Laminate, method for producing laminate, and pattern forming method

Abstract

To provide a laminate capable of forming a fine pattern by satisfying both high sensitivity and high resolution in photolithography using a high energy beam, a method for manufacturing the laminate, and a pattern forming method.SOLUTION: A laminate comprising a substrate, a silicon-containing resist underlayer film obtained from a silicon-containing resist underlayer film composition comprising a thermally crosslinkable polysiloxane having a specific structure, and a resist film obtained from a resist composition comprising a hypervalent iodine compound having a specific structure, a carboxy group-containing compound, and a solvent, in this order.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a laminate, a method for manufacturing a laminate, and a method for forming a pattern. [Background technology]

[0002] As the IoT market expands, there is a growing demand for higher integration, higher speeds, and lower power consumption in LSIs, leading to rapid progress in miniaturization of pattern rules. Logic devices, in particular, are driving this miniaturization. The most advanced miniaturization technology is ArF immersion lithography, with double patterning, triple patterning, and quadruple patterning being used to mass-produce 10nm-node devices. Furthermore, studies are underway to develop 7nm-node devices using next-generation extreme ultraviolet (EUV) lithography with a wavelength of 13.5nm.

[0003] As miniaturization progresses, image blurring due to acid diffusion has become a problem (Non-Patent Document 1). It has been suggested that in order to ensure resolution in fine patterns with processing dimensions of 45 nm and below, not only is it important to improve dissolution contrast, as has been proposed in the past, but also to control acid diffusion (Non-Patent Document 2). However, because chemically amplified resist compositions increase sensitivity and contrast through acid diffusion, attempts to minimize acid diffusion by lowering the post-exposure bake (PEB) temperature or shortening the PEB time result in significant decreases in sensitivity and contrast.

[0004] Adding an acid generator that generates bulky acid is effective in suppressing acid diffusion. Therefore, copolymerization of an onium salt acid generator with a polymerizable olefin into a polymer has been proposed. However, for resist film pattern formation with feature sizes of 16 nm or less, it is believed that chemically amplified resist compositions cannot be used to form patterns due to acid diffusion, and the development of non-chemically amplified resist compositions is desired.

[0005] One material for non-chemically amplified resist compositions is polymethyl methacrylate (PMMA), a positive resist material whose main chain is cleaved by EUV irradiation, resulting in a decrease in molecular weight, which improves its solubility in organic solvent developers.

[0006] Hydrogen silsesquioxane (HSQ) is a negative resist material that becomes insoluble in alkaline developers due to crosslinking caused by the condensation reaction of silanols generated by EUV irradiation. Chlorine-substituted calixarenes also function as negative resist materials. These negative resist materials have small molecular size before crosslinking and are free of blurring due to acid diffusion, resulting in low edge roughness and extremely high resolution, and are used as pattern transfer materials to indicate the resolution limit of exposure equipment. However, these materials have insufficient sensitivity, and further improvement is needed.

[0007] One of the challenges in developing materials for EUV lithography is the low photon count in EUV exposure. EUV energy is much higher than that of ArF excimer laser light, and the photon count in EUV exposure is one-fourteenth that of ArF exposure. Furthermore, the pattern dimensions formed with EUV exposure are less than half those of ArF exposure. This makes EUV exposure susceptible to variations in photon count. The variations in photon count in the extremely short wavelength radiation region are a physical phenomenon known as shot noise, and this effect cannot be eliminated. Therefore, so-called stochastics has attracted attention. While the effects of shot noise cannot be eliminated, methods for reducing this effect are being discussed. Shot noise not only increases dimensional uniformity (CDU) and line width roughness (LWR), but also causes hole blockage with a probability of one in several million. Blocked holes cause poor electrical conduction, preventing transistor operation and adversely affecting overall device performance. When considering practical sensitivity, resist compositions containing PMMA or HSQ as the main component are significantly affected by stochastics and are unable to achieve the desired resolution performance.

[0008] As a method for reducing the impact of shot noise on the resist side, the introduction of elements that have high absorption of EUV light has attracted attention. Patent Document 1 proposes a chemically amplified resist composition containing iodine atoms that have high absorption of EUV light. However, as mentioned above, chemically amplified resist compositions cannot achieve excellent resolution performance in EUV lithography, where processing dimensions will become increasingly finer in the future. In particular, in line and space patterns, as pattern dimensions become smaller, pattern collapse and line breakage increase significantly, and reducing these occurrences leads to an improvement in limiting resolution.

[0009] Patent Document 2 proposes a negative resist composition using a tin compound. Because this composition contains tin, which has high absorption of EUV light, as its main component, it has improved stochastics and can achieve high sensitivity and high resolution. However, so-called metal resists of this type have many issues, such as insufficient solubility in resist solvents, storage stability, and defects due to post-etching residues. Furthermore, since metal resists are negative resists in which the exposed areas become insoluble in developer solutions by primarily becoming metal oxides, applying them to contact hole patterning requires an additional reversal process, which raises cost concerns. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Japanese Patent Application Publication No. 2018-5224 [Patent Document 2] Special Publication No. 2021-503482

[0011] [Non-Patent Document 1] SPIE Vol. 5039 p1 (2003) [Non-patent document 2] SPIE Vol. 6520 p65203L-1 (2007) Summary of the Invention [Problem to be solved by the invention]

[0012] The present invention has been made in view of the above circumstances, and aims to provide a laminate comprising a resist film obtained from a non-chemically amplified resist composition that is applicable to photolithography using high-energy rays, particularly electron beam (EB) lithography and EUV lithography, and that has excellent sensitivity and limiting resolution, and a silicon-containing resist underlayer film thereunder, and a method for forming a pattern on the upper layer of the laminate. [Means for solving the problem]

[0013] In order to solve the above problems, the present invention provides: A substrate; a silicon-containing resist underlayer film obtained from a silicon-containing resist underlayer film composition containing a thermally crosslinkable polysiloxane including at least one repeating unit represented by the following general formulas (1) to (3) and at least one repeating unit represented by the following general formulas (4) to (6); a resist film obtained from a resist composition containing at least one hypervalent iodine compound selected from the group consisting of a hypervalent iodine compound represented by the following formula (7), a hypervalent iodine compound represented by the following formula (8), and a hypervalent iodine compound represented by the following formula (9), a carboxy group-containing compound, and a solvent; The present invention provides a laminate comprising the above in this order. [ka] (In the formula, R 1 is an organic group having a carboxyl group or an organic group having a carboxyl group substituted with an acid labile group, and R 2 , R 3 and R 4 are each a monovalent organic group having 1 to 30 carbon atoms, which may be the same or different. [ka] (In the formula, m is 0, 1, or 2. When m is 0, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, or 5, and 1≦n1+n2≦6. When m is 1, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1≦n1+n2≦8. When m is 2, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, or 5. , 5, 6, 7, 8, or 9, and 1≦n1+n2≦10. n3 is 1 or 2. n4 is 0, 1, 2, 3, or 4, provided that 1≦n3+n4≦5. n5 is 1 or 2. n6 is 0, 1, 2, 3, or 4, provided that 1≦n5+n6≦5. n7 is 0, 1, 2, 3, or 4. n8 is 1, 2, 3, or 4. R 11 ~R 18 are each independently a halogen atom or a hydrocarbyl group having 1 to 10 carbon atoms which may contain a heteroatom. 11 and R 12 , R 13 and R 14 , R 15 and R 16 , or R 17 and R 18 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms. R 21 ~R 24 are each independently a hydrocarbyl group having 1 to 40 carbon atoms which may contain a halogen atom or a heteroatom. When n2 is 2 or more, each R 21 may be the same or different, and multiple R 21 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n4 is 2 or more, each R 22 may be the same or different, and multiple R 22 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n6 is 2 or more, each R 23 may be the same or different, and multiple R 23may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n7 is 2 or more, each R24 may be the same or different, and multiple R 24 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are attached. R 25 is an (n8)-valent hydrocarbon group having 1 to 40 carbon atoms or an (n8)-valent heterocyclic group having 2 to 40 carbon atoms, and when n8 is 2, R 25 may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, a sulfonyl group, or a thioketone bond. In addition, some or all of the hydrogen atoms of the (n8)-valent hydrocarbon group or the (n8)-valent heterocyclic group may be substituted with a group containing a hetero atom, and some of the -CH2- of the (n8)-valent hydrocarbon group may be substituted with a group containing a hetero atom, and R 24 and R 25 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms.

[0014] Such a laminate exhibits excellent sensitivity and limiting resolution, making it applicable to photolithography using high-energy beams, particularly electron beam (EB) lithography and EUV lithography. The resist composition of the present invention contains iodine atoms that have high absorption ability for EUV light, and therefore reduces shot noise, making it possible to achieve higher resolution and lower LWR, particularly in EUV lithography.

[0015] In this case, it is preferable that a resist underlayer film is provided between the substrate and the silicon-containing resist underlayer film.

[0016] Such a laminate is extremely effective for microfabrication by precisely transferring the pattern of the resist film, which exhibits excellent resolution, onto a substrate.

[0017] The silicon-containing resist underlayer film composition preferably contains a siloxane polymerization crosslinking catalyst (Xc), an alcohol-based organic solvent, and water.

[0018] Such a silicon-containing resist underlayer film composition is stable and has excellent handleability, and the silicon-containing resist underlayer film produced is suitable in terms of pattern forming ability and film strength as a resist film.

[0019] The carboxy group-containing compound in the resist composition is preferably a polymer containing a repeating unit represented by the following formula (10) or a compound represented by the following formula (11). [ka] (In the formula, R A is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. X A is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OX A1 -X A1 is a saturated hydrocarbylene group having 1 to 10 carbon atoms, a phenylene group, or a naphthylene group, and the saturated hydrocarbylene group may contain a hydroxy group, an ether bond, an ester bond, or a lactone ring. * represents a bond to a carbon atom in the main chain. p is 1, 2, 3 or 4. R 31 is a p-valent hydrocarbon group having 1 to 40 carbon atoms or a p-valent heterocyclic group having 2 to 40 carbon atoms, and when p is 2, R 31 may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, or a sulfonyl group. Some or all of the hydrogen atoms of the p-valent hydrocarbon group or p-valent heterocyclic group may be substituted with a group containing a heteroatom, and some of the -CH2- groups of the p-valent hydrocarbon group may be substituted with a group containing a heteroatom. R 32is a single bond or a hydrocarbylene group having 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing a hetero atom, or some of the -CH2- of the hydrocarbylene group may be substituted with a group containing a hetero atom. 32 may be the same as or different from each other.)

[0020] If the carboxyl group-containing compound has such a structure, it has high solubility in a solvent and can be easily made into a composition, and because of its rigid skeleton, high etching resistance can be achieved.

[0021] Next, in the present invention, a step of forming a resist underlayer film on a substrate is performed. forming a silicon-containing resist underlayer film on the resist underlayer film from a silicon-containing resist underlayer film composition containing a thermally crosslinkable polysiloxane containing one or more repeating units represented by the following general formulas (1) to (3) and one or more repeating units represented by the following general formulas (4) to (6); The present invention provides a method for producing a laminate, which comprises the steps of: applying a resist composition onto the silicon-containing resist underlayer film, the resist composition comprising at least one hypervalent iodine compound selected from the group consisting of hypervalent iodine compounds represented by the following formula (7), hypervalent iodine compounds represented by the following formula (8), and hypervalent iodine compounds represented by the following formula (9); a carboxy group-containing compound; and a solvent; and performing a heat treatment to form a resist film. [ka] (In the formula, R 1 is an organic group having a carboxyl group or an organic group having a carboxyl group substituted with an acid labile group, and R 2 , R 3 and R 4 are each a monovalent organic group having 1 to 30 carbon atoms, which may be the same or different. [ka] (In the formula, m is 0, 1, or 2. When m is 0, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, or 5, and 1≦n1+n2≦6. When m is 1, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1≦n1+n2≦8. When m is 2, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, or 5. , 5, 6, 7, 8, or 9, and 1≦n1+n2≦10. n3 is 1 or 2. n4 is 0, 1, 2, 3, or 4, provided that 1≦n3+n4≦5. n5 is 1 or 2. n6 is 0, 1, 2, 3, or 4, provided that 1≦n5+n6≦5. n7 is 0, 1, 2, 3, or 4. n8 is 1, 2, 3, or 4. R 11 ~R 18 are each independently a halogen atom or a hydrocarbyl group having 1 to 10 carbon atoms which may contain a heteroatom. 11 and R 12 , R 13 and R 14 , R 15 and R 16 , or R 17 and R 18 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms. R 21 ~R 24 are each independently a hydrocarbyl group having 1 to 40 carbon atoms which may contain a halogen atom or a heteroatom. When n2 is 2 or more, each R 21 may be the same or different, and multiple R 21 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n4 is 2 or more, each R 22 may be the same or different, and multiple R 22 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n6 is 2 or more, each R 23 may be the same or different, and multiple R 23 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n7 is 2 or more, each R24 may be the same or different, and multiple R 24 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are attached. R 25 is an (n8)-valent hydrocarbon group having 1 to 40 carbon atoms or an (n8)-valent heterocyclic group having 2 to 40 carbon atoms, and when n8 is 2, R 25 may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, a sulfonyl group, or a thioketone bond. In addition, some or all of the hydrogen atoms of the (n8)-valent hydrocarbon group or the (n8)-valent heterocyclic group may be substituted with a group containing a hetero atom, and some of the -CH2- of the (n8)-valent hydrocarbon group may be substituted with a group containing a hetero atom, and R 24 and R 25 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms.

[0022] In this way, by forming a silicon-containing resist underlayer film and then forming thereon a resist film obtained from a resist composition containing a hypervalent iodine compound and a carboxy group-containing compound as main components, it is possible to form a resist film that exhibits excellent resolution and to produce a laminate that is extremely effective for precise microfabrication.

[0023] In this case, the resist underlayer film can be formed by applying an underlayer film forming material onto a substrate and then heat treating the applied material.

[0024] The resist underlayer film can also be formed by a CVD method or an ALD method.

