WO2019059398A1 - Method for producing polysiloxane having excellent storage stability - Google Patents

Abstract

[Problem] To provide: a production method which improves storage stability of a hydrogenated polysiloxane that has high heat resistance, insulating properties and etching resistance; and a hydrogenated polysiloxane composition which exhibits improved planarization properties in the form of a coating film due to the improved storage stability. [Solution] A compound for capping a silanol group of a polysiloxane, which has a structure represented by formula (1). (In formula (1), R1 represents an alkyl group or an aryl group; R2 represents an alkoxy group; and a represents an integer of 1 or 2.) A method for producing a polysiloxane, which comprises: a first step for obtaining a hydrolysis-condensation product of a hydrolyzable silane; and a second step for capping a silanol group in the hydrolysis-condensation product with use of the compound represented by formula (1). The hydrolyzable silane used in the first step includes a hydrolyzable silane represented by formula (2). (In formula (2), R3 represents a hydrogen atom.)

Description

Method for producing polysiloxane excellent in storage stability

The present invention relates to a method for producing hydrogenated polysiloxane having excellent storage stability, which is used in a lithography process of semiconductor production.

Conventionally, in the manufacture of a semiconductor device, fine processing by lithography using a photoresist has been performed. The fine processing is obtained by forming a thin film of photoresist on a semiconductor substrate such as a silicon wafer, and irradiating and developing active light such as ultraviolet light through a mask pattern on which the pattern of the semiconductor device is drawn. By etching the substrate using the photoresist pattern as a protective film, fine irregularities corresponding to the pattern are formed on the surface of the substrate. However, in recent years, the degree of integration of semiconductor devices has been increased, and active light rays used also tend to be shortened in wavelength from a KrF excimer laser (248 nm) to an ArF excimer laser (193 nm). Along with this, the influence of reflection of active light from the semiconductor substrate has become a major problem.

In addition, as a lower layer film between a semiconductor substrate and a photoresist, a film known as a hard mask containing a metal element such as silicon or titanium has been used. In this case, since the components of the resist and the hard mask are largely different from each other, the removal rate thereof by the dry etching largely depends on the gas species used for the dry etching. Then, by appropriately selecting the gas type, it is possible to remove the hard mask by dry etching without accompanied by a large decrease in the film thickness of the photoresist. As described above, in recent semiconductor device manufacturing, a resist underlayer film has been disposed between a semiconductor substrate and a photoresist in order to achieve various effects including the antireflection effect. Then, although a composition for a resist underlayer film has been studied up to now, development of a new material for a resist underlayer film is desired from the diversity of required characteristics and the like.

It is considered to improve the silicon content in the polysiloxane in order to improve the dry etching resistance. Since the complete polysiloxane which does not contain an organic component has a subject in a coating physical property etc., the polysiloxane containing an organic group is used. The silicon content in the polysiloxane can be improved by forming a hydrogenated polysiloxane in which part or all of the organic groups in the polysiloxane are replaced by hydrogen atoms.

Patent documents 1 to 6 can be cited as the hydrogenated polysiloxane.

There is a method of protecting the hydroxyl group of an organic compound containing polysiloxane with a ketalizing agent (see Patent Document 7).

JP 7-097548 JP-A-9-137121 JP-A-11-251310 Patent document 1: JP-A-2001-131479 Patent document 1: JP-A-2005-187657 Japanese Patent Application Laid-Open No. 2010-151923 International Publication WO2012 / 165235 Pamphlet

The present invention provides a method for producing a hydrogenated polysiloxane having high heat resistance, insulation, and etching resistance with improved storage stability, and improves the storage stability to planarize a coated film. It is an object of the present invention to provide a hydrogenated polysiloxane composition having improved properties.

According to a first aspect of the present invention, there is provided a compound for capping silanol groups of a polysiloxane, which is represented by the formula (1):

(In the formula (1), R ¹ represents an alkyl group or an aryl group, R ² represents an alkoxy group, and a represents an integer of 1 to 2.) the above compound having a structure represented by

As a second aspect, capping the silanol group in the hydrolytic condensate with the first step of obtaining a hydrolytic condensate of hydrolyzable silane and the compound represented by the formula (1) described in the first aspect A method of producing a polysiloxane comprising the second step of

As a third aspect, the hydrolyzable silane used in the first step has the following formula (2):

(In the formula (2), R ³ represents a hydrogen atom and represents a bond to a silicon atom through a Si—H bond, R ⁴ represents an alkoxy group, an acyloxy group or a halogen atom, b is 1 The method for producing a polysiloxane according to the second aspect, comprising a hydrolyzable silane represented by the following integer:

As a fourth aspect, the hydrolyzable silane used in the first step is a combination of the hydrolyzable silane represented by the above formula (2) and another hydrolyzable silane, and the other hydrolyzable silanes are formulas (3):

(In formula (3), R ⁵ represents an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkoxyaryl group, an alkenyl group, or an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group or a cyano group R ⁶ represents an alkoxy group, an acyloxy group, or a halogen atom, and c represents an integer of 1 to 2). Hydrolyzable silanes represented, and Formula (4):

(In the formula (4), R ⁷ represents an alkyl group and is bonded to a silicon atom by a Si—C bond, R ⁸ represents an alkoxy group, an acyloxy group or a halogen atom, and Y represents an alkylene group or And at least one hydrolyzable silane selected from the group consisting of hydrolyzable silanes represented by arylene group, d represents an integer of 0 or 1, and e represents an integer of 0 or 1. Yes,
The method for producing a polysiloxane according to the second or third aspect, wherein the hydrolyzable silane represented by the above formula (2) and the other hydrolyzable silane are present in a molar ratio of 100: 0 to 90:10,

As a fifth aspect, in the first step, the hydrolyzable silane represented by Formula (2) or the hydrolyzable silane represented by Formula (2) and other hydrolyzable silanes are hydrolyzed with an acid catalyst, The method for producing a polysiloxane according to any one of the second to fourth aspects, wherein a decomposition condensate is obtained,

As a sixth aspect, in the first step, the hydrolyzable silane represented by Formula (2) or the hydrolyzable silane represented by Formula (2) and other hydrolysable silanes are hydrolyzed to form a hydrolytic condensate Described in any one of the second to fifth aspects in which the silanol group in the hydrolytic condensate is capped with the compound of the formula (1) described in the first aspect under an acid catalyst in the second step Method of producing polysiloxane,

As a seventh aspect, in the first step, the hydrolyzable silane represented by the formula (2) or the hydrolyzable silane represented by the formula (2) and other hydrolysable silanes are hydrolyzed with an acid, and the hydrolysis is performed. The decomposition product is condensed to obtain a solution of a hydrolysis condensate, and the acid remaining in the solution of the hydrolysis condensate in the second step is used as a catalyst to describe the silanol group in the hydrolysis condensate as the first aspect The method for producing a polysiloxane according to any one of the second aspect to the fifth aspect, wherein the capping is carried out with the compound of the formula (1) of

As an eighth aspect, in any one of the second aspect to the seventh aspect, the above-mentioned polysiloxane is a polysiloxane used for a composition for forming a planarizing film used for planarizing a substrate including a level difference. Process for producing the described polysiloxane, and

According to a ninth aspect, the above-mentioned polysiloxane is a polysiloxane used for a composition for forming an intermediate film used as a hard mask between a resist and an organic film in a lithography process by a multilayer resist method. It is a manufacturing method of the polysiloxane as described in any one of 7 viewpoints.

In the polysiloxane material, when silanol groups remain, condensation between silanol groups occurs, increasing the molecular weight and decreasing the stability. By capping the silanol groups of the polysiloxane, it is possible to prevent the molecular weight from increasing and destabilizing due to the condensation of the silanol groups.

However, when the silanol group capping material uses alcohol, water may be generated by the capping, and the capped portion may return to the silanol group again.

The capping agent according to the present invention capping the silanol group by using a capping agent having a plurality of (for example, 2 to 3) alkoxy groups in the molecule such as 2,2-dimethoxypropane and trimethyl orthoacetate for capping the silanol group. The product is a polysiloxane containing a capped silanol group, a ketone or ester, and an alcohol, and no water is by-produced. Thus, the capped moiety does not revert to silanol groups.

A method for producing a hydrogenated polysiloxane having high heat resistance, insulation and etching resistance with improved storage stability, and the obtained polysiloxane is excellent in storage stability, so the molecular weight of the polymer during storage There is no change over time. Therefore, even when used as a component of the coating composition for planarizing the substrate having the unevenness, the change in molecular weight of the polymer is small, so that the coating composition can have high planarization.

The present invention is a compound for capping silanol groups of polysiloxane, and is the above-mentioned compound having a structure represented by the formula (1).

Then, a first step of obtaining a hydrolytic condensate of a hydrolyzable silane, and a second step of capping the silanol group in the hydrolytic condensate using the compound represented by the formula (1) A method of producing a polysiloxane comprising Here, the polysiloxane is one obtained by capping a part or all of the silanol groups of the hydrolytic condensate with the compound represented by the formula (1). The capping forms the alkoxysilane structure (Si-OR ² ) with an alkoxy group derived from R ² of formula (1).

The capping ratio can be, for example, 10 to 100 mol%, 30 to 100 mol%, 50 to 90 mol%, or 50 to 80 mol% with respect to the silanol group to be generated.

The capping of the silanol groups of the polysiloxane with the compound of the formula (1) is carried out in a solvent in the presence of an acid catalyst. For example, using a solvent used for hydrolysis and condensation of hydrolyzable silane, capping with a compound represented by formula (1), and using an acid catalyst used for hydrolysis at that time as an acid catalyst for capping can do. Capping may be performed at a temperature within room temperature to 100 ° C., for example, a temperature from room temperature to 80 ° C., or 50 to 70 ° C.

