and a comparative example was apply | coated on the base material which vacuum-deposited aluminum on the 6 inch silicon wafer using the method similar to photosensitive evaluation mentioned above, and softbaking (initial film thickness after softbaking is hardened After the film thickness was adjusted to 10 μm, and then heated at 180 ° C. for 2 hours under an air atmosphere, using a vertical cure (made by Koyo Thermo Systems, model name VF-2000B). The hardening process was performed and the resin film of 10 micrometers of film thicknesses after hardening was produced. This resin film was cut into 3.0 mm width using a dicing saw (Disco Co., Ltd., model name DAD-2H / 6T), immersed in 10% hydrochloric acid aqueous solution, peeled from the silicon wafer, and was made into a rectangular film sample. .

After leaving this film sample in the atmosphere of 23 degreeC and 55% RH for 24 hours, the tension test by the tensilon tensile tester based on ASTMD-882-88 was performed, and elongation was evaluated. The results are shown in Table 2 below.

Low volatility; Evaluation of 150 ° C Crack Weight Reduction Rate]

Using the rectangular film prepared for the tensile elongation evaluation as a sample, the weight reduction rate (unit%) at the time of 150 degreeC cracking process was measured using the thermogravimetry reduction apparatus (made by Shimadzu, model name TGA-50). It was set as an index of digasity. Measurement conditions are the temperature increase rate of 10 degreeC / min to 150 degreeC, the crack processing time at 150 degreeC for 22 hours, and nitrogen atmosphere. The results are shown in Table 2 below.

[Evaluation of Volume Shrinkage in Heat Curing]

The thickness of the coating film before and after the heat curing treatment (cure) for 2 hours at 180 ° C. using a vertical cure, which was carried out when the sample for tensile elongation evaluation was produced, was used as a stylus stepmeter (KLA Tencor Co., Ltd., model name P- 15), the change rate (residual film ratio, unit%) was calculated and used as an index of the volume shrinkage ratio. The results are shown in Table 2 below.

The embodiment of the present invention greatly improves the tackiness of the soft bake film, exhibits excellent photosensitivity and low temperature curing properties, very small volume shrinkage during heat curing, and the cured film is low volatility.

Comparative Example 1 is a case where only sodium hydroxide is used as a catalyst in the polymerization of polyorganosiloxane, and the system becomes cloudy during polymerization, whereby the varnish composition is also incapable of filtration and is not practical.

Comparative Example 2 does not contain any 5 to 6 membered nitrogen atom-containing heterocyclic groups (including those having no aromaticity) that do not contain a photopolymerizable carbon-carbon double bond in the structure of the polyorganosiloxane. However, compared with the embodiment of the present invention, there is a drawback in the tackiness of the soft bake film.

Comparative Example 3 and Comparative Example 4 do not contain any 5 to 6 membered nitrogen atom-containing heterocyclic groups (including those having no aromaticity) that do not contain a photopolymerizable carbon-carbon double bond in the structure of the polyorganosiloxane. Although it does not contain and the silicone resin which is one of the requirements of this invention is not added to the photosensitive polyorganosiloxane composition, it is naturally falling also about the comparative example 2 as well as the Example of this invention.

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) as a polyvalent thiol compound ) -Trion) (Carens MT NR1 manufactured by Showa Denko Co., Ltd.) was weighed and mixed in 25 parts by mass, respectively, and filtered through a filter made of Teflon (registered trademark) having a pore diameter of 0.2 micron, and having a varnish-shaped photosensitive poly Organosiloxane composition C-17 was obtained.

Example 14

(Preparation of carboxyl group-containing organosilicon compound S-1 solution)

Into a 1 L round bottom flask, 29.6 g (0.2 mol) of phthalic anhydride and 195 g of N-methyl-2-pyrrolidone were injected and stirring was started. The solution was cooled to 0 ° C. and a solution of 44.2 g (0.2 mol) of 100 g of N-methyl-2-pyrrolidone in 3-aminopropyltriethoxysilane 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 the carboxyl group-containing organosilicon compound S-1. The structure of S-1 is shown below.

[Formula 21]

(Preparation of carboxyl group-containing organosilicon compound S-2 solution)

32.2 g (0.1 mol) of 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride and 206 g of N-methyl- 2-pyrrolidone are injected | thrown-in to the 1 liter round bottom flask, and stirring is carried out, Started. The solution was cooled to 0 ° C. and a solution of 44.2 g (0.2 mol) of 100 g of N-methyl-2-pyrrolidone in 3-aminopropyltriethoxysilane 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 the carboxyl group-containing organosilicon compound S-2. The structure of S-2 is shown below.