[0025] Furthermore, the carboxy group-containing compound may be a polymer containing a repeating unit represented by the following formula (10) or a compound represented by the following formula (11). [ka] (In the formula, R Ais a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. X A is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OX A1 -X A1 is a saturated hydrocarbylene group having 1 to 10 carbon atoms, a phenylene group, or a naphthylene group, and the saturated hydrocarbylene group may contain a hydroxy group, an ether bond, an ester bond, or a lactone ring. * represents a bond to a carbon atom in the main chain. p is 1, 2, 3 or 4. R 31 is a p-valent hydrocarbon group having 1 to 40 carbon atoms or a p-valent heterocyclic group having 2 to 40 carbon atoms, and when p is 2, R 31 may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, or a sulfonyl group. Some or all of the hydrogen atoms of the p-valent hydrocarbon group or p-valent heterocyclic group may be substituted with a group containing a heteroatom, and some of the -CH2- groups of the p-valent hydrocarbon group may be substituted with a group containing a heteroatom. R 32 is a single bond or a hydrocarbylene group having 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing a hetero atom, or some of the -CH2- of the hydrocarbylene group may be substituted with a group containing a hetero atom. 32 may be the same as or different from each other.)

[0026] In the case of a production method using a composition containing such a carboxy group-containing compound with a specific structure, the composition is stable and a laminate having high etching resistance can be preferably produced.

[0027] The present invention provides a pattern forming method including the steps of exposing a resist film of the above-described laminate to i-line, KrF excimer laser, ArF excimer laser, electron beam, or extreme ultraviolet light, and developing the exposed resist film using a developer.

[0028] In the present invention, a highly sensitive and highly resolved micropattern can be formed by exposing a resist film to high energy rays and developing it with a developer.

[0029] The developer may be an organic solvent.

[0030] The resist film of the present invention is strong due to the effects of the hypervalent iodine compound and the carboxylic acid compound, and has excellent etching resistance and developer resistance to solvent developers, and is therefore suitable for use in pattern formation methods that involve development with a developer that uses an organic solvent. [Effects of the Invention]

[0031] The laminate of the present invention is extremely useful for forming fine patterns, achieving both high sensitivity and high resolution, particularly in i-line, KrF excimer laser, ArF excimer laser, EB lithography and EUV lithography. DETAILED DESCRIPTION OF THE INVENTION

[0032] As mentioned above, there was a need for the development of a material suitable for lithography that would form fine patterns with high sensitivity and high resolution, that would have excellent dimensional uniformity (CDU), small line width roughness (LWR), and would be less susceptible to the phenomenon of micro-hole clogging.

[0033] As a result of extensive research conducted to achieve the above object, the present inventors discovered that by laying a desired silicon-containing resist underlayer film underneath a resist film obtained from a resist composition containing a predetermined hypervalent iodine compound and a carboxy group-containing compound as main components, a resist film exhibiting excellent resolution can be obtained, which is extremely effective for precise microfabrication, and have led to the completion of the present invention.

[0034] The laminate of the present invention is extremely useful as a laminate for multi-layer resist processes such as a three-layer resist process using a resist underlayer film and a silicon-containing resist underlayer film.

[0035] The present invention will be described in detail below, but the present invention is not limited thereto.

[0036] That is, the present invention is a laminate comprising a substrate, a silicon-containing resist underlayer film, and a resist film in this order.

[0037] [Laminate] The laminate of the present invention is A substrate; a silicon-containing resist underlayer film obtained from a silicon-containing resist underlayer film composition containing a thermally crosslinkable polysiloxane including at least one repeating unit represented by the following general formulas (1) to (3) and at least one repeating unit represented by the following general formulas (4) to (6); a resist film obtained from a resist composition containing at least one hypervalent iodine compound selected from the group consisting of a hypervalent iodine compound represented by the following formula (7), a hypervalent iodine compound represented by the following formula (8), and a hypervalent iodine compound represented by the following formula (9), a carboxy group-containing compound, and a solvent; The laminate is characterized by comprising the above in this order. [ka] (In the formula, R 1 is an organic group having a carboxyl group or an organic group having a carboxyl group substituted with an acid labile group, and R 2 , R 3 and R 4 are each a monovalent organic group having 1 to 30 carbon atoms, which may be the same or different. [ka] (In the formula, m is 0, 1, or 2. When m is 0, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, or 5, and 1≦n1+n2≦6. When m is 1, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1≦n1+n2≦8. When m is 2, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, or 5. , 5, 6, 7, 8, or 9, and 1≦n1+n2≦10. n3 is 1 or 2. n4 is 0, 1, 2, 3, or 4, provided that 1≦n3+n4≦5. n5 is 1 or 2. n6 is 0, 1, 2, 3, or 4, provided that 1≦n5+n6≦5. n7 is 0, 1, 2, 3, or 4. n8 is 1, 2, 3, or 4. R 11 ~R 18 are each independently a halogen atom or a hydrocarbyl group having 1 to 10 carbon atoms which may contain a heteroatom. 11 and R 12 , R 13 and R 14 , R 15 and R 16 , or R 17 and R 18 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms. R 21 ~R 24 are each independently a hydrocarbyl group having 1 to 40 carbon atoms which may contain a halogen atom or a heteroatom. When n2 is 2 or more, each R 21 may be the same or different, and multiple R 21 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n4 is 2 or more, each R 22 may be the same or different, and multiple R 22 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n6 is 2 or more, each R 23 may be the same or different, and multiple R 23 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n7 is 2 or more, each R24 may be the same or different, and multiple R 24 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are attached. R 25 is an (n8)-valent hydrocarbon group having 1 to 40 carbon atoms or an (n8)-valent heterocyclic group having 2 to 40 carbon atoms, and when n8 is 2, R 25 may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, a sulfonyl group, or a thioketone bond. In addition, some or all of the hydrogen atoms of the (n8)-valent hydrocarbon group or the (n8)-valent heterocyclic group may be substituted with a group containing a hetero atom, and some of the -CH2- of the (n8)-valent hydrocarbon group may be substituted with a group containing a hetero atom, and R 24 and R 25 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms.

[0038] Hereinafter, the substrate, the silicon-containing resist underlayer film, and the resist film will be described in that order. [substrate] The substrate is preferably a substrate for manufacturing an integrated circuit (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, etc.) or a substrate for manufacturing a mask circuit (Cr, CrO, CrON, MoSi2, SiO2, etc.).

[0039] [Silicon-containing resist underlayer film] The silicon-containing resist underlayer film is obtained from a silicon-containing resist underlayer film composition containing a thermally crosslinkable polysiloxane having a specific structure described below.

[0040] [Thermal crosslinkable polysiloxane] The thermally crosslinkable polysiloxane of the present invention will be described below. The thermally crosslinkable polysiloxane of the present invention is a thermally crosslinkable polysiloxane containing one or more repeating units represented by the following general formulas (1) to (3) and one or more repeating units represented by the following general formulas (4) to (6). [ka] (In the formula, R 1 is an organic group having a carboxyl group or an organic group having a carboxyl group substituted with an acid labile group, and R 2 , R 3 and R 4 are each a monovalent organic group having 1 to 30 carbon atoms, which may be the same or different.

[0041] R in the above general formulas (1) to (3) 1 Examples of the bond include, but are not limited to, the following: In the following formula, (Si) is written to indicate the bonding site with Si. [ka]

[0042] [ka]

[0043] In the formula, R 2 , R 3 and R 4 R may be the same or different and are monovalent organic groups having 1 to 30 carbon atoms. 2 , R 3 is preferably a saturated or unsaturated organic group having 1 to 20 carbon atoms, which may have a substituent. Examples of the organic group include a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted linear, branched, or cyclic alkenyl group having 2 to 20 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, a vinyl group, an allyl group, a propenyl group, a phenyl group, and a tolyl group.

[0044] R 2 , R 3 , and R 4Another example of the organic group represented by the formula (Sm-R) is an organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds. Specifically, it is an organic group having one or more groups selected from the group consisting of ether bonds, ester bonds, alkoxy groups, hydroxy groups, and the like, excluding carboxy groups. Examples of such organic groups include those represented by the following general formula (Sm-R):

[0045] (P-Q1-(S1) v1 -Q2-)u-(T) v2 -Q3-(S2)v3-Q4- (Sm-R) (In general formula (Sm-R), P represents a hydrogen atom, a cyclic ether group, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 6 carbon atoms, or an alkylcarbonyl group having 2 to 6 carbon atoms; Q1, Q2, Q3, and Q4 each independently represent -CqH(2q-p)Pp- (wherein P is as defined above, p is an integer of 0 to 3, and q is an integer of 0 to 10 (with the proviso that q=0 represents a single bond)); u represents an integer of 0 to 3; S1 and S2 each independently represent -O-, -CO-, -OCO-, -COO-, or -OCOO-; v1, v2, and v3 each independently represent 0 or 1; and T represents a divalent group consisting of a divalent atom other than carbon, an alicyclic ring, an aromatic ring, or a heterocyclic ring.)

[0046] Examples of T that may contain a heteroatom such as an oxygen atom include an alicyclic ring, an aromatic ring, and a heterocyclic ring. The bonding positions of T to Q2 and Q3 are not particularly limited, but can be appropriately selected in consideration of steric reactivity, the availability of commercially available reagents used in the reaction, and the like.

[0047] [ka]

[0048] Preferred examples of the organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds in the general formula (Sm-R) include the following: In the following formula, (Si) is written to indicate the bonding site with Si.

[0049] [ka]

[0050] [ka]

[0051] Also, R 2 , R 3 , and R 4 As examples of the organic group, an organic group containing a silicon-silicon bond can also be used. Specific examples include the following: [ka]

[0052] Furthermore, R 2 , R 3 , and R 4 As an example of the organic group, an organic group having a fluorine atom can also be used. Specific examples include organic groups obtained from silicon compounds described in paragraphs (0059) to (0065) of JP-A No. 2012-53253.

[0053] The hydrolyzable monomer (Sm) has one, two or three hydrolyzable groups such as chlorine, bromine, iodine, acetoxy, methoxy, ethoxy, propoxy or butoxy groups bonded to the silicon atom represented by (Si) in the partial structure.

[0054] [Method for synthesizing thermally crosslinkable polysiloxane (raw materials)] The thermally crosslinkable polysiloxanes of the formulae (4) to (6) can be produced, for example, by hydrolysis and condensation of the following hydrolyzable monomers (Sm).

[0055] Specific examples of the hydrolyzable monomer (Sm) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrippropoxysilane, ethyltriisopropoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. Oxysilane, vinyl tripropoxysilane, vinyl triisopropoxysilane, propyl trimethoxysilane, propyl triethoxysilane, propyl tripropoxysilane, propyl triisopropoxysilane, isopropyl trimethoxysilane, isopropyl triethoxysilane, isopropyl tripropoxysilane, isopropyl triisopropoxysilane, butyl trimethoxysilane, butyl triethoxysilane, butyl tripropoxysilane, butyl triisopropoxysilane, isobutyl trimethoxysilane, isobutyl triethoxysilane Silane, isobutyl tripropoxysilane, isobutyl triisopropoxysilane, sec-butyl trimethoxysilane, sec-butyl triethoxysilane, sec-butyl tripropoxysilane, sec-butyl triisopropoxysilane, t-butyl trimethoxysilane, t-butyl triethoxysilane, t-butyl tripropoxysilane, t-butyl triisopropoxysilane, allyl trimethoxysilane, allyl triethoxysilane, allyl tripropoxysilane, allyl triisopropoxysilane, cyclopropyl trimethoxysilane, Cyclopropyltriethoxysilane, cyclopropyltripropoxysilane, cyclopropyltriisopropoxysilane, cyclobutyltrimethoxysilane, cyclobutyltriethoxysilane, cyclobutyltrippropoxysilane, cyclobutyltriisopropoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyltrippropoxysilane, cyclopentyltriisopropoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltrippropoxysilane,Cyclohexyltriisopropoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, cyclohexenyltripropoxysilane, cyclohexenyltriisopropoxysilane, cyclohexenylethyltrimethoxysilane, cyclohexenylethyltriethoxysilane, cyclohexenylethyltripropoxysilane, cyclohexenylethyltriisopropoxysilane, cyclooctyltrimethoxysilane, cyclooctyltriethoxysilane, cyclooctyltripropoxysilane, cyclooctyltriisopropoxysilane cyclopentadienylpropyltrimethoxysilane, cyclopentadienylpropyltriethoxysilane, cyclopentadienylpropyltripropoxysilane, cyclopentadienylpropyltriisopropoxysilane, bicycloheptenyltrimethoxysilane, bicycloheptenyltriethoxysilane, bicycloheptenyltrippropoxysilane, bicycloheptenyltriisopropoxysilane, bicycloheptyltrimethoxysilane, bicycloheptyltriethoxysilane, bicycloheptyltrippropoxysilane, bicycloheptyltriisopropoxysilane anisyltriisopropoxysilane, adamantyltrimethoxysilane, adamantyltriethoxysilane, adamantyltripropoxysilane, adamantyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrippropoxysilane, phenyltriisopropoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, benzyltrippropoxysilane, benzyltriisopropoxysilane, anisyltrimethoxysilane, anisyltriethoxysilane, anisyltrippropoxysilane, anisyl Triisopropoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, tolyltrippropoxysilane, tolyltriisopropoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, phenethyltrippropoxysilane, phenethyltriisopropoxysilane, naphthyltrimethoxysilane, naphthyltriethoxysilane, naphthyltrippropoxysilane, naphthyltriisopropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane,Dimethyldipropoxysilane, dimethyldiisopropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldiisopropoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dipropyldipropoxysilane, dipropyldiisopropoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldipropoxysilane, diisopropyldiisopropoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dibutyldipropoxy Silane, dibutyldiisopropoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyldipropoxysilane, di-sec-butyldiisopropoxysilane, di-t-butyldimethoxysilane, di-t-butyldiethoxysilane, di-t-butyldipropoxysilane, di-t-butyldiisopropoxysilane, dicyclopropyldimethoxysilane, dicyclopropyldiethoxysilane, dicyclopropyldipropoxysilane, dicyclopropyldiisopropoxysilane, dicyclobutyldimethoxysilane, dicyclopropyl Dicyclobutyldiethoxysilane, dicyclobutyldipropoxysilane, dicyclobutyldiisopropoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclopentyldipropoxysilane, dicyclopentyldiisopropoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclohexyldipropoxysilane, dicyclohexyldiisopropoxysilane, dicyclohexenyldimethoxysilane, dicyclohexenyldiethoxysilane, dicyclohexenyldipropoxysilane, dicyclo Hexenyl diisopropoxysilane, dicyclohexenyl ethyl dimethoxysilane, dicyclohexenyl ethyl diethoxysilane, dicyclohexenyl ethyl dipropoxysilane, dicyclohexenyl ethyl diisopropoxysilane, dicyclooctyl dimethoxysilane, dicyclooctyl diethoxysilane, dicyclooctyl dipropoxysilane, dicyclooctyl diisopropoxysilane, dicyclopentadienyl propyl dimethoxysilane, dicyclopentadienyl propyl diethoxysilane, dicyclopentadienyl propyl dipropoxysilane,Dicyclopentadienylpropyldiisopropoxysilane, bis(bicycloheptenyl)dimethoxysilane, bis(bicycloheptenyl)diethoxysilane, bis(bicycloheptenyl)dipropoxysilane, bis(bicycloheptenyl)diisopropoxysilane, bis(bicycloheptyl)dimethoxysilane, bis(bicycloheptyl)diethoxysilane, bis(bicycloheptyl)dipropoxysilane, bis(bicycloheptyl)diisopropoxysilane, diadamantyldimethoxysilane, diadamantyldiethoxysilane, diadamantyldipropoxysilane, diadamantyldi Examples include isopropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldiisopropoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethylethylmethoxysilane, dimethylethylethoxysilane, dimethylphenylmethoxysilane, dimethylphenylethoxysilane, dimethylbenzylmethoxysilane, dimethylbenzylethoxysilane, dimethylphenethylmethoxysilane, and dimethylphenethylethoxysilane.