In formula (1), R ¹ represents an alkyl group or an aryl group, R ² represents an alkoxy group, and a represents an integer of 1 to 2. The alkoxy group of R ² is particularly preferably a methoxy group, an ethoxy group or the like.

The hydrolyzable silane used in the first step can include a hydrolyzable silane represented by the following formula (2).

In formula (2), R ³ represents a hydrogen atom and represents a bond to a silicon atom through a Si—H bond, R ⁴ represents an alkoxy group, an acyloxy group or a halogen atom, and b is 1 to Indicates an integer of 2.

In addition, the hydrolyzable silane used in the first step is a combination of the hydrolyzable silane represented by the above formula (2) and other hydrolyzable silanes, and the other hydrolyzable silanes are the formula (3) And at least one hydrolyzable silane selected from the group consisting of hydrolyzable silanes represented by formula (4), and hydrolyzate represented by formula (2) above. Degradable silanes and other hydrolyzable silanes can be present in a molar ratio of 100: 0 to 90:10.

In formula (3), R ⁵ has an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkoxyaryl group, an alkenyl group, or an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group or a cyano group An organic group is shown, and one bonded to a silicon atom by a Si—C bond is shown, R ⁶ is an alkoxy group, an acyloxy group or a halogen atom, and c is an integer of 1 to 2.

In formula (4), R ⁷ represents an alkyl group and is bonded to a silicon atom by a Si-C bond, R ⁸ represents an alkoxy group, an acyloxy group or a halogen atom, and Y is an alkylene group or arylene Group represents, d represents an integer of 0 or 1, and e represents an integer of 0 or 1.

The alkyl group used in Formula (1), Formula (2), Formula (3), and Formula (4) is a linear or branched alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group and an ethyl group. Group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl- n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl -N-propyl group, n-hexyl, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1- Dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n- Ethyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n -Butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl and 1-ethyl-2-methyl And -n-propyl and the like.

A cyclic alkyl group can also be used, and examples of the cyclic alkyl group having 1 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, and a cyclopentyl group 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2 -Ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group Group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group Group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2- n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group Group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group and Examples include 2-ethyl-3-methyl-cyclopropyl group and the like. A bicyclo group can also be used.

The alkenyl group is an alkenyl group having a carbon number of 2 to 10, and ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group Group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2- Pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2 -Ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2- The Group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2 group -Propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl -1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2 -Methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3 Methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group Group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-ene Butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-s-butylethenyl, 1,3-dimethyl -1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3- Dimethyl-1-butenyl group, 2,3-dimethy group -2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1 -Ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2- Ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1 -Ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1-i-propyl-2-propenyl group, 1-methyl -2-cyclopentenyl group, 1-methyl 2-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2- Methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4 And -cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group and the like.

Examples of the aryl group include aryl groups having 6 to 40 carbon atoms, such as phenyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, o-chlorophenyl group, m-chlorophenyl group, p-Chlorophenyl group, o-fluorophenyl group, p-mercaptophenyl group, o-methoxyphenyl group, p-methoxyphenyl group, p-aminophenyl group, p-cyanophenyl group, α-naphthyl group, β-naphthyl group Group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group Groups and 9-phenanthryl groups.

Examples of the organic group having an epoxy group include glycidoxymethyl, glycidoxyethyl, glycidoxypropyl, glycidoxybutyl, epoxycyclohexyl and the like.

Acryloyl methyl, acryloyl ethyl, acryloyl propyl etc. are mentioned as an organic group which has an acryloyl group.

Examples of the organic group having a methacryloyl group include methacryloyl methyl, methacryloyl ethyl, methacryloyl propyl and the like.

Examples of the organic group having a mercapto group include ethyl mercapto, butyl mercapto, hexyl mercapto, octyl mercapto and the like.

Examples of the organic group having an amino group include an amino group, an aminomethyl group and an aminoethyl group.

Examples of the organic group having a cyano group include cyanoethyl, cyanopropyl and the like.

The alkoxyalkyl group is an alkyl group substituted with an alkoxy group, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group and an ethoxyethyl group.

The alkoxy group includes an alkoxy group having a linear, branched or cyclic alkyl moiety having 1 to 20 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group and an n-butoxy group. , I-butoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1, 1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n group -Pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1 -Ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl group -N-propoxy group and 1-ethyl-2-methyl-n-propoxy group etc., and as a cyclic alkoxy group, cyclopropoxy group, cyclobutoxy group, 1-methyl-cyclopropoxy group, 2-methyl-cyclopropoxy group Group, cyclopentyloxy group, 1-methyl-cyclobutoxy group, 2-methyl-cyclobutoxy group, 3-methyl-cyclobutoxy group, 1,2-dimethyl-cyclopropoxy group, 2,3-dimethyone -Cyclopropoxy group, 1-ethyl-cyclopropoxy group, 2-ethyl-cyclopropoxy group, cyclohexyloxy group, 1-methyl-cyclopentyloxy group, 2-methyl-cyclopentyloxy group, 3-methyl-cyclopentyloxy group Group, 1-ethyl-cyclobutoxy group, 2-ethyl-cyclobutoxy group, 3-ethyl-cyclobutoxy group, 1,2-dimethyl-cyclobutoxy group, 1,3-dimethyl-cyclobutoxy group, 2, 2- Dimethyl-cyclobutoxy group, 2,3-dimethyl-cyclobutoxy group, 2,4-dimethyl-cyclobutoxy group, 3,3-dimethyl-cyclobutoxy group, 1-n-propyl-cyclopropoxy group, 2-n- Propyl-cyclopropoxy group, 1-i-propyl-cyclopropoxy group, 2-i-propyl-cyclopropoxy group, 1,2, 2-trimethyl-cyclopropoxy group, 1,2,3-trimethyl-cyclopropoxy group, 2,2,3-trimethyl-cyclopropoxy group, 1-ethyl-2-methyl-cyclopropoxy group, 2-ethyl-1-yl Examples include methyl-cyclopropoxy group, 2-ethyl-2-methyl-cyclopropoxy group and 2-ethyl-3-methyl-cyclopropoxy group.

The above acyloxy group is, for example, methyl carbonyloxy group, ethyl carbonyloxy group, n-propyl carbonyloxy group, i-propyl carbonyloxy group, n-butyl carbonyloxy group, i-butyl carbonyloxy group, s-butyl carbonyloxy group , T-butylcarbonyloxy group, n-pentylcarbonyloxy group, 1-methyl-n-butylcarbonyloxy group, 2-methyl-n-butylcarbonyloxy group, 3-methyl-n-butylcarbonyloxy group, 1, 1-dimethyl-n-propylcarbonyloxy group, 1,2-dimethyl-n-propylcarbonyloxy group, 2,2-dimethyl-n-propylcarbonyloxy group, 1-ethyl-n-propylcarbonyloxy group, n- Hexyl carbonyloxy group, 1-methyl-n-pentyl Rubonyloxy group, 2-methyl-n-pentylcarbonyloxy group, 3-methyl-n-pentylcarbonyloxy group, 4-methyl-n-pentylcarbonyloxy group, 1,1-dimethyl-n-butylcarbonyloxy group, 1,2-Dimethyl-n-butylcarbonyloxy group, 1,3-dimethyl-n-butylcarbonyloxy group, 2,2-dimethyl-n-butylcarbonyloxy group, 2,3-dimethyl-n-butylcarbonyloxy Group, 3,3-dimethyl-n-butylcarbonyloxy group, 1-ethyl-n-butylcarbonyloxy group, 2-ethyl-n-butylcarbonyloxy group, 1,1,2-trimethyl-n-propylcarbonyloxy group Group, 1,2,2-trimethyl-n-propylcarbonyloxy group, 1-ethyl-1-methyl-n-propylcarbonyl group Oxy group, 1-ethyl-2-methyl -n- propyl carbonyl group, phenylcarbonyl group, and the like tosyl carbonyloxy group.

As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned.

As a compound of Formula (1), it can illustrate below.

The hydrolyzable silane of Formula (2) can be illustrated, for example below.

The hydrolyzable silane of the formula (3) is, for example, tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, methyltrimethoxysilane, Methyltrichlorosilane, Methyltriacetoxysilane, Methyltripropoxysilane, Methyltriacetoxysilane, Methyltributoxysilane, Methyltriamyloxysilane, Methyltriphenoxysilane, Methyltribenzyloxysilane, Methyltriphenethyloxysilane, Glycide Xymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethylene Trimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyl Triethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyl Triphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyl Triethoxysilane, δ- Glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4 (3,4) -Epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyl Tributoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, δ -(3, 4-D Xycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxy Silane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-g Cidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyl diethoxysilane Γ-Glycidoxypropylvinyldimethoxysilane, γ-Glycidoxypropylvinyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltriethoxysilane , Methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane, Toxibenzyltriethoxysilane, methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane, methoxyphenethyl trimethoxysilane, methoxyphenethyl triethoxysilane, methoxyphenethyl triacetoxysilane, methoxyphenethyl trichlorosilane, ethoxyphenyltrimethoxysilane, ethoxyphenyltriethoxy Silane, ethoxyphenyltriacetoxysilane, ethoxyphenyltrichlorosilane, ethoxybenzyltrimethoxysilane, ethoxybenzyltriethoxysilane, ethoxybenzyltriacetoxysilane, ethoxybenzyltrichlorosilane, isopropoxyphenyltrimethoxysilane, isopropoxyphenyltriethoxysilane, Isopropoxyphenyl triacetoxy Orchid, isopropoxyphenyltrichlorosilane, isopropoxybenzyltrimethoxysilane, isopropoxybenzyltriethoxysilane, isopropoxybenzyltriacetoxysilane, isopropoxybenzyltrichlorosilane, t-butoxyphenyltrimethoxysilane, t-butoxyphenyltriethoxysilane T-Butoxyphenyltriacetoxysilane, t-butoxyphenyltrichlorosilane, t-butoxybenzyltrimethoxysilane, t-butoxybenzyltriethoxysilane, t-butoxybenzyltriacetoxysilane, t-butoxybenzyltrichlorosilane, methoxynaphthyltrichlorosilane Methoxysilane, methoxynaphthyl triethoxysilane, methoxynaphthyl triacetoxysilane, methoxynaphthyl tri Lolosilane, ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane, ethoxynaphthyltriacetoxysilane, ethoxynaphthyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3 3, 3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, chloromethyltrimethoxysilane Chloromethyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, -Chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ- Mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane and the like can be mentioned.