[Formula 22]

(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 the carboxyl group-containing organosilicon compound S-1 prepared above (2 parts by mass as S-1 pure fraction) and a carboxyl group-containing organosilicon compound solution 5 mass parts (1 mass part as S-2 pure parts) of 20% NMP solution of S-2 was weighed-mixed, respectively, and it filtered with the filter made from Teflon (trademark) of 0.2 micron of pore diameters, and varnish-shaped photosensitive polyol Ganosiloxane composition C-18 was obtained.

Example 15

(Preparation of photosensitive polyorganosiloxane composition C-19)

In addition to the composition of Example 1, the following formula:

[Formula 23]

0.4 parts by mass of the nonionic surfactant (trade name, PolyFox Part No. PF-656 manufactured by OMNOVA Solutions) was weighed and mixed with a filter made of Teflon (registered trademark) having a pore diameter of 0.2 micron, and a varnish polyorganosiloxane was formed. Composition C-19 was obtained.

(Evaluation of Application (wetting))

A 10% methylethylketone solution (manufactured by Wako Pure Chemical Industries, Ltd.) of poly (methacrylate glycidyl) on a 6-inch silicon wafer using a spin coater (form name Clean Track Mark 7 manufactured by Tokyo Electron) It apply | coated and soft-baked for 10 minutes at 160 degreeC, and obtained the 6-inch silicon wafer in which the organic thin film which consists of poly (methacrylate glycidyl) of 0.8 micron in thickness was formed.

The photosensitive polyorganosiloxane composition C-1, C-17, C-18, C-19 which were obtained by Example 13-15 of this invention and Example 1 as a comparison to this is spin-coated (made by Tokyo Electron Corporation). Applying (spin coat) using the model name Clean Track Mark 7), and using cyclopentanone, edge cut (edge rinse) the width of 3 mm from the wafer edge, and soft bake at 125 ° C for 12 minutes. And a coating film having an initial film thickness of 45 microns was obtained.

The outer periphery of the wafer on which this coating film was formed was observed, and the distance of the coating film outermost circumference was measured from the wafer edge, and the coating property (wetting property) was evaluated (rank "A": 3 mm from the wafer edge and no retreat of the coating film. B ": 3 mm or more and 5 mm or less, and some backwards from a wafer edge Rank" C ": 5 mm or more backward from a wafer edge). The results are shown in Table 3 below.

Applicability (wetting) evaluation Example 13 A Example 14 A Example 15 A Comparison: Example 1 B

In Examples 13-15 of this invention, the photosensitive polyorganosiloxane composition excellent in the coatability (wetting property) on a base material can be obtained more than the Example 1 of this invention compared.

In this regard, evaluation of the tackiness, photosensitive characteristics, low temperature curing characteristics, low volatility, and volume shrinkage of the prebaked films of Examples 13 to 15 was equivalent to that of Example 1.

Industrial availability

The photosensitive polyorganosiloxane composition of this invention is a semiconductor in which the image sensor, the micromachine, or the micro actuator were mounted in formation of the surface protection film, interlayer insulation film, (alpha) -ray shielding film, etc. in the insulating material of an electronic component or a semiconductor device. It can use suitably as a resin composition used for the apparatus etc. and its formation.

Claims (19)

A photosensitive polyorganosiloxane composition containing the following (a) component and (b) component:
(a) 100 parts by mass of polyorganosiloxane, wherein the polyorganosiloxane is represented by the following general formula (1):
[Formula 1]

At least 1 type of silanol compound represented by {in formula, R is a C6-C18 monovalent group containing one aromatic group at least, and may all be same or different}, General formula (2) below:
(2)

{In formula, R 'is a C2-C11 organic group which has the 5-6-membered nitrogen atom containing heterocyclic group which does not contain a photopolymerizable carbon-carbon double bond, including the thing which does not have aromaticity, And R '' is a methyl group or an ethyl group, all of which may be the same or different} and at least one alkoxysilane compound represented by the following general formula (3):
(3)

(Wherein R '''is a C2-C17 organic group containing a photopolymerizable carbon-carbon double bond group, and R''''is a methyl group or an ethyl group, all of which may be the same or different} At least one alkoxysilane compound is represented by the following general formula (4):
[Chemical Formula 4]

A metal alkoxide represented by {wherein M is any one of silicon, germanium, titanium or zirconium, and R '''''is an alkyl group having 1 to 4 carbon atoms and may be the same or different} (5):
[Chemical Formula 5]