[0056] Preferred examples of the above compound include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, and cyclohexenyltrimethoxysilane. Examples of such silane include cyclohexenyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, trimethylmethoxysilane, dimethylethylmethoxysilane, dimethylphenylmethoxysilane, dimethylbenzylmethoxysilane, and dimethylphenethylmethoxysilane.

[0057] [Method (reaction) for synthesizing thermally crosslinkable polysiloxane] (Synthesis method 1: acid catalyst) The thermally crosslinkable polysiloxane used in the present invention can be produced by hydrolyzing and condensing one or a mixture of two or more hydrolyzable monomers (Sm) in the presence of an acid catalyst.

[0058] Examples of the acid catalyst used here include organic acids such as formic acid, acetic acid, oxalic acid, maleic acid, methanesulfonic acid, benzenesulfonic acid, and toluenesulfonic acid, as well as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, and phosphoric acid. The amount of the catalyst used is preferably 1×10 to 10 mol, more preferably 1×10 to 5 mol, and even more preferably 1×10 to 1 mol, per mol of the monomer.

[0059] When obtaining a thermally crosslinkable polysiloxane from these monomers by hydrolysis and condensation, the amount of water added is preferably 0.01 to 100 mol, more preferably 0.05 to 50 mol, and even more preferably 0.1 to 30 mol per mol of hydrolyzable substituent bonded to the monomer. If the amount is 100 mol or less, the equipment used for the reaction can be small and economical. If the amount is 0.01 mol or more, the reaction proceeds sufficiently.

[0060] The operation method is to add the monomer to the aqueous catalyst solution to initiate the hydrolysis condensation reaction. At this time, an organic solvent may be added to the aqueous catalyst solution, or the monomer may be diluted with an organic solvent, or both may be performed. The reaction temperature is preferably 0 to 100°C, more preferably 5 to 80°C. A preferred method is to maintain the temperature at 5 to 80°C during the dropwise addition of the monomer, and then mature the mixture at 20 to 80°C.

[0061] Examples of organic solvents that can be added to the aqueous catalyst solution or that can be used to dilute the monomer include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, ethylene glycol, propylene glycol, acetone, acetonitrile, tetrahydrofuran, toluene, hexane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, and butanediol monoethyl ether. Preferred are propylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, and mixtures thereof.

[0062] Among these organic solvents, water-soluble ones are preferred. Examples include alcohols such as methanol, ethanol, 1-propanol, and 2-propanol; polyhydric alcohols such as ethylene glycol and propylene glycol; polyhydric alcohol condensate derivatives such as butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, and ethylene glycol monopropyl ether; acetone, acetonitrile, and tetrahydrofuran. Among these, those having a boiling point of 100° C. or less are particularly preferred.

[0063] The amount of organic solvent used is preferably 0 to 1,000 ml, particularly 0 to 500 ml, per mole of monomer. A smaller amount of organic solvent used allows for a smaller reaction vessel, which is more economical.

[0064] Thereafter, if necessary, a neutralization reaction of the catalyst is carried out to obtain an aqueous reaction mixture. At this time, the amount of alkaline substance that can be used for neutralization is preferably 0.1 to 2 equivalents relative to the acid used in the catalyst. This alkaline substance may be any substance that exhibits alkaline properties in water.

[0065] Subsequently, by-products such as alcohol produced in the hydrolysis-condensation reaction are preferably removed from the aqueous reaction mixture by vacuum removal or the like. The temperature to which the aqueous reaction mixture is heated depends on the types of organic solvent added and alcohol produced in the reaction, but is preferably 0 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C. The degree of vacuum used here varies depending on the types of organic solvent and alcohol to be removed, the exhaust device, the condenser, and the heating temperature, but is preferably atmospheric pressure or less, more preferably 80 kPa or less absolute pressure, and even more preferably 50 kPa or less absolute pressure. While it is difficult to accurately determine the amount of alcohol removed, it is desirable to remove approximately 80 mass% or more of the produced alcohol.

[0066] Next, the acid catalyst used in the hydrolysis and condensation may be removed from the aqueous reaction mixture. To remove the acid catalyst, water and the thermally crosslinkable polysiloxane solution are mixed, and the thermally crosslinkable polysiloxane is extracted with an organic solvent. The organic solvent used here is preferably one that can dissolve the thermally crosslinkable polysiloxane and separates into two layers when mixed with water. Examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, and mixtures thereof.

[0067] Furthermore, a mixture of a water-soluble organic solvent and a poorly water-soluble organic solvent can be used. For example, a methanol-ethyl acetate mixture, an ethanol-ethyl acetate mixture, a 1-propanol-ethyl acetate mixture, a 2-propanol-ethyl acetate mixture, a butanediol monomethyl ether-ethyl acetate mixture, a propylene glycol monomethyl ether-ethyl acetate mixture, an ethylene glycol monomethyl ether-ethyl acetate mixture, a butanediol monoethyl ether-ethyl acetate mixture, a propylene glycol monoethyl ether-ethyl acetate mixture, an ethylene glycol monoethyl ether-ethyl acetate mixture, a butanediol monopropyl ether-ethyl acetate mixture, a propylene glycol monopropyl ether-ethyl acetate mixture, an ethylene glycol monopropyl ether-ethyl acetate mixture, a methanol-methyl isobutyl ketone mixture, an ethanol-methyl isobutyl ketone mixture, a 1-propanol-methyl isobutyl ketone mixture, a 2-propanol-methyl isobutyl ketone mixture, a propylene glycol monomethyl ether-methyl isobutyl ketone mixture, an ethylene glycol monomethyl ether-methyl isobutyl ketone mixture, ton mixture, propylene glycol monoethyl ether-methyl isobutyl ketone mixture, ethylene glycol monoethyl ether-methyl isobutyl ketone mixture, propylene glycol monopropyl ether-methyl isobutyl ketone mixture, ethylene glycol monopropyl ether-methyl isobutyl ketone mixture, methanol-cyclopentyl methyl ether mixture, ethanol-cyclopentyl methyl ether mixture, 1-propanol-cyclopentyl methyl ether mixture, 2-propanol-cyclopentyl methyl ether mixture, propylene glycol monomethyl ether-cyclopentyl methyl ether mixture, ethylene glycol monomethyl ether-cyclopentyl methyl ether mixture, propylene glycol monoethyl ether-cyclopentyl methyl ether mixture, ethylene glycol monoethyl ether-cyclopentyl methyl ether mixture, propylene glycol monopropyl ether-cyclopentyl methyl ether mixture, ethylene glycol monopropyl ether-cyclopentyl methyl ether mixture,Preferred combinations include, but are not limited to, a methanol-propylene glycol methyl ether acetate mixture, an ethanol-propylene glycol methyl ether acetate mixture, a 1-propanol-propylene glycol methyl ether acetate mixture, a 2-propanol-propylene glycol methyl ether acetate mixture, a propylene glycol monomethyl ether-propylene glycol methyl ether acetate mixture, an ethylene glycol monomethyl ether-propylene glycol methyl ether acetate mixture, a propylene glycol monoethyl ether-propylene glycol methyl ether acetate mixture, an ethylene glycol monoethyl ether-propylene glycol methyl ether acetate mixture, a propylene glycol monopropyl ether-propylene glycol methyl ether acetate mixture, and an ethylene glycol monopropyl ether-propylene glycol methyl ether acetate mixture.

[0068] The mixing ratio of the water-soluble organic solvent to the poorly water-soluble organic solvent is selected as appropriate, but is preferably 0.1 to 1,000 parts by mass of the water-soluble organic solvent per 100 parts by mass of the poorly water-soluble organic solvent, more preferably 1 to 500 parts by mass, and even more preferably 2 to 100 parts by mass.

[0069] Subsequently, the solution may be washed with neutral water. This water may be what is commonly called deionized water or ultrapure water. The amount of water used is preferably 0.01 to 100 L, more preferably 0.05 to 50 L, and even more preferably 0.1 to 5 L, per 1 L of the thermally crosslinkable polysiloxane solution. This washing method involves placing both solutions in the same container, stirring, and then leaving the solution to stand to separate the aqueous layer. Washing may be performed once or more, but washing 10 or more times will not provide the desired effect, so washing is preferably performed about 1 to 5 times.

[0070] Other methods for removing the acid catalyst include a method using an ion exchange resin and a method of neutralizing the acid catalyst with an epoxy compound such as ethylene oxide or propylene oxide and then removing the acid catalyst. These methods can be appropriately selected depending on the acid catalyst used in the reaction.

[0071] This water washing operation may cause a portion of the thermally crosslinkable polysiloxane to escape into the aqueous layer, thereby providing an effect substantially equivalent to that of the fractionation operation. Therefore, the number of water washes and the amount of washing water may be appropriately selected in consideration of the catalyst removal effect and the fractionation effect.

[0072] In both the thermally crosslinkable polysiloxane solution containing a residual acid catalyst and the thermally crosslinkable polysiloxane solution from which the acid catalyst has been removed, the desired thermally crosslinkable polysiloxane solution is obtained by adding a final solvent and performing solvent exchange under reduced pressure. The temperature for solvent exchange depends on the types of reaction solvent and extraction solvent to be removed, but is preferably 0 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C. The degree of vacuum varies depending on the type of extraction solvent to be removed, the exhaust device, the condenser, and the heating temperature, but is preferably atmospheric pressure or less, more preferably 80 kPa or less absolute pressure, and even more preferably 50 kPa or less absolute pressure.

[0073] In this case, the change in solvent may cause the thermally crosslinkable polysiloxane to become unstable. This occurs due to the compatibility between the final solvent and the thermally crosslinkable polysiloxane. To prevent this, a monohydric, dihydric, or polyhydric alcohol having a cyclic ether as a substituent, as described in paragraphs (0181) and (0182) of JP 2009-126940 A, may be added as a stabilizer. The amount added is preferably 0 to 25 parts by mass, more preferably 0 to 15 parts by mass, and even more preferably 0 to 5 parts by mass, per 100 parts by mass of the thermally crosslinkable polysiloxane in the solution before the solvent exchange. However, if added, 0.5 parts by mass or more is preferred. If necessary, the solvent exchange operation may be performed by adding a monohydric, dihydric, or polyhydric alcohol having a cyclic ether as a substituent to the solution before the solvent exchange.

[0074] The thermally crosslinkable polysiloxane is preferably kept in a solution state of an appropriate concentration. The concentration at this time is preferably 0.1 to 20% by mass. At such a concentration, further condensation reaction does not proceed, and the polysiloxane does not change to a state in which it cannot be redissolved in an organic solvent. Furthermore, the amount of solvent required is reduced, which is economical and preferable.

[0075] The final solvent to be added to the thermally crosslinkable polysiloxane solution is preferably an alcohol-based solvent, and particularly preferably a monoalkyl ether derivative such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, or butanediol. Specifically, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, or diacetone alcohol is preferred.

[0076] If these solvents are the main component, it is also possible to add a non-alcoholic solvent as an auxiliary solvent, such as acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, or cyclopentyl methyl ether.

[0077] Another reaction procedure using an acid catalyst is to add water or a water-containing organic solvent to a monomer or an organic solution of the monomer to initiate the hydrolysis reaction. The catalyst may be added to the monomer or the organic solution of the monomer, or may be added to the water or the water-containing organic solvent. The reaction temperature is preferably 0 to 100°C, more preferably 10 to 80°C. A preferred method involves heating the mixture to 10 to 50°C during the dropwise addition of water, and then raising the temperature to 20 to 80°C for aging.

[0078] When an organic solvent is used, it is preferably a water-soluble one, and examples thereof include polyhydric alcohol condensate derivatives such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate, and mixtures thereof.

[0079] The amount of organic solvent used is preferably 0 to 1,000 ml, particularly 0 to 500 ml, per mole of monomer. A smaller amount of organic solvent used allows for a smaller reaction vessel, which is more economical. The aqueous reaction mixture obtained can be post-treated in the same manner as described above to obtain a thermally crosslinkable polysiloxane.

[0080] (Synthesis method 2: Alkaline catalyst) The thermally crosslinkable polysiloxane can be produced by hydrolyzing and condensing one or a mixture of two or more hydrolyzable monomers (Sm) in the presence of an alkali catalyst. Examples of the alkali catalyst used in this case include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, hexamethylenediamine, dimethylamine, diethylamine, ethylmethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, dicyclohexylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclocyclononene, diazabicycloundecene, hexamethylenetetramine, aniline, N,N-dimethylaniline, pyridine, N,N-dimethylaminopyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, tetramethylammonium hydroxide, choline hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide. The amount of the catalyst used is preferably 1×10 −6 mol to 10 mol, more preferably 1×10 −5 mol to 5 mol, and even more preferably 1×10 −4 mol to 1 mol, per mol of the monomer.