The hydrolyzable silanes of the formula (4) are, for example, methylenebistrimethoxysilane, methylenebistrichlorosilane, methylenebistriacetoxysilane, ethylenebistriethoxysilane, ethylenebistrichlorosilane, ethylenebistrichlorosilane, ethylenebistriacetoxysilane, propylenebistriethoxysilane, butylenebistrimethoxysilane, Phenylenebistrimethoxysilane, phenylenebistriethoxysilane, phenylenebismethyldiethoxysilane, phenylenebismethyldimethoxysilane, naphthalenebistrimethoxysilane, bistrimethoxydisilane, bistriethoxydisilane, bisethyldiethoxydisilane, bismethyldimethoxydisilane, etc. Be

Specific examples of the hydrolytic condensate (polysiloxane) used in the present invention are exemplified below.

The hydrolytic condensate (polyorganosiloxane) of the above hydrolyzable silane can obtain a condensate having a weight average molecular weight of 1000 to 1,000,000, or 1,000 to 100,000. These molecular weights are molecular weights obtained by polystyrene conversion by GPC analysis.

The measurement conditions of GPC are, for example, GPC apparatus (trade name: HLC-8220GPC, manufactured by Tosoh Corp.), GPC column (trade name: Shodex KF803L, KF802, KF801, manufactured by Showa Denko), column temperature is 40 ° C., eluent (eluting solvent) Can be carried out using tetrahydrofuran, a flow rate (flow rate) of 1.0 ml / min, and a standard sample of polystyrene (manufactured by Showa Denko KK).

For hydrolysis of the alkoxysilyl group, the acyloxysilyl group or the halogenated silyl group, 0.5 to 100 moles, preferably 1 to 10 moles of water are used per mole of the hydrolyzable group.

In addition, 0.001 to 10 moles, preferably 0.001 to 1 mole of a hydrolysis catalyst can be used per mole of the hydrolysable group.

The reaction temperature at the time of carrying out hydrolysis and condensation is usually 20 to 80.degree.

The hydrolysis may be complete hydrolysis or partial hydrolysis. That is, the hydrolyzate or monomer may remain in the hydrolytic condensate.

A catalyst can be used when hydrolyzing and condensing.

An acid can be used as a hydrolysis catalyst.

Organic acids as hydrolysis catalysts are, for example, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, maleic acid, methyl malonic acid, adipic acid, sebacine Acid, gallic acid, butyric acid, butyric acid, mellitic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzene sulfone Acids, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like can be mentioned.

Examples of the inorganic acid as a hydrolysis catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like.

As an organic solvent used for hydrolysis, for example, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i- Aliphatic hydrocarbon solvents such as octane, cyclohexane and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, Aromatic hydrocarbon solvents such as -i-propylbenzene, n-amylnaphthalene and trimethylbenzene; acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl- Pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, phen Ketone solvents such as Chon et al .; diethyl ether, di-propyl ether, di n-butyl ether, di n-hexyl ether, diisoamyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyl ester Dioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-b Ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether , Diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxy triglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl The Ether, such as propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, and 2-methyltetrahydrofuran Solvents: diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, Sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethyl butyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclo acetate Hexyl, methyl acetate cyclohexyl, methyl n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate Propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetate, Propylene glycol monobutyl ether acetate, Dipropylene glycol monomethyl ether acetate, Dipropylene glycol monomethyl ether acetate, Dipropylene glycol monoethyl ether acetate, Glycos diacetate, Methoxy triglycol acetate , Ethyl propionate, n-Buty Propionate Esters such as i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate and diethyl phthalate Solvents: Nitrogen-containing systems such as N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone and the like Solvents: Sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, 1,3-propane sultone and the like can be mentioned. These solvents can be used alone or in combination of two or more.

In particular, ether solvents such as diisoamyl ether and dibutyl ether are preferable.

The composition containing the polysiloxane obtained by the present invention can contain a curing catalyst.

Ammonium salts, phosphines, phosphonium salts and sulfonium salts can be used as curing catalysts.

As the ammonium salt, a compound represented by formula (D-1):

(Wherein, m is an integer of 2 to 11, n is an integer of 2 to 3, R ²¹ is an alkyl group or an aryl group, and Y − represents an anion), a quaternary ammonium salt having a structure represented by
Formula (D-2):

(Wherein R ²² , R ²³ , R ²⁴ and R ²⁵ represent an alkyl group or an aryl group, N represents a nitrogen atom, Y ^- represents an anion, and R ²² , R ²³ , R ²⁴ and R ²⁵ represent A quaternary ammonium salt having a structure shown by each of the CN bonds to a nitrogen atom
Formula (D-3):

(Wherein R ²⁶ and R ^{27 each} represents an alkyl group or an aryl group, and Y ^- represents an anion), a quaternary ammonium salt,
Formula (D-4):

(Wherein R ²⁸ represents an alkyl group or an aryl group, and Y ^- represents an anion), a quaternary ammonium salt,
Formula (D-5):

(Wherein R ²⁹ and R ^{30 each} represents an alkyl group or an aryl group, and Y ^- represents an anion), a quaternary ammonium salt having a structure of
Formula (D-6):

(Wherein, m is an integer of 2 to 11, n is an integer of 2 to 3, H is a hydrogen atom, and Y ^- represents an anion).

Moreover, as a phosphonium salt, Formula (D-7):

(Wherein R ³¹ , R ³² , R ³³ , and R ³⁴ are an alkyl group or an aryl group, P is a phosphorus atom, Y ^- is an anion, and R ³¹ , R ³² , R ³³ , and R ³⁴ Are each bonded to a phosphorus atom via a C—P bond.

Moreover, as a sulfonium salt, Formula (D-8):

(Wherein R ³⁵ , R ³⁶ and R ³⁷ represent an alkyl or aryl group, S represents a sulfur atom, Y ^- represents an anion, and R ³⁵ , R ³⁶ and R ³⁷ each represent a C—S bond Are attached to the sulfur atom), and the tertiary sulfonium salt is raised.

The compound of the above formula (D-1) is a quaternary ammonium salt derived from an amine, m is an integer of 2 to 11, and n is an integer of 2 to 3. R ²¹ of this quaternary ammonium salt represents an alkyl or aryl group having 1 to 18 carbon atoms, preferably 2 to 10 carbon atoms, and includes, for example, linear alkyl groups such as ethyl, propyl and butyl, and benzyl And cyclohexyl group, cyclohexylmethyl group, dicyclopentadienyl group and the like. The anion (Y ^-), chlorine ion (Cl ^-), bromine ion (Br ^{-) -} or a halogen ion such as, carboxylate (-COO ^-), iodide ion (I), sulfonato (-SO ₃ ^-) , alcoholate (-O ^-) can be mentioned an acid group and the like.

The compound of the above formula (D-2) is a quaternary ammonium salt represented by R ²² R ²³ R ²⁴ R ²⁵ N ⁺ Y ⁻ . R ²² , R ²³ , R ²⁴ and R ²⁵ of this quaternary ammonium salt are an alkyl group having 1 to 18 carbon atoms or an aryl group, or a silane compound bonded to a silicon atom through a Si—C bond. Anion (Y ^-), chlorine ion (Cl ^-), bromine ion (Br ^{-) -} or a halogen ion such as, carboxylate (-COO ^-), iodide ion (I), sulfonato _(-SO ³ -), alcoholate (-O ^-) can be mentioned an acid group and the like. The quaternary ammonium salt is commercially available, and examples thereof include tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride and tributylbenzyl chloride. Ammonium, trimethylbenzylammonium chloride and the like are exemplified.

The compound of the above-mentioned formula (D-3) is a quaternary ammonium salt derived from 1-substituted imidazole, and R ²⁶ and R ²⁷ have 1 to 18 carbon atoms, and R ²⁶ and R ²⁷ have carbon atoms It is preferable that the sum total of is 7 or more. For example, R ²⁶ can be exemplified by methyl, ethyl, propyl, phenyl and benzyl, and R ²⁷ can be exemplified by benzyl, octyl and octadecyl. Anion (Y ^-), chlorine ion (Cl ^-), bromine ion (Br ^{-) -} or a halogen ion such as, carboxylate (-COO ^-), iodide ion (I), sulfonato _(-SO ³ -), alcoholate (-O ^-) can be mentioned an acid group and the like. Although this compound can be obtained as a commercial product, for example, an imidazole compound such as 1-methylimidazole or 1-benzylimidazole is reacted with an alkyl halide such as benzyl bromide or methyl bromide or an aryl halide. Can be manufactured.