Consisting of a metal alkoxide represented by {wherein M 'is boron or aluminum, and R''''''is an alkyl group having 1 to 4 carbon atoms and may be the same or different} and Ba (OH) ₂ It is obtained by mixing with at least one catalyst selected from the group and polymerizing without adding water, wherein the silanol compound represented by the general formula (1) versus the alkoxysilane compound represented by the general formula (2) and the general formula (3) The molar ratio of the sum total of the alkoxysilane compound represented by) is 50: 30-50: 70, and the molar ratio of the alkoxysilane compound represented by General formula (2) to the alkoxysilane compound represented by General formula (3) is 70: 30-30 Is 70,
(b) 0.1-20 mass parts of photoinitiators. The method of claim 1,
(c) Photosensitive polyorganosiloxane composition which contains 1-100 mass parts of compounds other than the (a) component which has two or more photopolymerizable unsaturated bond groups further with respect to (a) component. The method of claim 1,
(d) Silicone resins other than (a) component which show the three-dimensional network structure obtained by co-hydrolyzing and superposing | polymerizing the organosilane compound which has 2-4 hydrolyzable groups, 50-50 with respect to (a) component The photosensitive polyorganosiloxane composition further contains 200 mass parts. The method according to any one of claims 1 to 3,
The photosensitive polyorganosiloxane composition whose said catalyst is at least 1 metal alkoxide selected from the group which consists of a metal alkoxide represented by General formula (4), and a metal alkoxide represented by General formula (5). The method according to any one of claims 1 to 3,
The catalyst consists of 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 , potassium hydroxide, and sodium hydroxide. A photosensitive polyorganosiloxane composition which is a mixture of at least one catalyst selected from the group. The method according to any one of claims 1 to 3,
(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- At least selected from the group consisting of 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 in the left is an epoxy group). The photosensitive polyorganosiloxane composition which further contains 1 or more types of organosilicon compounds at 0.1-20 mass parts with respect to (a) component. The method according to any one of claims 1 to 3,
(f) The photosensitive polyorganosiloxane composition which further contains the polyhydric thiol compound containing at least 2 or more thiol groups in 1-50 mass parts with respect to (a) component. The method according to claim 1 or 2,
(g) the following general formula (6):
[Formula 6]

{Wherein h is an integer of 1 or 2, when h is 1, Xa is a divalent aromatic group, when h is 2, Xa is a tetravalent aromatic group and Xc is a carbon directly bonded to a silicon atom A divalent organic group containing an atom, d is an integer of 1-3, Re and Rf are a C1-C4 alkyl group, may be same or different, g is 0, 1 or 2, Rb is hydrogen A photosensitive polyorganosiloxane composition which further contains the carboxyl group-containing organosilicon compound shown to the atom or monovalent hydrocarbon group at 0.05-20 mass parts with respect to (a) component. The method according to any one of claims 1 to 3,
(h) The photosensitive polyorganosiloxane composition which further contains a nonionic surfactant at 0.01-10 mass parts with respect to (a) component. A method for forming a polyorganosiloxane film, comprising the step of applying the photosensitive polyorganosiloxane composition according to any one of claims 1 to 3 on a substrate. The polyorganosiloxane cured film obtained by hardening | curing the polyorganosiloxane film obtained by the method of Claim 10 by irradiating or heating an actinic light. A step of forming a polyorganosiloxane film on a substrate by the method according to claim 10, a step of irradiating the film with active rays through a patterning mask to photocuring the exposed portion, and removing the uncured portion of the film using a developer. And a method for forming a polyorganosiloxane cured relief pattern, which includes a step of heating and a step of heating each substrate. The polyorganosiloxane hardening relief pattern obtained by the method of Claim 12. The semiconductor device containing the polyorganosiloxane cured film of Claim 11. The semiconductor device containing the polyorganosiloxane hardening relief pattern of Claim 12. A semiconductor device having 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, wherein the spacer material is a twelfth embodiment. The semiconductor device which is a polyorganosiloxane hardening relief pattern of Claim. 17. The method of claim 16,
A semiconductor device in which the integrated circuit comprises a photodiode. 17. The method of claim 16,
A semiconductor device wherein the microstructure is a micro lens. Forming a polyorganosiloxane film directly on the microstructure or via a thin film layer; irradiating the active light to the film via a patterning mask to photocuring the exposed portion; removing the uncured portion of the film using a developer The method of manufacturing the semiconductor device according to claim 16, which includes a step and a step of heating each substrate.