[0081] When obtaining a thermally crosslinkable polysiloxane from the above monomers by hydrolysis and condensation, the amount of water added is preferably 0.1 to 50 moles per mole of hydrolyzable substituent bonded to the monomer. If the amount is 50 moles or less, the equipment used for the reaction can be small and economical. If the amount is 0.1 mole or more, the reaction proceeds sufficiently.

[0082] The operation method is to add the monomer to the aqueous catalyst solution to initiate the hydrolysis condensation reaction. At this time, an organic solvent may be added to the aqueous catalyst solution, or the monomer may be diluted with an organic solvent, or both may be performed. The reaction temperature is preferably 0 to 100°C, more preferably 5 to 80°C. A preferred method is to maintain the temperature at 5 to 80°C during the dropwise addition of the monomer, and then mature the mixture at 20 to 80°C.

[0083] As the organic solvent that can be added to the aqueous alkali catalyst solution or that can dilute the monomer, the same organic solvents as those exemplified as those that can be added to the aqueous acid catalyst solution are preferably used. The amount of organic solvent used is preferably 0 to 1,000 ml per mole of monomer, in order to carry out the reaction economically.

[0084] Thereafter, if necessary, a neutralization reaction of the catalyst is carried out to obtain an aqueous reaction mixture. At this time, the amount of the acidic substance that can be used for neutralization is preferably 0.1 to 2 equivalents relative to the alkaline substance used in the catalyst. This acidic substance may be any substance that is acidic in water.

[0085] Subsequently, by-products such as alcohol produced in the hydrolysis-condensation reaction are preferably removed from the aqueous reaction mixture by vacuum removal or the like. The temperature to which the aqueous reaction mixture is heated depends on the type of organic solvent added and the type of alcohol produced in the reaction, but is preferably 0 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C. The degree of vacuum used here varies depending on the type of organic solvent and alcohol to be removed, the exhaust device, the condenser, and the heating temperature, but is preferably atmospheric pressure or less, more preferably 80 kPa or less absolute pressure, and even more preferably 50 kPa or less absolute pressure. While it is difficult to accurately determine the amount of alcohol removed, it is desirable to remove approximately 80 mass% or more of the produced alcohol.

[0086] Next, to remove the catalyst used in the hydrolysis and condensation, the thermally crosslinkable polysiloxane is extracted with an organic solvent. The organic solvent used here is preferably one that can dissolve the thermally crosslinkable polysiloxane and separates into two layers when mixed with water. Examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, and mixtures thereof.

[0087] Furthermore, it is also possible to use a mixture of a water-soluble organic solvent and a slightly water-soluble organic solvent.

[0088] Specific examples of the organic solvent used when removing the alkali catalyst include the organic solvents specifically exemplified above as those used when removing the acid catalyst, and mixtures of water-soluble organic solvents and poorly water-soluble organic solvents.

[0089] The mixing ratio of the water-soluble organic solvent to the poorly water-soluble organic solvent is appropriately selected, but is preferably 0.1 to 1,000 parts by mass of the water-soluble organic solvent per 100 parts by mass of the poorly water-soluble organic solvent, more preferably 1 to 500 parts by mass, and even more preferably 2 to 100 parts by mass.

[0090] The mixture is then washed with neutral water. This water may be what is commonly called deionized water or ultrapure water. The amount of water used is preferably 0.01 to 100 L, more preferably 0.05 to 50 L, and even more preferably 0.1 to 5 L per 1 L of the thermally crosslinkable polysiloxane solution. This washing method involves placing both components in the same container, stirring, and then allowing the mixture to stand to separate the aqueous layer. Washing may be performed once or more, but washing more than 10 times will not provide the desired effect, so washing is preferably performed about 1 to 5 times.

[0091] The final solvent is added to the washed thermally crosslinkable polysiloxane solution, and solvent exchange is performed under reduced pressure to obtain the desired thermally crosslinkable polysiloxane solution. The temperature for solvent exchange depends on the type of extraction solvent to be removed, but is preferably 0 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C. The degree of vacuum varies depending on the type of extraction solvent to be removed, the exhaust device, the condenser, and the heating temperature, but is preferably atmospheric pressure or less, more preferably 80 kPa or less absolute pressure, and even more preferably 50 kPa or less absolute pressure.

[0092] The final solvent to be added to the thermally crosslinkable polysiloxane solution is preferably an alcohol-based solvent, and particularly preferably a monoalkyl ether derivative such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, or dipropylene glycol.Specifically, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, or diacetone alcohol is preferred.

[0093] Another reaction procedure using an alkali catalyst involves adding water or a water-containing organic solvent to a monomer or an organic solution of the monomer to initiate the hydrolysis reaction. The catalyst may be added to the monomer or the organic solution of the monomer, or may be added to the water or the water-containing organic solvent. The reaction temperature is preferably 0 to 100°C, more preferably 10 to 80°C. A preferred method involves heating the mixture to 10 to 50°C during the dropwise addition of water, and then raising the temperature to 20 to 80°C for aging.

[0094] The organic solvent that can be used as the organic solution of the monomer or the aqueous organic solvent is preferably a water-soluble one, and examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, polyhydric alcohol condensate derivatives such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate, and mixtures thereof.

[0095] The molecular weight of the thermally crosslinkable polysiloxane obtained by synthesis method 1 or 2 can be adjusted not only by the selection of monomers but also by controlling the reaction conditions during polymerization, but a weight-average molecular weight of 100,000 or less prevents the generation of foreign matter or coating spots, so it is preferable to use one of 100,000 or less, more preferably 200 to 50,000, and even more preferably 300 to 30,000. Note that the data regarding the weight-average molecular weight above was measured by gel permeation chromatography (GPC) using RI as a detector and tetrahydrofuran as an eluent, and polystyrene as a standard substance, and the molecular weight was expressed in terms of polystyrene.

[0096] The physical properties of the thermally crosslinkable polysiloxane used in the present invention vary depending on the type of acid or alkali catalyst used during hydrolysis and condensation and the reaction conditions, and therefore can be appropriately selected depending on the desired performance of the resist underlayer film.

[0097] Furthermore, a polysiloxane derivative produced from a mixture of one or more hydrolyzable monomers (Sm) and a hydrolyzable metal compound represented by the following general formula (Mm) under the conditions using the acid or alkali catalyst can be used as a component of a composition for forming a resist underlayer film. U(OR 7 )m7(OR 8 )m8 (Mm) (In the general formula (Mm), R 7 , and R 8 are each independently an organic group having 1 to 30 carbon atoms, m7 + m8 is the same as the valence determined by the type of U, m7 and m8 are integers of 0 or more, and U is an element of Group III, IV, or V of the periodic table, excluding carbon and silicon.

[0098] Examples of the hydrolyzable metal compound represented by the general formula (Mm) used in this case include the following: When U is boron, examples of the hydrolyzable metal compound represented by the general formula (Mm) include boron methoxide, boron ethoxide, boron propoxide, boron butoxide, boron amyloxide, boron hexyloxide, boron cyclopentoxide, boron cyclohexyloxide, boron allyloxide, boron phenoxide, boron methoxyethoxide, boric acid, and boron oxide.

[0099] When U is aluminum, examples of the hydrolyzable metal compound represented by the general formula (Mm) include aluminum methoxide, aluminum ethoxide, aluminum propoxide, aluminum butoxide, aluminum amyloxide, aluminum hexyloxide, aluminum cyclopentoxide, aluminum cyclohexyloxide, aluminum allyloxide, aluminum phenoxide, aluminum methoxyethoxide, aluminum ethoxyethoxide, aluminum dipropoxyethyl acetoacetate, aluminum dibutoxyethyl acetoacetate, aluminum propoxybisethyl acetoacetate, aluminum butoxybisethyl acetoacetate, aluminum 2,4-pentanedionate, and aluminum 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0100] When U is gallium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include gallium methoxide, gallium ethoxide, gallium propoxide, gallium butoxide, gallium amyloxide, gallium hexyloxide, gallium cyclopentoxide, gallium cyclohexyloxide, gallium allyloxide, gallium phenoxide, gallium methoxyethoxide, gallium ethoxyethoxide, gallium dipropoxyethyl acetoacetate, gallium dibutoxyethyl acetoacetate, gallium propoxybisethyl acetoacetate, gallium butoxybisethyl acetoacetate, gallium 2,4-pentanedionate, and gallium 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0101] When U is yttrium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include yttrium methoxide, yttrium ethoxide, yttrium propoxide, yttrium butoxide, yttrium amyloxide, yttrium hexyloxide, yttrium cyclopentoxide, yttrium cyclohexyloxide, yttrium allyloxide, yttrium phenoxide, yttrium methoxyethoxide, yttrium ethoxyethoxide, yttrium dipropoxyethyl acetoacetate, yttrium dibutoxyethyl acetoacetate, yttrium propoxybisethyl acetoacetate, yttrium butoxybisethyl acetoacetate, yttrium 2,4-pentanedionate, and yttrium 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0102] When U is germanium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include germanium methoxide, germanium ethoxide, germanium propoxide, germanium butoxide, germanium amyloxide, germanium hexyloxide, germanium cyclopentoxide, germanium cyclohexyloxide, germanium allyloxide, germanium phenoxide, germanium methoxyethoxide, and germanium ethoxyethoxide.

[0103] When U is titanium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include titanium methoxide, titanium ethoxide, titanium propoxide, titanium butoxide, titanium amyloxide, titanium hexyloxide, titanium cyclopentoxide, titanium cyclohexyloxide, titanium allyloxide, titanium phenoxide, titanium methoxyethoxide, titanium ethoxyethoxide, titanium dipropoxybisethylacetoacetate, titanium dibutoxybisethylacetoacetate, titanium dipropoxybis2,4-pentanedionate, and titanium dibutoxybis2,4-pentanedionate.

[0104] When U is hafnium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include hafnium methoxide, hafnium ethoxide, hafnium propoxide, hafnium butoxide, hafnium amyloxide, hafnium hexyloxide, hafnium cyclopentoxide, hafnium cyclohexyloxide, hafnium allyloxide, hafnium phenoxide, hafnium methoxyethoxide, hafnium ethoxyethoxide, hafnium dipropoxybisethylacetoacetate, hafnium dibutoxybisethylacetoacetate, hafnium dipropoxybis 2,4-pentanedionate, and hafnium dibutoxybis 2,4-pentanedionate.

[0105] When U is tin, examples of the hydrolyzable metal compound represented by the general formula (Mm) include methoxytin, ethoxytin, propoxytin, butoxytin, phenoxytin, methoxyethoxytin, ethoxyethoxytin, tin 2,4-pentanedionate, and tin 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0106] When U is arsenic, examples of the hydrolyzable metal compound represented by the general formula (Mm) include methoxy arsenic, ethoxy arsenic, propoxy arsenic, butoxy arsenic, and phenoxy arsenic.

[0107] When U is antimony, examples of the hydrolyzable metal compound represented by the general formula (Mm) include methoxyantimony, ethoxyantimony, propoxyantimony, butoxyantimony, phenoxyantimony, antimony acetate, and antimony propionate.

[0108] When U is niobium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include methoxy niobium, ethoxy niobium, propoxy niobium, butoxy niobium, and phenoxy niobium.

[0109] When U is tantalum, examples of the hydrolyzable metal compound represented by the general formula (Mm) include methoxytantalum, ethoxytantalum, propoxytantalum, butoxytantalum, and phenoxytantalum.

[0110] When U is bismuth, examples of the hydrolyzable metal compound represented by the general formula (Mm) include methoxybismuth, ethoxybismuth, propoxybismuth, butoxybismuth, and phenoxybismuth.

[0111] When U is phosphorus, examples of the hydrolyzable metal compound represented by the general formula (Mm) include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, and diphosphorus pentoxide.

[0112] When U is vanadium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include vanadium oxide bis(2,4-pentanedionate), vanadium 2,4-pentanedionate, vanadium tributoxide oxide, and vanadium tripropoxide oxide.

[0113] When U is zirconium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include methoxyzirconium, ethoxyzirconium, propoxyzirconium, butoxyzirconium, phenoxyzirconium, zirconium dibutoxide bis(2,4-pentanedionate), and zirconium dipropoxide bis(2,2,6,6-tetramethyl-3,5-heptanedionate).

[0114] [Amount of thermally crosslinkable polysiloxane added] In the silicon-containing resist underlayer film composition of the present invention, the blend amount of the thermally crosslinkable polysiloxane is preferably, for example, 0.1 to 10% by mass relative to the solvent.

[0115] [Siloxane polymerization crosslinking catalyst] The silicon-containing resist underlayer film composition of the present invention contains, in addition to the thermally crosslinkable polysiloxane, a compound represented by the following general formula (Xc): Hereinafter, this compound may also be referred to as a siloxane polymerization crosslinking catalyst or simply a crosslinking catalyst:

[0116] In the present invention, the crosslinking catalyst for siloxane polymerization may be a sulfonium salt, an iodonium salt, a phosphonium salt, an ammonium salt, a polysiloxane having any of these as part of its structure, or an alkali metal salt.

[0117] Examples of the siloxane polymerization crosslinking catalyst (Xc) include compounds represented by the following general formula (Xc0). LaHbA (Xc0) (In the formula, L is lithium, sodium, potassium, rubidium, cesium, sulfonium, iodonium, phosphonium, or ammonium, A is a non-nucleophilic counter ion, a is an integer of 1 or more, b is an integer of 0 or 1 or more, and a+b is the valence of the non-nucleophilic counter ion.)

[0118] Specific examples of (Xc0) include sulfonium salts of the following general formula (Xc-1), iodonium salts of (Xc-2), phosphonium salts of (Xc-3), and ammonium salts and alkali metal salts of (Xc-4).