The compound of the above formula (D-4) is a quaternary ammonium salt derived from pyridine, and R ²⁸ is an alkyl or aryl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, For example, butyl, octyl, benzyl and lauryl can be exemplified. Anion (Y ^-), chlorine ion (Cl ^-), bromine ion (Br ^{-) -} or a halogen ion such as, carboxylate (-COO ^-), iodide ion (I), sulfonato _(-SO ³ -), alcoholate (-O ^-) can be mentioned an acid group and the like. Although this compound can be obtained as a commercial product, it is produced, for example, by reacting pyridine with alkyl halide such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, octyl bromide and the like, or aryl halide. You can do it. Examples of this compound include N-laurylpyridinium chloride, N-benzylpyridinium bromide and the like.

The compound of the above formula (D-5) is a quaternary ammonium salt derived from a substituted pyridine represented by picoline and the like, and R ²⁹ is an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms or It is an aryl group, and examples thereof include a methyl group, an octyl group, a lauryl group and a benzyl group. R ³⁰ is an alkyl or aryl group having 1 to 18 carbon atoms. For example, in the case of quaternary ammonium derived from picoline, R ³⁰ is a methyl group. Anion (Y ^-), chlorine ion (Cl ^-), bromine ion (Br ^{-) -} or a halogen ion such as, carboxylate (-COO ^-), iodide ion (I), sulfonato _(-SO ³ -), alcoholate (-O ^-) can be mentioned an acid group and the like. Although this compound can be obtained as a commercial product, for example, reaction of substituted pyridine such as picoline with alkyl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, benzyl bromide or aryl halide It can be manufactured. Examples of this compound include N-benzylpicolinium chloride, N-benzylpicolinium bromide, N-laurylpicolinium chloride and the like.

The compound of the above formula (D-6) is a tertiary ammonium salt derived from an amine, m is an integer of 2 to 11 and n is an integer of 2 to 3. The anion (Y ^-), chlorine ion (Cl ^-), bromine ion (Br ^{-) -} or a halogen ion such as, carboxylate (-COO ^-), iodide ion (I), sulfonato (-SO ₃ ^-) , alcoholate (-O ^-) can be mentioned an acid group and the like. It can be produced by the reaction of an amine and a weak acid such as a carboxylic acid or phenol. As the carboxylic acid include formic acid and acetic acid, in the case of using formic acid, the anion (Y ^{-) -,} and the case of using acetic acid, the anion (HCOO) (Y ^-) is _(CH 3 COO ^- ) If phenol is used also, the anion (Y ^{-) -} a _{(C 6 H} 5 O).

The compound of the above formula (D-7) is a quaternary phosphonium salt having a structure of R ³¹ R ³² R ³³ R ³⁴ P ⁺ Y ⁻ . R ³¹ , R ³² , R ³³ and R ^{34 each} represent an alkyl group having 1 to 18 carbon atoms or an aryl group, or a silane compound bonded to a silicon atom through a Si-C bond, preferably R ³¹ to R ^Among the four substituents of ³⁴ , three are a phenyl group or a substituted phenyl group, for example, a phenyl group or a tolyl group can be exemplified, and the remaining one is an alkyl group having 1 to 18 carbon atoms, It is a silane compound bonded to a silicon atom by an aryl group or a Si-C bond. The anion (Y ^-), chlorine ion (Cl ^-), bromine ion (Br ^{-) -} or a halogen ion such as, carboxylate (-COO ^-), iodide ion (I), sulfonato (-SO ₃ ^-) , alcoholate (-O ^-) can be mentioned an acid group and the like. This compound can be obtained as a commercial product, and for example, halogenated trialkylbenzyl such as halogenated tetraalkylphosphonium such as halogenated tetra n-butylphosphonium and halogenated tetra n-propylphosphonium halogenated trialkylbenzyl such as halogenated triethylbenzylphosphonium halogenated Phosphonium, triphenylmethylphosphonium halide, triphenylethylphosphonium halide such as triphenylethylphosphonium halide, triphenylmonoalkylphosphonium halide, triphenylbenzylphosphonium halide, tetraphenylphosphonium halide, tritolyl monoarylphosphonium halide, or tritolyl halide mono The alkyl phosphonium (a halogen atom is a chlorine atom or a bromine atom) is mentioned. In particular, halogens such as triphenylmonophosphorous halides such as triphenylmethylphosphonium halides, triphenylethylphosphonium halides, triphenylmonoarylphosphonium halides such as halogenated triphenylbenzylphosphonium halides, tritolyl monophenylphosphonium halides, etc. A tolylyl monoarylphosphonium halide and a tolylyl monoalkylphosphonium halide (a halogen atom is a chlorine atom or a bromine atom) such as a tolylyl monoarylphosphonium halide or a tolylyl monomethyl phosphonium halide is preferable.

Also, as phosphines, primary phosphines such as methyl phosphine, ethyl phosphine, propyl phosphine, isopropyl phosphine, isobutyl phosphine, phenyl phosphine, etc., dimethyl phosphine, diethyl phosphine, diisopropyl phosphine, diisoamyl phosphine, secondary phosphines such as diphenyl phosphine And tertiary phosphines such as trimethyl phosphine, triethyl phosphine, triphenyl phosphine, methyl diphenyl phosphine, and dimethyl phenyl phosphine.

Compounds of formula (D-8) described ^{above, R 35 R 36 R 37 S} + Y - is a tertiary sulfonium salt having a structure. R ³⁵ , R ³⁶ and R ^{37 each} represent an alkyl group having 1 to 18 carbon atoms or an aryl group, or a silane compound bonded to a silicon atom via a Si—C bond, preferably 4 of R ³⁵ to R ³⁷ Among the three substituents, three may be phenyl or substituted phenyl, such as phenyl and tolyl, and the remaining one may be an alkyl or aryl having 1 to 18 carbon atoms. It is. The anion (Y ^-), chlorine ion (Cl ^-), bromine ion (Br ^{-) -} or a halogen ion such as, carboxylate (-COO ^-), iodide ion (I), sulfonato (-SO ₃ ^-) , alcoholate (-O ^-), maleic acid anion, there can be mentioned an acid group such as a nitrate anion. This compound can be obtained as a commercially available product, and for example, trialkylbenzyl halides such as tri-n-butylsulfonium halide, tetra-alkylsulfonium halides such as tri-n-propylsulfonium halide, and diethylbenzylsulfonium halides Halogenated diphenyl monoalkyl sulfonium such as sulfonium, halogenated diphenylmethyl sulfonium, halogenated diphenylethyl sulfonium, etc., halogenated triphenyl sulfonium, (halogen atom is chlorine atom or bromine atom), tri n-butyl sulfonium carboxylate, tri n- Tetraalkyl phosphonium carboxylates such as propyl sulfonium carboxylate, and trialkyl benzils such as diethyl benzyl sulfonium carboxylate Sulfonium carboxylate, diphenylmethyl sulfonium carboxylate, diphenyl monoalkyl sulfonium carboxylate, triphenylsulfonium carboxylate such as diphenylethyl sulfonium carboxylate. In addition, halogenated triphenylsulfonium and triphenylsulfonium carboxylate can be preferably used.

In the present invention, a nitrogen-containing silane compound can be added as a curing catalyst. Examples of nitrogen-containing silane compounds include imidazole ring-containing silane compounds such as N- (3-triethoxysilylyl) -4,5-dihydroimidazole.

The curing catalyst is 0.01 to 10 parts by mass, 0.01 to 5 parts by mass, or 0.01 to 3 parts by mass with respect to 100 parts by mass of the polyorganosiloxane.

The hydrolyzable silane is hydrolyzed and condensed using a catalyst in a solvent, and the obtained hydrolytic condensate (polymer) simultaneously removes alcohol by-product alcohol and the hydrolysis catalyst used and water by reduced pressure distillation etc. be able to. Moreover, the acid used for hydrolysis can be removed by neutralization or ion exchange. And, in the coating composition containing the polysiloxane of the present invention, the coating composition containing the hydrolysis condensate (polysiloxane) can be added with an organic acid for stabilization.

Examples of the organic acid include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, citric acid, lactic acid, salicylic acid and the like. Among them, oxalic acid, maleic acid and the like are preferable. The amount of the organic acid to be added is 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the condensate (polyorganosiloxane).

In the present invention, a composition containing a polysiloxane can be obtained using the obtained polysiloxane. The composition comprising the polysiloxane can comprise one or more selected from the group consisting of water, an acid, and a curing catalyst.

The composition containing the polysiloxane of the present invention can contain, in addition to the above components, an organic polymer compound, a photoacid generator, a surfactant and the like as required.

By using the organic polymer compound, the dry etching rate (reduction in film thickness per unit time), attenuation coefficient, refractive index, etc. of the resist underlayer film formed from the composition containing the polysiloxane of the present invention is adjusted. be able to.

When a photoacid generator is used, the proportion thereof is 0.01 to 30 parts by mass, 0.01 to 15 parts by mass, or 0.1 to 10 parts by mass with respect to 100 parts by mass of the condensate (polyorganosiloxane). It is 10 parts by mass.

The surfactant is effective in suppressing the occurrence of pinholes, wear and the like when the composition containing the polysiloxane of the present invention is applied to a substrate.