[0119] Examples of the sulfonium salt (Xc-1), iodonium salt (Xc-2), and phosphonium salt (Xc-3) are as follows: [ka]

[0120] Further, examples of the ammonium salt (Xc-4) include the following. [ka] (In the formula, R 204 , R 205 , R 206 , R 207represents a linear, branched or cyclic alkyl group, alkenyl group, oxoalkyl group or oxoalkenyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxoalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with an alkoxy group or the like. 205 and R 206 may form a ring, and when a ring is formed, R 205 , R 206 Each represents an alkylene group having 1 to 6 carbon atoms. A- represents a non-nucleophilic counter ion. R 208 , R 209 , R 210 , R 211 is R 204 , R 205 , R 206 , R 207 R is the same as R, but may also be a hydrogen atom. 208 and R 209 , R 208 and R209 and R 210 may form a ring, and when a ring is formed, R 208 and R 209 and R208 and R 209 and R 210 represents an alkylene group having 3 to 10 carbon atoms.

[0121] Above R 204 , R 205 , R 206 , R 207 , R 208 , R 209 , R 210 , R 211may be the same or different, and specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl. Examples of alkenyl groups include vinyl, allyl, propenyl, butenyl, hexenyl, and cyclohexenyl. Examples of oxoalkyl groups include 2-oxocyclopentyl and 2-oxocyclohexyl groups, such as 2-oxopropyl, 2-cyclopentyl-2-oxoethyl, 2-cyclohexyl-2-oxoethyl, and 2-(4-methylcyclohexyl)-2-oxoethyl. Examples of the aryl group include a phenyl group, a naphthyl group, etc., alkoxyphenyl groups such as p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, and m-tert-butoxyphenyl group, alkylphenyl groups such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, and dimethylphenyl group, alkylnaphthyl groups such as methylnaphthyl group and ethylnaphthyl group, alkoxynaphthyl groups such as methoxynaphthyl group and ethoxynaphthyl group, dialkylnaphthyl groups such as dimethylnaphthyl group and diethylnaphthyl group, and dialkoxynaphthyl groups such as dimethoxynaphthyl group and diethoxynaphthyl group, etc. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group. Examples of the aryloxoalkyl group include 2-aryl-2-oxoethyl groups such as a 2-phenyl-2-oxoethyl group, a 2-(1-naphthyl)-2-oxoethyl group, and a 2-(2-naphthyl)-2-oxoethyl group.

[0122] Non-nucleophilic counter ions of A- include hydroxide ion, formate ion, acetate ion, propionate ion, butanoate ion, pentanoate ion, hexanoate ion, heptanoate ion, octanoate ion, nonanoate ion, decanoate ion, oleate ion, stearate ion, linoleate ion, linolenate ion, benzoate ion, phthalate ion, isophthalate ion, terephthalate ion, salicylate ion, trifluoroacetate ion, monochloroacetate ion, dichloroacetate ion, trichloroacetate ion, fluoride ion, chloride ion, bromide ion, iodide ion, and nitrate ion. Examples of ions include monovalent ions such as nitrite ion, chlorate ion, bromate ion, methanesulfonate ion, paratoluenesulfonate ion, and monomethylsulfate ion; monovalent or divalent oxalate ion, malonate ion, methylmalonate ion, ethylmalonate ion, propylmalonate ion, butylmalonate ion, dimethylmalonate ion, diethylmalonate ion, succinate ion, methylsuccinate ion, glutarate ion, adipate ion, itaconate ion, maleate ion, fumarate ion, citraconic acid ion, citrate ion, carbonate ion, and sulfate ion.

[0123] Examples of alkali metal salts include monovalent salts such as hydroxide, formate, acetate, propionate, butanoate, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, oleate, stearate, linoleate, linolenate, benzoate, phthalate, isophthalate, terephthalate, salicylate, trifluoroacetate, monochloroacetate, dichloroacetate, and trichloroacetate; monovalent or divalent oxalate; malonate, methylmalonate, ethylmalonate, propylmalonate, butylmalonate, dimethylmalonate, diethylmalonate, succinate, methylsuccinate, glutarate, adipate, itaconate, maleate, fumarate, citraconate, citrate, and carbonate of lithium, sodium, potassium, and cesium.

[0124] (Sulfonium salt (Xc-1)) Specifically, examples of the sulfonium salt (Xc-1) include triphenylsulfonium formate, triphenylsulfonium acetate, triphenylsulfonium propionate, triphenylsulfonium butanoate, triphenylsulfonium benzoate, triphenylsulfonium phthalate, triphenylsulfonium isophthalate, triphenylsulfonium terephthalate, triphenylsulfonium salicylate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium monochloroacetate, triphenylsulfonium dichloroacetate, triphenylsulfonium trichloroacetate, triphenylsulfonium hydroxide, triphenylsulfonium nitrate, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenylsulfonium oxalate, triphenylsulfonium malonate, triphenylsulfonium methylmalonate, ethylenediamine, ethylenediamine, ethylenediamine, ethylenediamine, ethylenediamine, ethylenediamine Examples of the alkyl esters include triphenylsulfonium ethylmalonate, triphenylsulfonium propylmalonate, triphenylsulfonium butylmalonate, triphenylsulfonium dimethylmalonate, triphenylsulfonium diethylmalonate, triphenylsulfonium succinate, triphenylsulfonium methylsuccinate, triphenylsulfonium glutarate, triphenylsulfonium adipate, triphenylsulfonium itaconate, triphenylsulfonium maleate, triphenylsulfonium fumarate, triphenylsulfonium citraconic acid, triphenylsulfonium citrate, triphenylsulfonium carbonate, bistriphenylsulfonium oxalate, bistriphenylsulfonium maleate, bistriphenylsulfonium fumarate, bistriphenylsulfonium citraconic acid, bistriphenylsulfonium citrate, and bistriphenylsulfonium carbonate.

[0125] (Iodonium salt (Xc-2)) Specific examples of the iodonium salt (Xc-2) include diphenyliodonium formate, diphenyliodonium acetate, diphenyliodonium propionate, diphenyliodonium butanoate, diphenyliodonium benzoate, diphenyliodonium phthalate, diphenyliodonium isophthalate, diphenyliodonium terephthalate, diphenyliodonium salicylate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium monochloroacetate, diphenyliodonium dichloroacetate, diphenyliodonium trichloroacetate, diphenyliodonium hydroxide, Examples of the diphenyliodonium carbonate include bisdiphenyliodonium oxalate, bisdiphenyliodonium maleate, bisdiphenyliodonium fumarate, bisdiphenyliodonium citraconic acid, bisdiphenyliodonium citrate, and bisdiphenyliodonium carbonate.

[0126] (Phosphonium salt (Xc-3)) Specific examples of the phosphonium salt (Xc-3) include tetraethylphosphonium formate, tetraethylphosphonium acetate, tetraethylphosphonium propionate, tetraethylphosphonium butanoate, tetraethylphosphonium benzoate, tetraethylphosphonium phthalate, tetraethylphosphonium isophthalate, tetraethylphosphonium terephthalate, tetraethylphosphonium salicylate, tetraethylphosphonium trifluoromethanesulfonate, tetraethylphosphonium trifluoroacetate, tetraethylphosphonium monochloroacetate, tetraethylphosphonium dichloroacetate, tetraethylphosphonium trichloroacetate, tetraethylphosphonium hydroxide, tetraethylphosphonium nitrate, tetraethylphosphonium chloride, tetraethylphosphonium bromide, tetraethylphosphonium iodide, tetraethylphosphonium oxalate, tetraethylphosphonium maleate, tetraethylphosphonium fumarate, tetraethylphosphonium citraconic acid, tetraethylphosphonium citrate, tetraethylphosphonium carbonate, bistetraethylphosphonium oxalate, bistetraethylphosphonium maleate, thiaminyl phosphonium, bistetraethylphosphonium fumarate, bistetraethylphosphonium citraconic acid, bistetraethylphosphonium citrate, bistetraethylphosphonium carbonate, tetraphenylphosphonium formate, tetraphenylphosphonium acetate, tetraphenylphosphonium propionate, tetraphenylphosphonium butanoate, tetraphenylphosphonium benzoate, tetraphenylphosphonium phthalate, tetraphenylphosphonium isophthalate, tetraphenylphosphonium terephthalate, tetraphenylphosphonium salicylate, tetraphenylphosphonium trifluoromethanesulfonate, tetraphenylphosphonium trifluoroacetate, tetraphenylphosphonium monochloroacetate, tetraphenylphosphonium dichloroacetate, tetraphenylphosphonium trichloroacetate, tetraphenylphosphonium hydroxide, tetraphenylphosphonium nitrate, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, tetraphenylphosphonium oxalate, tetraphenylphosphonium maleate, tetraphenylphosphonium fumarate,Examples of such tetraphenylphosphonium compounds include tetraphenylphosphonium citrate, tetraphenylphosphonium carbonate, bistetraphenylphosphonium oxalate, bistetraphenylphosphonium maleate, bistetraphenylphosphonium fumarate, bistetraphenylphosphonium citraconic acid, bistetraphenylphosphonium citrate, and bistetraphenylphosphonium carbonate.

[0127] (Ammonium salt (Xc-4)) On the other hand, specific examples of the ammonium salt (Xc-4) include tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butanoate, tetramethylammonium benzoate, tetramethylammonium phthalate, tetramethylammonium isophthalate, tetramethylammonium terephthalate, tetramethylammonium salicylate, tetramethylammonium trifluoromethanesulfonate, tetramethylammonium trifluoroacetate, tetramethylammonium monochloroacetate, tetramethylammonium dichloroacetate, tetramethylammonium trichloroacetate, tetramethylammonium hydroxide, tetramethylammonium nitrate, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium monomethylsulfate, tetramethylammonium oxalate, tetramethylammonium malonate, tetramethylammonium maleate, tetramethylammonium fumarate, tetramethylammonium citraconate, tetramethylammonium citrate, and tetramethylammonium carbonate. ammonium, bistetramethylammonium oxalate, bistetramethylammonium malonate, bistetramethylammonium maleate, bistetramethylammonium fumarate, bistetramethylammonium citraconate, bistetramethylammonium citrate, bistetramethylammonium carbonate, tetraethylammonium formate, tetraethylammonium acetate, tetraethylammonium propionate, tetraethylammonium butanoate, tetraethylammonium benzoate, tetraethylammonium phthalate, tetraethylammonium isophthalate, tetraethylammonium terephthalate, tetraethylammonium salicylate, tetraethylammonium trifluoromethanesulfonate, tetraethylammonium trifluoroacetate, tetraethylammonium monochloroacetate, tetraethylammonium dichloroacetate, tetraethylammonium trichloroacetate, tetraethylammonium hydroxide, tetraethylammonium nitrate, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetraethylammonium monomethylsulfate,Tetraethylammonium oxalate, tetraethylammonium malonate, tetraethylammonium maleate, tetraethylammonium fumarate, tetraethylammonium citraconate, tetraethylammonium citrate, tetraethylammonium carbonate, bistetraethylammonium oxalate, bistetraethylammonium malonate, bistetraethylammonium maleate, bistetraethylammonium fumarate, bistetraethylammonium citraconate, bistetraethylammonium citrate, bistetraethylammonium carbonate, tetrapropylammonium formate, tetrapropylammonium acetate, tetrapropylammonium propionate, tetrapropylammonium butanoate, tetrapropylammonium benzoate, tetrapropylammonium phthalate, tetrapropylammonium isophthalate, tetrapropylammonium terephthalate, tetrapropylammonium salicylate, tetrapropylammonium trifluoromethanesulfonate, tetrapropylammonium trifluoroacetate, tetrapropylammonium monochloroacetate, dipropylammonium benzoate, tetrapropylammonium phthalate, tetrapropylammonium isophthalate, tetrapropylammonium terephthalate, tetrapropylammonium salicylate, tetrapropylammonium trifluoromethanesulfonate, tetrapropylammonium trifluoroacetate, tetrapropylammonium monochloroacetate, dipropylammonium benzoate, tetrapropylammonium phthalate, tetrapropylammonium benzoate, tetrapropylammonium phthalate, tetrapropylammonium isophthalate, tetrapropylammonium terephthalate, tetrapropylammonium salicylate, tetrapropylammonium trifluoromethanesulfonate, tetrapropylammonium trifluoroacetate, tetrapropylammonium monochloroacetate, dipropylammonium benzoate, tetra ...benzoate, Tetrapropylammonium dichloroacetate, tetrapropylammonium trichloroacetate, tetrapropylammonium hydroxide, tetrapropylammonium nitrate, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium iodide, tetrapropylammonium monomethylsulfate, tetrapropylammonium oxalate, tetrapropylammonium malonate, tetrapropylammonium maleate, tetrapropylammonium fumarate, tetrapropylammonium citraconate, tetrapropylammonium citrate, tetrapropylammonium carbonate, bistetrapropylammonium oxalate, bistetrapropylammonium malonate, bistetrapropylammonium maleate, bistetrapropylammonium fumarate, bistetrapropylammonium citraconate, bistetrapropylammonium citrate, bistetrapropylammonium carbonate, tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, tetrabutylammonium butanoate, tetrabutylammonium benzoate,Tetrabutylammonium phthalate, tetrabutylammonium isophthalate, tetrabutylammonium terephthalate, tetrabutylammonium salicylate, tetrabutylammonium trifluoromethanesulfonate, tetrabutylammonium trifluoroacetate, tetrabutylammonium monochloroacetate, tetrabutylammonium dichloroacetate, tetrabutylammonium trichloroacetate, tetrabutylammonium hydroxide, tetrabutylammonium nitrate, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium methanesulfonate, tetrabutylammonium monomethylsulfate, tetrabutylammonium oxalate, tetrabutylammonium malonate, tetrabutylammonium maleate, tetrabutylammonium fumarate, tetrabutylammonium citraconic acid, tetrabutylammonium citrate, tetrabutylammonium carbonate, bistetrabutylammonium oxalate, bistetrabutylammonium malonate, bistetrabutylammonium maleate, bistetrabutylammonium fumarate, citric acid Bistetrabutylammonium citrate, bistetrabutylammonium carbonate, trimethylphenylammonium formate, trimethylphenylammonium acetate, trimethylphenylammonium propionate, trimethylphenylammonium butanoate, trimethylphenylammonium benzoate, trimethylphenylammonium phthalate, trimethylphenylammonium isophthalate, trimethylphenylammonium terephthalate, trimethylphenylammonium salicylate, trimethylphenylammonium trifluoromethanesulfonate, trimethylphenylammonium trifluoroacetate, trimethylphenylammonium monochloroacetate, trimethylphenylammonium dichloroacetate, trimethylphenylammonium trichloroacetate, trimethylphenylammonium hydroxide, trimethylphenylammonium nitrate, trimethylphenylammonium chloride, trimethylphenylammonium bromide, trimethylphenylammonium iodide, trimethylphenylammonium methanesulfonate, trimethylphenylammonium monomethylsulfate,Trimethylphenylammonium oxalate, trimethylphenylammonium malonate, trimethylphenylammonium maleate, trimethylphenylammonium fumarate, trimethylphenylammonium citraconate, trimethylphenylammonium citrate, trimethylphenylammonium carbonate, bistrimethylphenylammonium oxalate, bistrimethylphenylammonium malonate, bistrimethylphenylammonium maleate, bistrimethylphenylammonium fumarate, bistrimethylphenylammonium citraconate, bistrimethylphenylammonium citrate, bistrimethylphenylammonium carbonate, triethylphenylammonium formate, triethylphenylammonium acetate, triethylphenylammonium propionate, triethylphenylammonium butanoate, triethylphenylammonium benzoate, triethylphenylammonium phthalate, triethylphenylammonium isophthalate, triethylphenylammonium terephthalate, triethylphenylammonium salicylate, triethyltrifluoromethanesulfonate triethylphenylammonium, triethylphenylammonium trifluoroacetate, triethylphenylammonium monochloroacetate, triethylphenylammonium dichloroacetate, triethylphenylammonium trichloroacetate, triethylphenylammonium hydroxide, triethylphenylammonium nitrate, triethylphenylammonium chloride, triethylphenylammonium bromide, triethylphenylammonium iodide, triethylphenylammonium methanesulfonate, triethylphenylammonium monomethylsulfate, triethylphenylammonium oxalate, triethylphenylammonium malonate, triethylphenylammonium maleate, triethylphenylammonium fumarate, triethylphenylammonium citraconate, triethylphenylammonium citrate, triethylphenylammonium carbonate, bistriethylphenylammonium oxalate, bistriethylphenylammonium malonate, bistriethylphenylammonium maleate, bistriethylphenylammonium fumarate, bistriethylphenylammonium citraconateBistriethylphenylammonium citrate, bistriethylphenylammonium carbonate, benzyldimethylphenylammonium formate, benzyldimethylphenylammonium acetate, benzyldimethylphenylammonium propionate, benzyldimethylphenylammonium butanoate, benzyldimethylphenylammonium benzoate, benzyldimethylphenylammonium phthalate, benzyldimethylphenylammonium isophthalate, benzyldimethylphenylammonium terephthalate, benzyldimethylphenylammonium salicylate, benzyldimethylphenylammonium trifluoromethanesulfonate, benzyldimethylphenylammonium trifluoroacetate, benzyldimethylphenylammonium monochloroacetate, benzyldimethylphenylammonium dichloroacetate, benzyldimethylphenylammonium trichloroacetate, benzyldimethylphenylammonium hydroxide, benzyldimethylphenylammonium nitrate, benzyldimethylphenylammonium chloride Examples of the ammonium salt include ammonium bromide, benzyldimethylphenylammonium iodide, benzyldimethylphenylammonium methanesulfonate, benzyldimethylphenylammonium monomethylsulfate, benzyldimethylphenylammonium oxalate, benzyldimethylphenylammonium malonate, benzyldimethylphenylammonium maleate, benzyldimethylphenylammonium fumarate, benzyldimethylphenylammonium citraconate, benzyldimethylphenylammonium citrate, benzyldimethylphenylammonium carbonate, bisbenzyldimethylphenylammonium oxalate, bisbenzyldimethylphenylammonium malonate, bisbenzyldimethylphenylammonium maleate, bisbenzyldimethylphenylammonium fumarate, bisbenzyldimethylphenylammonium citraconate, bisbenzyldimethylphenylammonium citrate, and bisbenzyldimethylphenylammonium carbonate.

[0128] (alkali metal salts) Examples of alkali metal salts include lithium formate, lithium acetate, lithium propionate, lithium butanoate, lithium benzoate, lithium phthalate, lithium isophthalate, lithium terephthalate, lithium salicylate, lithium trifluoromethanesulfonate, lithium trifluoroacetate, lithium monochloroacetate, lithium dichloroacetate, lithium trichloroacetate, lithium hydroxide, lithium nitrate, lithium chloride, lithium bromide, lithium iodide, lithium methanesulfonate, lithium hydrogen oxalate, lithium hydrogen malonate, lithium hydrogen maleate, Lithium hydrogen fumarate, lithium hydrogen citraconic acid, lithium hydrogen citrate, lithium hydrogen carbonate, lithium oxalate, lithium malonate, lithium maleate, lithium fumarate, lithium citraconic acid, lithium citrate, lithium carbonate, sodium formate, sodium acetate, sodium propionate, sodium butanoate, sodium benzoate, sodium phthalate, sodium isophthalate, sodium terephthalate, sodium salicylate, sodium trifluoromethanesulfonate, sodium trifluoroacetate, sodium monochloroacetate, Sodium dichloroacetate, sodium trichloroacetate, sodium hydroxide, sodium nitrate, sodium chloride, sodium bromide, sodium iodide, sodium methanesulfonate, sodium hydrogen oxalate, sodium hydrogen malonate, sodium hydrogen maleate, sodium hydrogen fumarate, sodium hydrogen citraconate, sodium hydrogen citrate, sodium bicarbonate, sodium oxalate, sodium malonate, sodium maleate, sodium fumarate, sodium citraconate, sodium citrate, sodium carbonate, potassium formate, potassium acetate, potassium propionate, potassium butanoate, potassium benzoate, potassium phthalate, potassium isophthalate, potassium terephthalate, potassium salicylate, potassium trifluoromethanesulfonate, potassium trifluoroacetate, potassium monochloroacetate, potassium dichloroacetate, potassium trichloroacetate, potassium hydroxide, potassium nitrate, potassium chloride, potassium bromide, potassium iodide, potassium methanesulfonate, potassium hydrogen oxalate, potassium hydrogen malonate, potassium hydrogen maleate, potassium hydrogen fumarate, potassium hydrogen citraconate,Examples include potassium hydrogen citrate, potassium hydrogen carbonate, potassium oxalate, potassium malonate, potassium maleate, potassium fumarate, potassium citraconate, potassium citrate, and potassium carbonate.

[0129] [Thermosetting polysiloxanes having ammonium salts, sulfonium salts, phosphonium salts, or iodonium salts as part of their structure as curing catalysts (Xc)] In the present invention, examples of the polymerization crosslinking catalyst (Xc) include thermosetting polysiloxanes (Xc-10) having an ammonium salt, a sulfonium salt, a phosphonium salt, or an iodonium salt as part of their structure.

[0130] As a raw material used to produce (Xc-10) used here, a compound represented by the following general formula (Xm) can be used. R 1 AA1R2AA2R3AA3Si(OR0A)(4-A1-A2-A3) (Xm) (In the formula, R0A is a hydrocarbon group having 1 to 6 carbon atoms, at least one of R1A, R2A, and R3A is an organic group having an ammonium salt, a sulfonium salt, a phosphonium salt, or an iodonium salt, and the others are a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms. A1, A2, and A3 are 0 or 1, and 1≦A1+A2+A3≦3.) Here, examples of OROA include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, and a phenyl group.

[0131] (Hydrolyzable silicon compound (Xm-1) having a sulfonium salt as part of its structure) As Xm, for example, the following general formula (Xm-1) can be exemplified as a hydrolyzable silicon compound having a sulfonium salt as part of its structure. [ka]

[0132] (In the formula, R SA1 , R SA2 each represents a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxyalkyl group having 7 to 20 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with an alkoxy group, an amino group, an alkylamino group, a halogen atom, or the like. SA1 and R SA2 may form a ring together with the sulfur atom to which they are attached, and when they form a ring, R SA1 , R SA2 R represents an alkylene group having 1 to 6 carbon atoms. SA3 R is a linear, branched or cyclic alkylene group or alkenylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene or aralkylene group having 6 to 20 carbon atoms, some or all of the hydrogen atoms of these groups may be substituted with an alkoxy group, an amino group, an alkylamino group or the like. SA1 , R SA2 , R SA3 may have an oxygen atom or a nitrogen atom in the middle of the chain or ring.

[0133] In the above general formula (Xm-1), (Si) is written to indicate the bonding site with Si.

[0134] X- can be hydroxide ion, formate ion, acetate ion, propionate ion, butanoate ion, pentanoate ion, hexanoate ion, heptanoate ion, octanoate ion, nonanoate ion, decanoate ion, oleate ion, stearate ion, linoleate ion, linolenate ion, benzoate ion, p-methylbenzoate ion, pt-butylbenzoate ion, phthalate ion, isophthalate ion, terephthalate ion, salicylate ion, trifluoroacetate ion, monochloroacetate ion, dichloroacetate ion, Acid ions, trichloroacetate ions, nitrate ions, chlorate ions, perchlorate ions, bromate ions, iodate ions, oxalate ions, malonate ions, methylmalonate ions, ethylmalonate ions, propylmalonate ions, butylmalonate ions, dimethylmalonate ions, diethylmalonate ions, succinate ions, methylsuccinate ions, glutarate ions, adipate ions, itaconate ions, maleate ions, fumarate ions, citraconic acid ions, citrate ions, and carbonate ions.

[0135] Specific examples of the cation moiety of the compound represented by the above general formula (Xm-1) include the following ions (X − is the same as above). [ka]

[0136] (Hydrolyzable silicon compounds having iodonium salts as part of their structure) For example, the following hydrolyzable silicon compound having an iodonium salt as part of its structure is An example is the general formula (Xm-2). [ka]

[0137] (In the formula, R IA1represents a linear, branched or cyclic alkyl group, alkenyl group, oxoalkyl group or oxoalkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxoalkyl group having 7 to 20 carbon atoms, and some or all of the hydrogen atoms in this group may be substituted with an alkoxy group, an amino group, an alkylamino group, a halogen atom or the like. IA1 and R IA2 may form a ring together with the nitrogen atom to which they are attached, and when they form a ring, R IA1 , R IA2 R represents an alkylene group having 1 to 6 carbon atoms. IA2 R is a linear, branched or cyclic alkylene group or alkenylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene or aralkylene group having 6 to 20 carbon atoms, some or all of the hydrogen atoms of these groups may be substituted with an alkoxy group, an amino group, an alkylamino group or the like. IA1 ~R IA2 may have an oxygen atom or a nitrogen atom in the middle of the chain or ring.

[0138] In the above general formula (Xm-2), (Si) is written to indicate the bonding site with Si. X- is as defined above.

[0139] Specific examples of the cation moiety of the compound represented by the above general formula (Xm-2) include the following ions (X − is the same as above). [ka]

[0140] (Hydrolyzable silicon compounds having phosphonium salts as part of their structure) For example, the following general formula (Xm-3) can be given as an example of a hydrolyzable silicon compound having a phosphonium salt as part of its structure. [ka]

[0141] (In the formula, R PA1 , R PA2 , R PA3 represents a linear, branched or cyclic alkyl group, alkenyl group, oxoalkyl group or oxoalkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxoalkyl group having 7 to 20 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with an alkoxy group, an amino group, an alkylamino group, a halogen atom or the like. PA1 and R PA2 may form a ring together with the phosphorus atom to which they are attached, and when they form a ring, R PA1 , R PA2 R represents an alkylene group having 1 to 6 carbon atoms. PA4 R is a linear, branched or cyclic alkylene group or alkenylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene or aralkylene group having 6 to 20 carbon atoms, some or all of the hydrogen atoms of these groups may be substituted with an alkoxy group, an amino group, an alkylamino group or the like. PA1 ~R PA4 may have an oxygen atom or a nitrogen atom in the middle of the chain or ring.

[0142] In the above general formula (Xm-3), (Si) is written to indicate the bonding site with Si. X- is as defined above.

[0143] Specific examples of the cation moiety of the compound represented by the above general formula (Xm-3) include the following ions (X − is the same as above).

[0144] [ka]

[0145] (Hydrolyzable silicon compounds having ammonium salts as part of their structure) For example, the following general formula (Xm-4) can be given as an example of a hydrolyzable silicon compound having an ammonium salt as part of its structure. [ka]

[0146] (In the formula, R NA1 , R NA2 , R NA3 are each a hydrogen atom, a linear, branched or cyclic alkyl group, alkenyl group, oxoalkyl group or oxoalkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxyalkyl group having 7 to 20 carbon atoms, and are monovalent organic groups in which some or all of the hydrogen atoms of these groups may be substituted with an alkoxy group, an amino group, an alkylamino group or the like. NA1 and R NA2 may form a ring together with the nitrogen atom to which they are attached, and when they form a ring, R NA1 , R NA2 R represents an alkylene group having 1 to 6 carbon atoms, or a nitrogen-containing heterocyclic ring or heteroaromatic ring. NA4 represents a linear, branched or cyclic alkylene group or alkenylene group having 1 to 23 carbon atoms, a substituted or unsubstituted arylene group having 6 to 29 carbon atoms, or a divalent organic group in which some or all of the hydrogen atoms of these groups may be substituted with an alkoxy group, an amino group, an alkylamino group or the like; R NA1 and R NA2 , R NA1 and R NA4 If the ring structure is formed and further contains an unsaturated nitrogen, nNA3 = 0, otherwise nNA3 = 1.)

[0147] In the above general formula (Xm-4), (Si) is written to indicate the bonding site with Si. X- is as defined above.

[0148] Specific examples of the cation moiety of the compound represented by the above general formula (Xm-4) include the following ions (X − is the same as above). [ka]

[0149] [ka]

[0150] [ka]

[0151] [ka]

[0152] [ka]

[0153] [ka]

[0154] [ka]

[0155] (organic solvent) The silicon-containing resist underlayer film composition of the present invention can contain a solvent.Preferably, the solvent is an alcohol-based organic solvent, and more preferably, monoalkyl ether derivatives such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, etc.Specifically, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, etc. are preferred.