As surfactant contained in the composition containing the polysiloxane of the present invention, for example, polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, etc. , Polyoxyethylene alkyl allyl ethers such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate Fatty acid esters such as sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, etc. Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as bitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. Agent, trade name F-top EF301, EF303, EF352 (made by Tochem Products), trade name Megafac F171, F173, R-08, R-30, R-30N, R-40LM (made by DIC Corporation) Florard FC430, FC431 (Sumitomo 3M Co., Ltd.), trade name Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), etc. Tsu Motokei surfactant, and organosiloxane polymer -KP341 (manufactured by Shin-Etsu Chemical Co.) and the like. These surfactants may be used alone or in combination of two or more. When a surfactant is used, the ratio thereof is 0.0001 to 5 parts by mass, or 0.001 to 1 parts by mass, or 0.01 to 1 parts by mass with respect to 100 parts by mass of the condensate (polyorganosiloxane). It is a mass part.

Moreover, a rheology regulator, an adhesion adjuvant, etc. can be added to the composition containing the polysiloxane of this invention. The rheology modifier is effective to improve the fluidity of the underlayer film forming composition. The adhesion aiding agent is effective to improve the adhesion between the semiconductor substrate or the resist and the underlayer film.

As a solvent used for the composition containing polysiloxane of this invention, if it is a solvent which can melt | dissolve said solid content, it can be used without a restriction | limiting especially. As such solvent, for example, diethyl ether, di-propyl ether, di n-butyl ether, di n-hexyl ether, diisoamyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4 -Methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol Mono-2-ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol Cole monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripro Polyethylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl isobutyl carbinol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monoether ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate Ethyl, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, pyruvate Methyl, ethyl pyruvate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol Monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl Ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate Methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, amyl formate, methyl acetate, ethyl acetate, amyl acetate, amyl acetate, isobutyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propionate Propyl, isopropyl propionate, butyl propionate, isobutyl propionate, dairy Methyl, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, 2-hydroxy-3-methyl Methyl butyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3- Methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptene Tanone, 3-heptanone, 4-heptanone, cyclohexanone, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, 4-methyl-2-pentanol, and γ-butyrolactone Can be mentioned. Ether solvents such as di-n-butyl ether and di-iso-amyl ether can be preferably used. These solvents can be used alone or in combination of two or more.

Hereinafter, the composition containing the polysiloxane of the present invention will be described for use as a resist underlayer film forming composition.

Substrates used for manufacturing semiconductor devices (for example, silicon wafer substrates, silicon / silicon dioxide coated substrates, silicon nitride substrates, glass substrates, ITO substrates, polyimide substrates, and low dielectric constant material (low-k material) coated substrates The resist underlayer film forming composition of the present invention is coated on a etc.) by a suitable coating method such as a spinner or a coater, and thereafter, a resist underlayer film is formed by baking. The firing conditions are appropriately selected from a firing temperature of 80 ° C. to 250 ° C. and a firing time of 0.3 to 60 minutes. Preferably, the firing temperature is 150 ° C. to 250 ° C., and the firing time is 0.5 to 2 minutes. Here, the film thickness of the lower layer film to be formed is, for example, 5 to 1000 nm, 20 to 500 nm, 50 to 300 nm, or 50 to 200 nm.

Then, a layer of photoresist, for example, is formed on the resist underlayer film. The formation of a layer of photoresist can be performed by a known method, that is, application of a photoresist composition solution on an underlying film and baking. The film thickness of the photoresist is, for example, 50 to 10000 nm, or 50 to 2000 nm, or 50 to 1000 nm.

In the present invention, after the organic lower layer film is formed on the substrate, the resist lower layer film of the present invention can be formed thereon, and a photoresist can be further coated thereon. As a result, the pattern width of the photoresist becomes narrow, and even when the photoresist is thinly coated in order to prevent pattern collapse, the substrate can be processed by selecting an appropriate etching gas. For example, it is possible to process the resist underlayer film of the present invention using a fluorine-based gas having a sufficiently high etching rate to the photoresist as an etching gas, and to etch the photoresist underlayer film of the present invention sufficiently fast. The organic lower layer film can be processed using the oxygen-based gas as an etching gas, and the substrate can be processed using a fluorine-based gas having a sufficiently high etching rate to the organic lower layer film as an etching gas.

The photoresist formed on the resist underlayer film of the present invention is not particularly limited as long as it is sensitive to light used for exposure. Both negative and positive photoresists can be used. Positive-working photoresist consisting of novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester, chemically amplified photoresist consisting of a binder having a group which is decomposed by an acid to increase alkali dissolution rate, and a photo-acid generator, acid A chemically amplified photoresist comprising a low molecular weight compound which decomposes to increase the alkali dissolution rate of the photoresist, an alkali soluble binder and a photoacid generator, and a binder having a group which is decomposed by an acid to increase the alkali dissolution rate There is a chemically amplified photoresist comprising a low molecular weight compound which is decomposed by an acid to increase the alkali dissolution rate of the photoresist and a photoacid generator. For example, trade name APEX-E manufactured by Shipley, trade name PAR710 manufactured by Sumitomo Chemical Co., Ltd., trade name SEPR 430 manufactured by Shin-Etsu Chemical Co., Ltd., and the like. Also, for example, Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. Mention may be made of fluorine-containing atomic polymer based photoresists as described in 3999, 365-374 (2000).

Next, exposure is performed through a predetermined mask. For exposure, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 nm), EUV, etc. can be used. After exposure, post exposure bake can also be performed if necessary. Post-exposure heating is performed under conditions appropriately selected from heating temperatures of 70 ° C. to 150 ° C. and heating times of 0.3 to 10 minutes.

In the present invention, a resist for electron beam lithography or a resist for EUV lithography can be used instead of a photoresist as the resist. As the electron beam resist, either negative or positive type can be used. Chemically amplified resist comprising a binder having a group that changes the alkali dissolution rate by being decomposed by an acid generator and an acid, a low molecular weight compound that changes the alkali dissolution rate of the resist by being decomposed by an alkali soluble binder, an acid generator and an acid A chemically amplified resist comprising a acid generator and a binder having a group capable of changing an alkali dissolution rate by an acid generator and an acid, and a chemically amplified resist comprising a low molecular compound capable of changing an alkali dissolution rate of the resist by being decomposed by an acid and an acid There are a non-chemically amplified resist comprising a binder having a group which is decomposed by an electron beam to change an alkali dissolution rate, a non-chemically amplified resist comprising a binder which has a site which is cut by an electron beam to change an alkali dissolution rate. Also in the case of using these electron beam resists, a resist pattern can be formed in the same manner as in the case of using a photoresist with the irradiation source as electron beams.

Further, as the EUV resist, a methacrylate resin based resist, a methacrylate-polyhydroxystyrene hybrid resin based resist, or a polyhydroxystyrene resin based resist can be used. As an EUV resist, either a negative type or a positive type can be used. Chemically amplified resist comprising a binder having a group that changes the alkali dissolution rate by being decomposed by an acid generator and an acid, a low molecular weight compound that changes the alkali dissolution rate of the resist by being decomposed by an alkali soluble binder, an acid generator and an acid A chemically amplified resist comprising a acid generator and a binder having a group capable of changing an alkali dissolution rate by an acid generator and an acid, and a chemically amplified resist comprising a low molecular compound capable of changing an alkali dissolution rate of the resist by being decomposed by an acid and an acid There are a non-chemically amplified resist comprising a binder having a group which is decomposed by EUV light to change the alkali dissolution rate, a non-chemically amplified resist consisting of a binder having a site which is cleaved by EUV light and changes the alkali dissolution rate.

Next, development is performed with a developer (for example, an alkali developer). Thus, for example, when a positive photoresist is used, the photoresist in the exposed portion is removed to form a photoresist pattern.

Examples of the developer include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as choline, ethanolamine, propylamine, An alkaline aqueous solution such as an aqueous amine solution such as ethylene diamine can be mentioned as an example. Furthermore, surfactants and the like can also be added to these developers. The conditions for development are suitably selected from a temperature of 5 to 50 ° C. and a time of 10 to 600 seconds.

In the present invention, an organic solvent can be used as a developer. After exposure, development is performed with a developer (solvent). As a result, for example, when a positive photoresist is used, the photoresist in the non-exposed portion is removed to form a photoresist pattern.

As a developer, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, methoxyethyl acetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl Ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, 2-methoxybutyl ether Tate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-Methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, Pyrene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, butyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate Methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl- 3-methoxy propionate, ethyl 3-ethoxy propionate, propyl 3-methoxy propionate and the like can be mentioned as an example. Furthermore, surfactants and the like can also be added to these developers. The conditions for development are suitably selected from a temperature of 5 to 50 ° C. and a time of 10 to 600 seconds.

Then, the resist underlayer film (intermediate layer) of the present invention is removed using the pattern of the photoresist (upper layer) thus formed as a protective film, and then the patterned photoresist and the resist underlayer film of the present invention Removal of the organic lower layer film (lower layer) is performed using the film formed of (intermediate layer) as a protective film. Finally, the semiconductor substrate is processed using the patterned resist lower layer film (intermediate layer) and organic lower layer film (lower layer) of the present invention as a protective film.

First, the resist underlayer film (intermediate layer) of the present invention in the portion where the photoresist is removed is removed by dry etching to expose the semiconductor substrate. For dry etching of the resist underlayer film of the present invention, tetrafluoromethane (CF ₄ ), trifluoromethane (CHF ₃ ), perfluorocyclobutane (C ₄ F ₈ ), perfluoropropane (C ₃ F ₈ ), trifluoromethane, Gases such as carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride and chlorine trifluoride, chlorine, trichloroborane and dichloroborane can be used. It is preferable to use a halogen-based gas for dry etching of the resist underlayer film. In dry etching using a halogen-based gas, basically, a photoresist made of an organic substance is difficult to remove. On the other hand, the resist underlayer film of the present invention containing a large amount of silicon atoms is rapidly removed by the halogen-based gas. Therefore, it is possible to suppress the decrease in the film thickness of the photoresist accompanying the dry etching of the resist underlayer film. And as a result, it becomes possible to use a photoresist in a thin film. The dry etching of the resist underlayer film is preferably performed using a fluorine-based gas. Examples of the fluorine-based gas include tetrafluoromethane (CF ₄ ), trifluoromethane (CHF ₃ ), perfluorocyclobutane (C ₄ F ₈ ), and perfluoro Propane (C ₃ F ₈ ), trifluoromethane, difluoromethane (CH ₂ F ₂ ) and the like can be mentioned.