[0156] If these solvents are the main component, it is also possible to add a non-alcoholic organic solvent as an auxiliary solvent, such as acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, or cyclopentyl methyl ether.

[0157] (water) Water may be added to the silicon-containing resist underlayer film composition of the present invention. Adding water hydrates the polysiloxane compound in the composition, thereby improving lithography performance. The water content in the solvent component of the silicon-containing resist underlayer film composition of the present invention is preferably greater than 0% by mass and less than 50% by mass, more preferably 0.3 to 30% by mass, and even more preferably 0.5 to 20% by mass. When the water content is less than 50% by mass, the silicon-containing resist underlayer film has good uniformity and does not bleed.

[0158] The silicon-containing resist underlayer film composition preferably contains a siloxane polymerization crosslinking catalyst (Xc), an alcohol-based organic solvent, and water.

[0159] (High boiling point solvent) Furthermore, a high-boiling solvent having a boiling point of 180° C. or higher can be added to the silicon-containing resist underlayer film composition of the present invention as needed. Examples of such high-boiling solvents include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecal, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, gamma butyrolactone, tripropylene glycol monomethyl ether, and diacetone alcohol. Examples of the high-boiling point solvent include ethanol, n-nonyl acetate, ethylene glycol monoethyl ether acetate, 1,2-diacetoxyethane, 1-acetoxy-2-methoxyethane, 1,2-diacetoxypropane, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, etc. The amount of the high-boiling point solvent to be blended is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, based on the solvent components.

[0160] The amount of the total solvent including water used is preferably 100 to 100,000 parts by mass, particularly 200 to 50,000 parts by mass, per 100 parts by mass of the polysiloxane compound as the base polymer.

[0161] [Other ingredients] (organic acid) To improve the stability of the silicon-containing resist underlayer film composition of the present invention, it is preferable to add a monovalent or divalent or higher organic acid having 1 to 30 carbon atoms. Examples of the acid to be added include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, dimethylmalonic acid, diethylmalonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and citric acid. Oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, and citric acid are particularly preferred. To maintain stability, two or more acids may be mixed and used. The amount added is 0.001 to 25 parts by mass, preferably 0.01 to 15 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of silicon contained in the composition.

[0162] (Photoacid generator) In the present invention, a photoacid generator may be added to the silicon-containing resist underlayer film composition. Specific examples of the photoacid generator used in the present invention include materials described in paragraphs (0160) to (0179) of JP-A-2009-126940.

[0163] (Photoacid generator (P-0)) Additionally, the present invention may include one or more compounds (photoacid generators) having an anion moiety and a cation moiety in one molecule, which are represented by the following general formula (P-0). [ka] (where R 300 is a divalent organic group substituted with one or more fluorine atoms, R 301and R302 each independently represent a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a heteroatom or which may be interrupted by a heteroatom. 303 represents a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with or may be interrupted by a heteroatom. 301 and R 302 , or R 301 and R 303 may be bonded to each other to form a ring together with the sulfur atom in the formula. 304 represents a single bond or a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with or interrupted by a heteroatom.

[0164] By combining such a compound (photoacid generator) with the thermosetting silicon-containing material of the present invention, it is possible to obtain a resist underlayer film that can contribute to rectangularizing the cross-sectional shape while maintaining the LWR of the upper layer resist.

[0165] In the above general formula (P-0), R 300 is a divalent organic group substituted with one or more fluorine atoms. The divalent organic group is, for example, a divalent hydrocarbon group having 1 to 20 carbon atoms, such as a linear, branched, or cyclic alkylene group, alkenylene group, or arylene group. R 300 Specific examples of the structure include the following:

[0166] [ka]

[0167] In the above formula, (SO3-) is written to indicate the bonding position with the SO3- group in the above general formula (P-0). 350 ) is a group in which the cation moiety in the general formula (P-0) is connected to R via L 300 This is to indicate the bonding point with the part that is bonded to the

[0168] R 301 and R 302are each independently a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, which may be substituted with or interrupted by a heteroatom, such as an alkyl group, alkenyl group, aryl group, or aralkyl group. Examples of alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group, and adamantyl group. Examples of alkenyl groups include vinyl group, allyl group, propenyl group, butenyl group, hexenyl group, and cyclohexenyl group. Examples of the oxoalkyl group include a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, a 2-oxopropyl group, a 2-oxoethyl group, a 2-cyclopentyl-2-oxoethyl group, a 2-cyclohexyl-2-oxoethyl group, and a 2-(4-methylcyclohexyl)-2-oxoethyl group. Examples of the aryl group include a phenyl group, a naphthyl group, a thienyl group, and the like; alkoxyphenyl groups such as a 4-hydroxyphenyl group, a 4-methoxyphenyl group, a 3-methoxyphenyl group, a 2-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-tert-butoxyphenyl group, and a 3-tert-butoxyphenyl group; alkylphenyl groups such as a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, a 4-tert-butylphenyl group, a 4-n-butylphenyl group, and a 2,4-dimethylphenyl group; alkylnaphthyl groups such as a methylnaphthyl group and an ethylnaphthyl group; alkoxynaphthyl groups such as a methoxynaphthyl group, an ethoxynaphthyl group, an n-propoxynaphthyl group, and an n-butoxynaphthyl group; dialkylnaphthyl groups such as a dimethylnaphthyl group and a diethylnaphthyl group; and dialkoxynaphthyl groups such as a dimethoxynaphthyl group and a diethoxynaphthyl group. Examples of the aralkyl group include a benzyl group, a 1-phenylethyl group, and a 2-phenylethyl group.Examples of the aryloxoalkyl group include 2-aryl-2-oxoethyl groups such as 2-phenyl-2-oxoethyl, 2-(1-naphthyl)-2-oxoethyl, and 2-(2-naphthyl)-2-oxoethyl. 301 and R 302 may be bonded to each other to form a ring together with the sulfur atom in the formula, and in that case, examples include groups represented by the following formula:

[0169] [ka] (Dashed lines represent bonds.)

[0170] In the above general formula (P-0), R 303 R represents a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with or may be interrupted by a heteroatom. 303 Specific examples of the alkyl group include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, and the like. Examples of suitable alkanediyl groups include linear alkanediyl groups such as tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, and heptadecane-1,17-diyl; saturated cyclic hydrocarbon groups such as cyclopentanediyl, cyclohexanediyl, norbornanediyl, and adamantanediyl; and unsaturated cyclic hydrocarbon groups such as phenylene and naphthylene. Some of the hydrogen atoms in these groups may be substituted with alkyl groups such as methyl, ethyl, propyl, n-butyl, and tert-butyl. Alternatively, they may be substituted with heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms, resulting in the formation of hydroxy groups, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate ester bonds, carbonate bonds, lactone rings, sultone rings, carboxylic acid anhydrides, and haloalkyl groups. Furthermore, R301 and R 303 may be bonded to each other to form a ring together with the sulfur atom in the formula, and in that case, examples include groups represented by the following formula:

[0171] [ka] (Dashed lines represent bonds.)

[0172] In the above general formula (P-0), L 304 represents a single bond or a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with or interrupted by a heteroatom. 304 Specific examples of the alkyl group include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, and the like. Examples of such alkyl groups include linear alkanediyl groups such as tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, and heptadecane-1,17-diyl; saturated cyclic hydrocarbon groups such as cyclopentanediyl, cyclohexanediyl, norbornanediyl, and adamantanediyl; and unsaturated cyclic hydrocarbon groups such as phenylene and naphthylene. Some of the hydrogen atoms in these groups may be substituted with alkyl groups such as methyl, ethyl, propyl, n-butyl, and tert-butyl. Alternatively, they may be substituted with heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms, resulting in the formation of hydroxy groups, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate ester bonds, carbonate bonds, lactone rings, sultone rings, carboxylic acid anhydrides, and haloalkyl groups.

[0173] The compound (photoacid generator) represented by the above general formula (P-0) is preferably represented by the following general formula (P-1). [ka] In the general formula (P-1), X 305 , X 306 are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but cannot all be hydrogen atoms. n307 is an integer of 1 to 4. R 301 , R 302 , R 303 and L 304 is as described above.

[0174] The photoacid generator represented by the above general formula (P-0) is more preferably represented by the following general formula (P-1-1). [ka]

[0175] In the above general formula (P-1-1), R 308 , R 309 and R 310each independently represents a hydrogen atom or a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, optionally interrupted by a heteroatom. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a tert-amyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, an n-nonyl group, an n-decyl group, a cyclopentyl group, a cyclohexyl group, a 2-ethylhexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclopentylbutyl group, a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylbutyl group, a norbornyl group, an oxanorbornyl group, a tricyclo[5.2.1.02,6]decanyl group, and an adamantyl group. In addition, some of the hydrogen atoms in these groups may be replaced with heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, or heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms may be present, resulting in the formation or presence of a hydroxy group, cyano group, carbonyl group, ether bond, ester bond, sulfonate ester bond, carbonate bond, lactone ring, sultone ring, carboxylic acid anhydride, haloalkyl group, etc. Preferred are a methyl group, a methoxy group, a tert-butyl group, and a tert-butoxy group.

[0176] In the above general formula (P-1-1), n 308 and n 309 Each represents an integer of 0 to 5, preferably 0 or 1. 310 represents an integer of 0 to 4, preferably 0 or 2. 304 , X 305 , X 306 , n 307 is as described above.

[0177] The compound (photoacid generator) represented by the above general formula (P-0) is more preferably represented by the following general formula (P-1-2). [ka] In the above general formula (P-1-2), A311 represents a hydrogen atom or a trifluoromethyl group. 308 , R 309, R 310 , n 308 , n 309 , n 310 , L 304 is as described above.

[0178] More specifically, the photoacid generators represented by the general formulae (P-0), (P-1), (P-1-1) and (P-1-2) above include the structures shown below, although the photoacid generators are not limited thereto.

[0179] [ka]

[0180] [ka]

[0181] [ka]

[0182] [ka]

[0183] [ka]

[0184] [ka]

[0185] The amount of the compound represented by the general formula (P-0) added is 0.001 to 40 parts by mass, preferably 0.1 to 40 parts by mass, and more preferably 0.1 to 20 parts by mass, relative to 100 parts by mass of the thermally crosslinkable polysiloxane. By adding such a photoacid generator, it is possible to reduce the residue in the exposed area of ​​the upper resist layer and form a pattern with a small LWR.

[0186] (stabilizer) Furthermore, in the present invention, a stabilizer can be added to the silicon-containing resist underlayer film composition. A monohydric or polyhydric alcohol having a cyclic ether as a substituent can be added as the stabilizer. In particular, the addition of a stabilizer described in paragraphs (0181) and (0182) of JP 2009-126940 A can improve the stability of the silicon-containing resist underlayer film-forming composition. The amount of stabilizer added can be preferably 0.001 to 50 parts by mass, more preferably 0.01 to 40 parts by mass, per 100 parts by mass of the thermally crosslinkable polysiloxane.

[0187] (surfactant) Furthermore, in the present invention, a surfactant can be blended into the composition as needed. Specific examples of such surfactants include those described in paragraph (0185) of JP-A No. 2009-126940. The amount of surfactant added is preferably 0 to 10 parts by mass, and more preferably 0 to 5 parts by mass, per 100 parts by mass of the thermally crosslinkable polysiloxane.

[0188] The silicon-containing resist underlayer film has the effect of preventing collapse of a fine pattern in the formation of a line and space pattern in a fine patterning process using a multilayer resist method in the manufacturing process of a semiconductor device, and has the effect of enabling the formation of a pattern with excellent CDU in the formation of a contact hole pattern.

[0189] When the silicon-containing resist underlayer film has a carboxyl group protected by an acid labile group, the acid labile group can be thermally decomposed in the baking step during the formation of the silicon-containing resist underlayer film, thereby exposing the carboxyl group to the surface of the silicon-containing resist underlayer film.

[0190] When the silicon-containing resist underlayer film has a carboxyl group protected by an acid labile group, the silicon-containing resist underlayer film composition contains a thermal acid generator, which makes it possible to lower the thermal decomposition temperature of the acid labile group and thereby reduce the process temperature.

[0191] The high adhesion between the silicon-containing resist underlayer film and the resist film is due to the presence of carboxy groups in the silicon-containing resist underlayer film after the baking process. By using the resist composition described below, the carboxy groups on the surface of the silicon-containing resist underlayer film and the carboxy groups of the carboxy group-containing compound contained in the resist composition are crosslinked by the hypervalent iodine compound during baking after application of the resist composition. Because the resist composition described below is a positive resist composition, crosslinking occurs between the pattern in the unexposed areas and the surface of the adhesive film, making the resist composition resistant to stresses during development and preventing collapse of the line-and-space pattern, making it useful for producing resist patterns with high aspect ratios. Meanwhile, in contact hole patterns, the high adhesion between the resist film and the silicon-containing resist underlayer film prevents the developer from penetrating between the resist film and the resist underlayer film and causing swelling, thereby forming contact hole patterns with excellent CDU.

[0192] [Resist film] The resist film used in the present invention will now be described. The resist film is obtained from a resist composition containing a predetermined hypervalent iodine compound, a carboxy group-containing compound, and a solvent.

[0193] [Hypervalent iodine compounds] The hypervalent iodine compound is a three-coordinate hypervalent iodine compound represented by the following formula (7), (8) or (9). [ka]

[0194] In formulas (7) to (9), m is 0, 1, or 2. When m is 0, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, or 5, and 1≦n1+n2≦6. When m is 1, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1≦n1+n2≦8. When m is 2, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, and 1≦n1+n2≦10. n3 is 1 or 2. n4 is 0, 1, 2, 3, or 4, with the proviso that 1≦n3+n4≦5. n5 is 1 or 2. n6 is 0, 1, 2, 3, or 4, with the proviso that 1≦n5+n6≦5. n7 is 0, 1, 2, 3, or 4. n8 is 1, 2, 3, or 4.

[0195] In formulas (7) to (9), R 11 ~R 18 are each independently a halogen atom or a hydrocarbyl group having 1 to 10 carbon atoms which may contain a heteroatom. 13 and R 14 , R 15 and R 16 , or R 17 and R 18 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms.