Thereafter, removal of the organic lower layer film is performed using a film made of the patterned photoresist and the resist lower layer film of the present invention as a protective film. The organic lower layer film (lower layer) is preferably performed by dry etching using an oxygen-based gas. This is because the resist underlayer film of the present invention containing a large amount of silicon atoms is difficult to remove by dry etching with an oxygen-based gas.

Finally, processing of the semiconductor substrate is performed. The processing of the semiconductor substrate is preferably performed by dry etching with a fluorine-based gas.

As the fluorine-based gas, for example, tetrafluoromethane (CF ₄ ), trifluoromethane (CHF ₃ ), perfluorocyclobutane (C ₄ F ₈ ), perfluoropropane (C ₃ F ₈ ), trifluoromethane, and difluoromethane ( CH ₂ F ₂ ) and the like.

In addition, on the upper layer of the resist underlayer film of the present invention, an organic antireflective film can be formed before the formation of the photoresist. There is no particular limitation on the antireflective film composition to be used there, and any one of those conventionally used in the lithography process can be optionally selected and used, and a commonly used method, for example, a spinner The antireflective film can be formed by coating with a coater and baking.

In addition, the substrate to which the resist underlayer film forming composition of the present invention is applied may have an organic or inorganic antireflective film formed on the surface thereof by a CVD method or the like, The underlayer film of the invention can also be formed.

The resist underlayer film formed from the resist underlayer film forming composition of the present invention may also have absorption for the light depending on the wavelength of light used in the lithography process. And in such a case, it can function as an anti-reflective film which has the effect of preventing the reflected light from a board | substrate. Furthermore, the underlayer film of the present invention has a layer for preventing interaction between the substrate and the photoresist, a material used for the photoresist, and a function to prevent adverse effects on the substrate of a substance generated upon exposure to the photoresist. Used as a barrier layer for reducing the poisoning effect of a photoresist layer by a dielectric layer of a semiconductor substrate, and a layer having a function of preventing the diffusion of a substance generated from a substrate to an upper layer photoresist during heating and firing It is also possible.

In addition, a resist underlayer film formed from the resist underlayer film forming composition is applied to a substrate on which a via hole used in a dual damascene process is formed, and can be used as a filling material capable of filling holes without gaps. Moreover, it can also be used as a planarizing material for planarizing the surface of a semiconductor substrate with unevenness.

In addition to the function as a hard mask, the lower layer film of the EUV resist can also be used for the following purposes. Without intermixing with the EUV resist, it is possible to prevent the reflection of unwanted exposure light during EUV exposure (wavelength 13.5 nm), for example UV or DUV (ArF light, KrF light) mentioned above, from the substrate or interface The above resist underlayer film forming composition can be used as a lower layer antireflection film of a resist. Reflection can be efficiently prevented in the lower layer of the EUV resist. When used as an EUV resist underlayer film, the process can be performed in the same manner as the photoresist underlayer film.

The composition containing the polysiloxane obtained by the present invention can be used as a reverse material. Step of applying a resist on a substrate (1) Step of exposing and developing a resist (2) Step of applying a composition containing a polysiloxane obtained in the present invention to a resist pattern during or after development (3) And the step (4) of removing the resist pattern by etching and inverting the pattern.

The above composition is to be coated on a resist pattern having a rough and dense layout.

The composition may be used in which a resist pattern before coating is formed by nanoimprinting.

The above-mentioned resist can be used as a photoresist used at a process (1).

After coating, the resist solution is baked at a baking temperature of 70 to 150 ° C. for a baking time of 0.5 to 5 minutes, and a resist film thickness of 10 to 1000 nm can be obtained. Although a resist solution, a developing solution, and the coating material shown below can be coat | covered by a spin coat, a dip method, a spray method etc., a spin coat method is especially preferable. The exposure of the resist is performed through a predetermined mask. For the exposure, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), EUV light (wavelength 13.5 nm), an electron beam or the like can be used. After exposure, post exposure baking (PEB: Post Exposure Bake) can also be performed if necessary. Post-exposure heating is appropriately selected from heating temperatures of 70 ° C. to 150 ° C. and heating times of 0.3 to 10 minutes.

Before the step (1), the step (1-1) of forming a resist underlayer film on the substrate can be included. The resist underlayer film has anti-reflection and an organic hard mask function.

In the formation of the resist in the step (1), a resist underlayer film can be formed on the semiconductor substrate, and the step (1-1) of forming a resist can be performed.

In addition, in the step (1-1), a resist underlayer film can be formed on a semiconductor substrate, a hard mask of silicon can be formed thereon, and a resist can be formed thereon.

The resist underlayer film used in the step (1-1) prevents irregular reflection during exposure of the upper layer resist, and is used for the purpose of improving the adhesion to the resist, for example, an acrylic resin or the like Novolak resins can be used. The resist underlayer film can form a film with a thickness of 1 to 1000 nm on a semiconductor substrate.

The resist underlayer film used in the step (1-1) is a hard mask using an organic resin, and a material having a high carbon content and a low hydrogen content is used. For example, polyvinyl naphthalene resin, carbazole novolac resin, phenol novolac resin, naphthol novolac resin and the like can be mentioned. These can form a film with a film thickness of 5 to 1000 nm on a semiconductor substrate.

As a silicon hard mask used in the step (1-1), polysiloxane obtained by hydrolyzing a hydrolyzable silane can be used. For example, tetraethoxysilane, methyltrimethoxysilane, and a polysiloxane obtained by hydrolyzing phenyltriethoxysilane can be exemplified. These can form a film with a film thickness of 5 to 200 nm on the resist underlayer film.

In step (2), exposure is performed through a predetermined mask. For the exposure, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), EUV (wavelength 13.5 nm) or the like can be used. After exposure, post exposure bake can also be performed if necessary. Post-exposure heating is performed under conditions appropriately selected from heating temperatures of 70 ° C. to 150 ° C. and heating times of 0.3 to 10 minutes.

Next, development is performed with a developer. Thus, for example, when a positive photoresist is used, the photoresist in the exposed portion is removed to form a photoresist pattern.

As a developing solution, the developing solution of the above-mentioned alkaline developing solution and the organic solvent can be used.

Furthermore, a surfactant or the like can be added to the developer. The conditions for development are suitably selected from a temperature of 5 to 50 ° C. and a time of 10 to 600 seconds.

In the step (3), the coating composition of the present invention is applied to the resist during or after development. The coating composition can be formed by heating in the step (3). The heating is performed at a baking temperature of 50 to 180 ° C. for 0.5 to 5 minutes.

Then, in the present application, after the step (3), the step (3-1) of etching back the coated film surface to expose the resist pattern surface can be included. Thereby, in the subsequent step (4), the surface of the resist pattern matches the surface of the coating composition, and only the resist component is removed from the difference between the resist pattern and the gas etching rate of the coating composition, and the component by the coating composition Remain, resulting in pattern inversion. In the etch back, the resist pattern is exposed by a gas (for example, a fluorine-based gas) that can remove the coating composition.

In the step (4), the resist pattern is etched away to invert the pattern. In step (4), dry etching is performed using tetrafluoromethane, perfluorocyclobutane (C ₄ F ₈ ), perfluoropropane (C ₃ F ₈ ), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride Gas such as difluoromethane, nitrogen trifluoride and chlorine trifluoride. In particular, dry etching is preferably performed using an oxygen-based gas.

As a result, the original resist pattern is removed, and a reverse pattern is formed by the pattern inversion forming polysiloxane contained in the coating composition.

Synthesis Example 1
The silanol groups of the polysiloxane prepared from HTEOS: MTEOS = 95 mole%: 5 mole% are capped with methoxy groups.

49.28 g of triethoxysilane (HTEOS) (95 mol% in total silane), 2.82 g of methyltriethoxysilane (MTEOS) (5 mol% in total silane) and 104.20 g of acetone in a flask I put it in. A dropping funnel containing a mixed solution of 8.53 mg of acetic acid, 8.53 g of water, and 104.20 g of acetone was attached to the flask and slowly dropped while maintaining the temperature at 30 ° C. or less. Thereafter, the reaction was carried out at room temperature for 65 hours. Thereafter, 62.82 g of 2,2-dimethoxypropane (capping agent) was added, and the mixture was allowed to react at 65 ° C. for 1 hour. After completion of the reaction, 77.30 g of diisoamyl ether was charged and set in an evaporator to remove low-boiling components generated during the reaction to obtain 97.32 g of a polysiloxane solution (corresponding to the formula (5-1)). The solid content in the obtained reaction product was 18.2% by mass as a result of measurement by a firing method.

¹ H-NMR (500 MHz, CD ₃ COCD ₃ ): δ = 6.901 (br, 0.08 H), 4.337 (br, 1.06 H), 3.880 (br, 0.09 H), 280 (br, 0.38 H), 1.095 (br, 0.11 H), 0.264 (br, 0.15 H)
* Assuming that the integral value of Si-Me is 0.15 H: capping ratio:
(Methoxy group + ethoxy group) / (methoxy group + ethoxy group + SiOH group) × 100 = 69.2 mol%

The capping rate was calculated by capping the unhydrolyzed ethoxy group (Si-OC ₂ H ₅ ) of the starting silane and the hydrolyzed silanol group with a methoxy group (Si-OCH ₃ ), so methoxy and ethoxy groups The capping rate was calculated from
GPC (polystyrene conversion): Mw = 7325

Thereafter, the polysiloxane obtained as described above was diluted in the proportions in the following table, and filtered through a filter with a pore diameter of 0.1 μm to obtain a polysiloxane composition.

(Composition example 2)
The silanol groups of the polysiloxane prepared from HTEOS: MTEOS = 95 mole%: 5 mole% are capped with methoxy groups.

32.86 g of triethoxysilane (HTEOS) (95 mol% in total silane), 1.88 g of methyltriethoxysilane (MTEOS) (5 mol% in total silane) and 46.31 g of acetone in a flask I put it in. A dropping funnel containing a mixed solution of 5.68 mg of acetic acid, 5.68 g of water, and 34.73 g of acetone was attached to the flask and slowly dropped while maintaining the temperature at 30 ° C. or less. The reaction was then allowed to proceed for 41 hours at room temperature. Thereafter, 41.88 g of 2,2-dimethoxypropane (capping agent) was added and reacted at 65 ° C. for 1 hour. After completion of the reaction, 60.66 g of diisoamyl ether was charged and set in an evaporator to remove low-boiling components generated during the reaction to obtain 73.95 g of a polysiloxane solution (corresponding to the formula (5-1)). In addition, as a result of measuring solid content in the obtained reaction product by a baking method, it was 15.68 mass%.

¹ H-NMR (500 MHz, CD ₃ COCD ₃ ): δ = 6.941 (br, 0.11 H), 4.345 (br, 0.87 H), 3.849 (br, 0.09 H), 306 (br, 0.31 H), 1.286 (br, 0.20 H), 0.258 (br, 0.15 H)
* Assuming that the integral value of Si-Me is 0.15 H: capping ratio:
(Methoxy group + ethoxy group) / (methoxy group + ethoxy group + SiOH group) x 100 = 56.9 mol%

The capping rate was calculated by capping the unhydrolyzed ethoxy group (Si-OC ₂ H ₅ ) of the starting silane and the hydrolyzed silanol group with a methoxy group (Si-OCH ₃ ), so methoxy and ethoxy groups The capping rate was calculated from
GPC (polystyrene conversion): Mw = 17251

Thereafter, the polysiloxane obtained as described above was diluted in the proportions in the following table, and filtered through a filter with a pore diameter of 0.1 μm to obtain a polysiloxane composition.

(Comparative Example 1)
Preparation of a polysiloxane solution prepared from HTEOS: MTEOS = 95 mol%: 5 mol%.

49.28 g of triethoxysilane (HTEOS) (95 mol% in total silane), 2.82 g of methyltriethoxysilane (MTEOS) (5 mol% in total silane) and 104.20 g of acetone in a flask I put it in. A dropping funnel containing a mixed solution of 8.53 mg of acetic acid, 8.53 g of water, and 104.20 g of acetone was attached to the flask and slowly dropped while maintaining the temperature at 30 ° C. or less. Thereafter, the reaction was carried out at room temperature for 65 hours. After completion of the reaction, 82.61 g of diisoamyl ether was charged and set in an evaporator to remove low-boiling components generated during the reaction to obtain 102.17 g of a polysiloxane solution (corresponding to the formula (5-1)). In addition, as a result of measuring solid content in the obtained reaction product by a baking method, it was 17.66 mass%.

¹ H-NMR (500 MHz, CD ₃ COCD ₃ ): δ = 6.849 (br, 0.19 H), 4.355 (br, 0.98 H), 3.848 (br, 0.02 H), 217 (br, 0.05 H), 0.262 (br, 0.15 H)
* Assuming that the integral value of Si-Me is 0.15 H: capping ratio:
(Methoxy group + ethoxy group) / (methoxy group + ethoxy group + SiOH group) x 100 = 0.0 mol%
GPC (polystyrene conversion): Mw = 8196

Thereafter, the polysiloxane obtained as described above was diluted in the proportions in the following table, and filtered through a filter with a pore diameter of 0.1 μm to obtain a polysiloxane composition.

(Comparative Synthesis Example 2)
Preparation of a polysiloxane solution prepared from HTEOS: MTEOS = 95 mol%: 5 mol%.

32.86 g of triethoxysilane (HTEOS) (95 mol% in total silane), 1.88 g of methyltriethoxysilane (MTEOS) (5 mol% in total silane) and 46.31 g of acetone in a flask I put it in. A dropping funnel containing a mixed solution of 5.68 mg of acetic acid, 5.68 g of water, and 34.73 g of acetone was attached to the flask and slowly dropped while maintaining the temperature at 30 ° C. or less. The reaction was then allowed to proceed for 41 hours at room temperature. After completion of the reaction, 58.07 g of diisoamyl ether was charged and set in an evaporator to remove low-boiling components generated during the reaction to obtain 72.66 g of a polysiloxane solution (corresponding to the formula (5-1)). In addition, as a result of measuring solid content in the obtained reaction product by a baking method, it was 15.69 mass%.

¹ H-NMR (500 MHz, CD ₃ COCD ₃ ): δ = 6.925 (br, 0.23 H), 4.320 (br, 0.88 H), 0.254 (br, 0.15 H)
* Assuming that the integral value of Si-Me is 0.15 H: capping ratio:
(Methoxy group + ethoxy group) / (methoxy group + ethoxy group + SiOH group) x 100 = 0.0 mol%
GPC (polystyrene conversion): Mw = 20181

Thereafter, the polysiloxane obtained as described above was diluted in the proportions in the following table, and filtered through a filter with a pore diameter of 0.1 μm to obtain a polysiloxane composition.

(Comparative synthesis example 3)
A flask was charged with 53.9 g of tetraethoxysilane (containing 50 mole% in total silane), 46.1 g of methyltriethoxysilane (containing 50 mole% in total silane) and 100 g of acetone. To the flask, a condenser was attached and a dropping funnel containing 32.6 g of a hydrochloric acid aqueous solution (0.01 mol / liter) prepared and set was set, and the hydrochloric acid aqueous solution was slowly dropped at room temperature and stirred for several minutes. Then, it was made to react at 85 ° C. for 4 hours in an oil bath. After completion of the reaction, the flask containing the reaction solution was allowed to cool and then set in an evaporator to remove ethanol generated during the reaction to obtain a reaction product (polysiloxane) (corresponding to the formula (6-1)) . Further, acetone was replaced with propylene glycol monoethyl ether using an evaporator. The solid content in the obtained reaction product was 13% by mass as a result of measurement by the firing method.
GPC (polystyrene conversion): Mw = 3700

Thereafter, the polysiloxane obtained as described above was diluted in the proportions in the following table, and filtered through a filter with a pore diameter of 0.1 μm to obtain a polysiloxane composition.

(Preparation of polysiloxane composition)
The polysiloxanes obtained in the above Synthesis Examples 1 and 2 and Comparative Synthesis Examples 1 and 2 and 3 and the solvents are mixed in the proportions shown in Tables 1 and 2 and filtered through a 0.1 μm filter made of a fluororesin. And solutions of the polysiloxane composition were prepared. The addition ratio of the polymer in the following table indicates the addition amount of the polymer itself, not the addition amount of the polymer solution.

In the following table, diisoamyl ether is DIAE, maleic acid as curing catalyst is MA, N- (3-triethoxypropyl) -4,5-dihydroimidazole is curing IMIDTEOS as curing catalyst, propylene glycol monomethyl ether acetate is PGMEA as solvent, Propylene glycol monoethyl ether as a solvent is abbreviated as PGEE, and propylene glycol monomethyl ether as a solvent is abbreviated as PGME. Each addition amount was shown by the mass part.

[Table 1]
Table 1
―――――――――――――――――――――――――――――――――――
Polymer Solvent------------------------
Example 1 Synthesis Example 1 DIAE
(Parts by mass) 15.00 85.00
Example 2 Synthesis Example 2 DIAE
(Parts by mass) 15.00 85.00
Comparative Example 1 Comparative Synthesis Example 1 DIAE
(Parts by mass) 15.00 85.00
Comparative Example 2 Comparative Synthesis Example 2 DIAE
(Parts by mass) 15.00 85.00
―――――――――――――――――――――――――――――――――――

[Table 2]
Table 2
―――――――――――――――――――――――――――――――――――――
Polymer Curing catalyst 1 Curing catalyst 2 Solvent------------------------
Comparative Example 3 Comparative Synthesis Example 3 MA IMIDTEOS PGME PGMEA Water
(Parts by mass) 6.9 0.01 0.01 4.6 9.2 67.2 11.1
―――――――――――――――――――――――――――――――――――――

(Storage stability of polysiloxane)
The capping polysiloxane solutions of Synthesis Examples 1 and 2 and the polysiloxane solutions of Comparative Synthesis Examples 1 and 2 were stored at 40 ° C. and −20 ° C., and Mw (weight-average molecular weight) was compared by GPC. The evaluation results are shown in Tables 3 and 4.

[Table 3]
Table 3
―――――――――――――――――――――――――――――――――――――
Example 1 Example 1 Example 2 Example 2
―――――――――――――――――――――――――――――――――――――
Polymer Synthesis Example 1 Synthesis Example 1 Synthesis Example 2 Synthesis Example 2
Temperature -20 ° C 40 ° C -20 ° C 40 ° C
Time 1 week 1 week 1 week 1 week
―――――――――――――――――――――――――――――――――――――
Mw 8596 18938 18314 22032
―――――――――――――――――――――――――――――――――――――

[Table 4]
Table 4
―――――――――――――――――――――――――――――――――――――
Comparative Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 2
―――――――――――――――――――――――――――――――――――――
Polymer Comparative Synthesis Example 1 Comparative Synthesis Example 1 Comparative Synthesis Example 2 Comparative Synthesis Example 2
Temperature -20 ° C 40 ° C -20 ° C 40 ° C
Time 1 week 1 week 1 week 1 week
―――――――――――――――――――――――――――――――――――――
Mw 33313 Gelation 103127 Gelation----------------------------

As shown in the above table, the polysiloxane solution in which the silanol group is protected has a small increase in Mw (weight average molecular weight) compared to the polysiloxane solution in which the silanol group is unprotected, and gelation hardly occurs, so storage stability It is understood that it is excellent in sex.

(Evaluation of flatness on Si substrate)
With respect to the polysiloxane compositions in Examples 1 and 2 and Comparative Examples 1 and 2, the flatness evaluation was performed as follows. The evaluation results are shown in Table 5.

The polysiloxane composition of Example 1 is applied on a stepped substrate having a groove depth of 200 nm and a width of 800 nm using a spin coater under the conditions of a rotation number of 1,500 rpm for 60 seconds, and then baked at 100 ° C. for 1 minute did. Similarly, the polysiloxane compositions of Example 2 and Comparative Examples 1 and 2 were applied, and heated at 100 ° C. for 1 minute on a hot plate to form a polysiloxane composition film (prepared to have a film thickness of 180 nm). Next, with respect to the obtained polysiloxane composition film, the shape of the cross section was observed by a cross section SEM to evaluate the flatness. Observe the groove pattern with a depth of 200 nm and a width of 800 nm, measure the film thickness at the area with the lowest film thickness and the area with the highest film thickness with reference to the groove bottom, calculate the film thickness difference, and reduce the film thickness difference Flatness was evaluated to be good as it was.

[Table 5]
Table 5
――――――――――――――――――――――――
Thickness difference---------------
Example 1 35.8 nm
Example 2 57.5 nm
Comparative Example 1 89.3 nm
Comparative Example 2 99.2 nm
――――――――――――――――――――――――

As shown in the above-mentioned table, the siloxane coating film formed using the composition of the present invention showed a good planarization property to the comparative example.

(Evaluation of dry etching rate)
A solution of a composition containing the polysiloxane of Examples 1 and 2 and Comparative Examples 1 and 2 is coated on a wafer using a spin coater under the conditions of a rotation number of 1500 rpm for 60 seconds, and then baked at 100 ° C. for 1 minute To form a film of polysiloxane composition (prepared to a film thickness of 180 nm).

The dry etching of these coatings was performed, the etching rate of chlorine gas (etching rate: nm / min) was measured, and the results are shown in Table 6.

The etcher used was LAM-2300 (manufactured by Ram Research Inc.) for the measurement of the dry etching rate.

[Table 6]
Table 6
―――――――――――――――――――――――――――
Chlorine gas etching rate--------------
Example 1 4.9
Example 2 5.6
Comparative Example 1 3.6
Comparative Example 2 4.0
―――――――――――――――――――――――――――

As shown in the above-mentioned table, the siloxane coating film formed using the composition of the present invention showed a good etching resistance similar to that of the comparative example. This shows good etching resistance when processing a base using the formed pattern, when it is used as a coating composition or a resist composition.

(Electrical insulation evaluation)
A solution of the composition containing the polysiloxane of Example 1 is coated on a wafer using a spin coater at a rotational speed of 1000 rpm for 60 seconds, and then baked at 110 ° C. for 1 minute to form a polysiloxane composition film It formed. Similarly, the solution of Comparative Example 3 was applied at a rotational speed of 1000 rpm for 60 seconds, and then baked at 205 ° C. for 1 minute to form a polysiloxane composition film. Regarding the electrical insulation of the obtained resin film, the leak current density A / cm ² was measured when an electric field strength of 1 MV / cm and 3 MV / cm was applied to the resin film by a mercury prober (CVmap 92A manufactured by Four Dimensions). . The results are shown in Table 7.

[Table 7]
Table 7
―――――――――――――――――――――――――――――――――――――
Film thickness 1MV / cm 3MV / cm
―――――――――――――――――――――――――――――――――――――
Example 1 273 nm 3.78E-09 2.03E-07
Comparative Example 3 177 nm 2.63E-07 6.02E-06
―――――――――――――――――――――――――――――――――――――

As shown in the above table, the siloxane coating film formed using the composition of the present invention showed excellent insulation.

(Heat resistance evaluation)
A solution of the composition containing the polysiloxane of Example 1 is coated on a wafer using a spin coater at a rotational speed of 1500 rpm for 60 seconds, and then baked at 110 ° C. for 1 minute to form a polysiloxane composition film. It formed. The obtained resin film was scraped off with a scraper, and the heat resistance of the obtained sample was measured by TG-DTA (TG / DTA2010SR manufactured by NETZSCH). The gas was nitrogen and the sample was ramped up to 500 ° C. at 10 ° C./min and subsequently held at 500 ° C. for 1 hour to assess weight loss. The measurement results are shown in Table 8.

[Table 8]
Table 8
―――――――――――――――――――――――――――――――――――――
The weight loss when the weight is reduced to 1 hour at room temperature from 500 ° C to 500 ° C-------------------- ―――――
Example 1 -4.8% 0.4%
Comparative example 3 7.2% 1.6%
―――――――――――――――――――――――――――――――――――――

As shown in the above table, the siloxane coated film formed using the composition of the present invention showed a small weight loss at 500 ° C. and showed excellent heat resistance.

A hydrogenated polysiloxane having high heat resistance, insulation, and etching resistance, which is improved in storage stability, and improved in storage stability so as to improve flatness as a coating film. It is a polysiloxane composition part.

Claims (9)

1. A compound for capping silanol groups of polysiloxane, which is a compound of the formula (1):
   

   

   The above compound having a structure represented by (In the formula (1), R ¹ represents an alkyl group or an aryl group, R ² represents an alkoxy group, and a represents an integer of 1 to 2).
2. A first step of obtaining a hydrolytic condensate of a hydrolyzable silane, and a second step of capping a silanol group in the hydrolytic condensate using the compound represented by the formula (1) according to claim 1 Method of producing polysiloxane containing.
3. The hydrolyzable silane used in the first step has the following formula (2):
   

   

   (In the formula (2), R ³ represents a hydrogen atom and represents a bond to a silicon atom through a Si—H bond, R ⁴ represents an alkoxy group, an acyloxy group or a halogen atom, b is 1 The method for producing a polysiloxane according to claim 2, which comprises a hydrolyzable silane represented by the following formula:
4. The hydrolyzable silane used in the first step is a combination of the hydrolyzable silane represented by the above formula (2) and another hydrolyzable silane, and the other hydrolyzable silanes are represented by the formula (3):
   

   

   (In formula (3), R ⁵ represents an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkoxyaryl group, an alkenyl group, or an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group or a cyano group R ⁶ represents an alkoxy group, an acyloxy group, or a halogen atom, and c represents an integer of 1 to 2). Hydrolyzable silanes represented, and Formula (4):
   

   

   (In the formula (4), R ⁷ represents an alkyl group and is bonded to a silicon atom by a Si—C bond, R ⁸ represents an alkoxy group, an acyloxy group or a halogen atom, and Y represents an alkylene group or And at least one hydrolyzable silane selected from the group consisting of hydrolyzable silanes represented by arylene group, d represents an integer of 0 or 1, and e represents an integer of 0 or 1. Yes,
   The method for producing a polysiloxane according to claim 2 or 3, wherein the hydrolyzable silane represented by the above formula (2) and the other hydrolyzable silane are present in a molar ratio of 100: 0 to 90:10.
5. In the first step, the hydrolyzable silane represented by the formula (2) or the hydrolyzable silane represented by the formula (2) and other hydrolysable silanes are hydrolyzed with an acid to obtain a hydrolytic condensate The manufacturing method of the polysiloxane of any one of Claim 2 thru | or 4.
6. In the first step, the hydrolyzable silane represented by the formula (2) or the hydrolyzable silane represented by the formula (2) and other hydrolyzable silanes are hydrolyzed to obtain a hydrolytic condensate; The method according to any one of claims 2 to 5, wherein the silanol group in the hydrolytic condensate is capped with the compound of the formula (1) according to claim 1 under an acid catalyst in the step.
7. In the first step, the hydrolyzable silane represented by the formula (2) or the hydrolyzable silane represented by the formula (2) and other hydrolyzable silanes are hydrolyzed with an acid, and the hydrolyzate is condensed. A solution of hydrolytic condensate is obtained, and the silanol group in the hydrolytic condensate is catalyzed by the acid remaining in the solution of the hydrolytic condensate in the second step as formula (1) according to claim 1. The method according to any one of claims 2 to 5, wherein the compound is capped with a compound of
8. The polysiloxane according to any one of claims 2 to 7, wherein the polysiloxane is a polysiloxane used for a composition for forming a planarizing film used for planarizing a substrate including a level difference. Production method.
9. 8. The polysiloxane according to any one of claims 2 to 7, wherein the polysiloxane is a composition for forming an intermediate film used as a hard mask between a resist and an organic film in a lithography process by a multilayer resist method. The manufacturing method of the polysiloxane of 1 item.