[0196] R 11 ~R 18 Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. 11 ~R 18The hydrocarbyl group having 1 to 10 carbon atoms represented by the formula (I) may be saturated or unsaturated, and may be linear, branched or cyclic. Specific examples thereof include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclic saturated hydrocarbyl groups having 3 to 10 carbon atoms, such as cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, tricyclo[5.2.1.02,6]decanyl, and adamantyl; alkenyl groups, such as vinyl and allyl; aryl groups having 6 to 10 carbon atoms, such as phenyl and naphthyl; and groups obtained by combining these groups. In addition, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom, and some of the -CH2- groups of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom, resulting in the hydrocarbyl group containing a hydroxy group, a cyano group, a halogen atom, a carbonyl group, an ether bond, a thioether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a carbamate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), or the like. 11 ~R 18 is preferably a hydrocarbyl group having 1 to 4 carbon atoms.

[0197] In formulas (7) to (9), R 21 ~R 24 are each independently a hydrocarbyl group having 1 to 40 carbon atoms which may contain a halogen atom or a heteroatom. When n2 is 2 or more, each R 21 may be the same or different, and multiple R 21 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n4 is 2 or more, each R 22may be the same or different, and multiple R 22 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n6 is 2 or more, each R 23 may be the same or different, and multiple R 23 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n7 is 2 or more, each R 24 may be the same or different, and multiple R 24 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are attached.

[0198] R 21 ~R 24 Specific examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. 21 ~R 24The hydrocarbyl group having 1 to 40 carbon atoms represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 40 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclic saturated hydrocarbyl groups having 3 to 40 carbon atoms, such as cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, tricyclo[5.2.1.02,6]decanyl, adamantyl, and adamantylmethyl; and aryl groups having 6 to 40 carbon atoms, such as phenyl, naphthyl, and anthracenyl. Furthermore, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom, and some of the -CH- groups of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom, and as a result, the hydrocarbyl group may contain a hydroxy group, a cyano group, a halogen atom, a carbonyl group, an ether bond, a thioether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a carbamate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), etc.

[0199] In formula (9), R 25 is an (n8)-valent hydrocarbon group having 1 to 40 carbon atoms or an (n8)-valent heterocyclic group having 2 to 40 carbon atoms, and when n8 is 2, R 25 may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, a sulfonyl group, or a thioketone bond. In addition, some or all of the hydrogen atoms of the (n8)-valent hydrocarbon group or the (n8)-valent heterocyclic group may be substituted with a group containing a hetero atom, and some of the -CH2- of the (n8)-valent hydrocarbon group may be substituted with a group containing a hetero atom, and R 24 and R 25may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms.

[0200] R 25 The (n8)-valent hydrocarbon group represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. The (n8)-valent hydrocarbon group is a group obtained by eliminating (n8) hydrogen atoms from a hydrocarbon. Examples of the hydrocarbon include alkanes having 1 to 40 carbon atoms, alkenes having 2 to 40 carbon atoms, alkynes having 2 to 40 carbon atoms, saturated cyclic hydrocarbons having 3 to 40 carbon atoms, unsaturated cyclic hydrocarbons having 3 to 40 carbon atoms, and aromatic hydrocarbons having 6 to 40 carbon atoms.

[0201] Specific examples of the alkanes having 1 to 40 carbon atoms include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, and structural isomers thereof.

[0202] Specific examples of the alkenes having 2 to 40 carbon atoms include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, and structural isomers thereof.

[0203] Specific examples of the alkyne having 2 to 40 carbon atoms include acetylene, propyne, butyne, pentyne, hexyne, heptyne, octyne, nonyne, decyne, and structural isomers thereof.

[0204] Specific examples of the cyclic saturated hydrocarbon having 3 to 40 carbon atoms include cyclopropane, cyclobutane, cyclohexane, cycloheptane, cyclooctane, adamantane, and norbornane.

[0205] Specific examples of the cyclic unsaturated hydrocarbon having 3 to 40 carbon atoms include cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and norbornene.

[0206] Specific examples of the aromatic hydrocarbon having 6 to 40 carbon atoms include benzene, naphthalene, and biphenyl.

[0207] R 25 The (n8)-valent heterocyclic group represented by the following formula is a group obtained by eliminating (n8) hydrogen atoms from a heterocyclic compound. Specific examples of the heterocyclic compound include furan, pyridine, pyrazole, and thiazolidine.

[0208] The (n8)-valent hydrocarbon group or (n8)-valent heterocyclic group may have some or all of its hydrogen atoms substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom, and as a result, may contain a hydroxy group, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Furthermore, the (n8)-valent hydrocarbon group may have some of its -CH2- groups substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom, and as a result, may contain a carbonyl group, an ether bond, a thioether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a carbamate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), etc.

[0209] Specific examples of the hypervalent iodine compound represented by formula (7) include, but are not limited to, the following: [ka]

[0210] [ka]

[0211] [ka]

[0212] [ka]

[0213] [ka]

[0214] [ka]

[0215] [ka]

[0216] [ka]

[0217] [ka]

[0218] [ka]

[0219] [ka]

[0220] [ka]

[0221] Specific examples of the hypervalent iodine compound represented by formula (8) include, but are not limited to, the following: [ka]

[0222] [ka]

[0223] [ka]

[0224] [ka]

[0225] Specific examples of the hypervalent iodine compound represented by formula (9) include, but are not limited to, the following: [ka]

[0226] [ka]

[0227] [ka]

[0228] [ka]

[0229] [ka]

[0230] [ka]

[0231] The carboxy group-containing compound is preferably a polymer containing a repeating unit represented by the following formula (10) or a compound represented by the following formula (11). [ka]

[0232] In formula (10), R A is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. A is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OX A1 -X A1 is a saturated hydrocarbylene group having 1 to 10 carbon atoms, a phenylene group, or a naphthylene group, and the saturated hydrocarbylene group may contain a hydroxy group, an ether bond, an ester bond, or a lactone ring. * represents a bond to a carbon atom in the main chain.

[0233] In formula (11), p is 1, 2, 3 or 4.

[0234] In formula (11), R 31 is a p-valent hydrocarbon group having 1 to 40 carbon atoms or a p-valent heterocyclic group having 2 to 40 carbon atoms, and when p is 2, R 31 may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, or a sulfonyl group. Some or all of the hydrogen atoms of the p-valent hydrocarbon group or p-valent heterocyclic group may be substituted with a group containing a heteroatom, and some of the -CH2- groups of the p-valent hydrocarbon group may be substituted with a group containing a heteroatom.

[0235] In formula (11), R 32 is a single bond or a hydrocarbylene group having 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing a hetero atom, or some of the -CH2- of the hydrocarbylene group may be substituted with a group containing a hetero atom. When p is 2, 3, or 4, each R 32 may be the same as or different from each other.

[0236] R 31The p-valent hydrocarbon group represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. The p-valent hydrocarbon group is a group obtained by eliminating p hydrogen atoms from a hydrocarbon. Examples of the hydrocarbon include alkanes having 1 to 40 carbon atoms, alkenes having 2 to 40 carbon atoms, alkynes having 2 to 40 carbon atoms, saturated cyclic hydrocarbons having 3 to 40 carbon atoms, unsaturated cyclic hydrocarbons having 3 to 40 carbon atoms, and aromatic hydrocarbons having 6 to 40 carbon atoms.

[0237] Examples of the alkanes having 1 to 40 carbon atoms include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, and structural isomers thereof.

[0238] Examples of the alkenes having 2 to 40 carbon atoms include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, and structural isomers thereof.

[0239] Examples of the alkyne having 2 to 40 carbon atoms include acetylene, propyne, butyne, pentyne, hexyne, heptyne, octyne, nonyne, decyne, and structural isomers thereof.

[0240] Examples of the cyclic saturated hydrocarbon having 3 to 40 carbon atoms include cyclopropane, cyclobutane, cyclohexane, cycloheptane, cyclooctane, adamantane, and norbornane.

[0241] Examples of the cyclic unsaturated hydrocarbon having 3 to 40 carbon atoms include cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and norbornene.

[0242] Examples of the aromatic hydrocarbon having 6 to 40 carbon atoms include benzene, naphthalene, and biphenyl.

[0243] R 31The p-valent heterocyclic group represented by the following formula is a group obtained by eliminating p hydrogen atoms from a heterocyclic compound. Examples of the heterocyclic compound include furan, pyridine, pyrazole, and thiazolidine.

[0244] The p-valent hydrocarbon group or p-valent heterocyclic group may have some or all of its hydrogen atoms substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom, and as a result, may contain a hydroxy group, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Furthermore, the p-valent hydrocarbon group may have some of its -CH- groups substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom, and as a result, may contain a carbonyl group, an ether bond, a thioether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a carbamate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride (-C(=O)-OC(=O)-), etc.

[0245] R 32The hydrocarbylene group represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include a methanediyl group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,1 alkanediyl groups having 1 to 20 carbon atoms, such as a 2-diyl group; cyclic saturated hydrocarbylene groups having 3 to 20 carbon atoms, such as a cyclopentanediyl group, a cyclohexanediyl group, a norbornanediyl group, and an adamantanediyl group; unsaturated aliphatic hydrocarbylene groups having 2 to 20 carbon atoms, such as a vinylene group and a propene-1,3-diyl group; arylene groups having 6 to 20 carbon atoms, such as a phenylene group and a naphthylene group; and groups obtained by combining these. In addition, some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom, or some of the -CH- constituting the hydrocarbylene group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom, and as a result, the hydrocarbylene group may contain a hydroxy group, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a carbonyl group, an ether bond, a thioether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a carbamate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride or the like.

[0246] Among the carboxylic acid compounds represented by formula (11), those in which p is 2, 3, or 4 are preferred. In this case, when mixed with a hypervalent iodine compound, a strong resist film with a high molecular weight is easily formed, which is preferred from the viewpoints of etching resistance and developer resistance.

[0247] In the carboxyl group-containing polymer represented by formula (10), specific examples of the carboxyl group-containing repeating unit represented by formula (10) include, but are not limited to, those shown below, where R A is the same as defined above. [ka]

[0248] [ka]

[0249] Examples of the carboxylic acid compound represented by formula (11) include, but are not limited to, the compounds shown below. [ka]

[0250] [ka]

[0251] [ka]

[0252] [ka]

[0253] [ka]

[0254] [ka]

[0255] The carboxyl group-containing polymer containing the repeating unit represented by formula (10) may further contain a repeating unit other than the repeating unit represented by formula (10) (hereinafter also referred to as "other repeating units"). The other repeating units are not particularly limited, but are preferably those that can improve the solubility in a solvent of a polymer that is poorly soluble in the carboxyl group-containing repeating unit alone. The other repeating units are preferably repeating units having a cyclic structure with a rigid skeleton that is expected to have high etching resistance, or repeating units containing a styrene skeleton.

[0256] Specific examples of the other repeating units include, but are not limited to, those shown below. A is the same as above, and X B are each independently —CH— or —O—. [ka]

[0257] [ka]

[0258] [ka]

[0259] [ka]

[0260] [ka]

[0261] [ka]

[0262] [ka]

[0263]

change

[0264]

change

[0265]

change

[0266]

change

[0267]

change

[0268]

change

[0269]

change

[0270]

change

[0271]

change

[0272]

change

[0273]

change

[0274]

change

[0275]

change

[0276]

change

[0277]

change

[0278]

change

[0279]

change

[0280]

change

[0281]

change

[0282]

change

[0283]

change

[0284] [ka]

[0285] [ka]

[0286] In the resist composition, the molar ratio of the hypervalent iodine compound to the carboxy group-containing compound (when the carboxy group-containing compound is a carboxy group-containing polymer, the molar ratio of the hypervalent iodine compound to the carboxylic acid-containing repeating units in the polymer) is preferably 10:90 to 90:10, more preferably 20:80 to 80:20, and even more preferably 30:70 to 70:30. The hypervalent iodine compounds may be used alone, or two or more compounds having different composition ratios, Mw, and / or Mw / Mn may be used in combination. The carboxy group-containing polymers may be used alone, or two or more compounds having different composition ratios, Mw, and / or Mw / Mn may be used in combination.

[0287] In the carboxyl group-containing polymer, the molar ratio of the carboxyl group-containing repeating units to the other repeating units is preferably 10:90 to 90:10, more preferably 15:85 to 85:15, and even more preferably 20:80 to 80:20.

[0288] The weight average molecular weight (Mw) of the carboxy group-containing polymer is preferably 1,000 to 500,000, more preferably 3,000 to 100,000. In the present invention, Mw is a value measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

[0289] Furthermore, if the carboxyl group-containing polymer has a broad molecular weight distribution (Mw / Mn), the presence of low-molecular-weight and high-molecular-weight polymers may result in the appearance of foreign matter on the pattern after exposure, or the pattern shape may be deteriorated. Therefore, since the effects of Mw and Mw / Mn tend to become greater as the pattern rule becomes finer, in order to obtain a resist composition that is suitable for use with fine pattern dimensions, it is preferable that the carboxyl group-containing polymer have a narrow Mw / Mn distribution of 1.0 to 2.0.

[0290] The carboxyl group-containing polymer can be synthesized, for example, by polymerizing a monomer that provides the repeating unit described above in an organic solvent with the addition of a radical polymerization initiator by heating.

[0291] Specific examples of organic solvents used in the polymerization reaction include toluene, benzene, THF, diethyl ether, dioxane, cyclohexane, cyclopentane, cyclopentanone, cyclohexanone, methyl ethyl ketone (MEK), propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), and γ-butyrolactone (GBL). Specific examples of the polymerization initiator include 2,2-azobisisobutyronitrile (AIBN), 2,2-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2-azobis(2-methylpropionate), 1,1-azobis(1-acetoxy-1-phenylethane), benzoyl peroxide, and lauroyl peroxide. The amount of the polymerization initiator added is preferably 0.01 to 25 mol% based on the total amount of monomers to be polymerized. The reaction temperature is preferably 50 to 150°C, more preferably 60 to 100°C. The reaction time is preferably 2 to 24 hours, and more preferably 2 to 12 hours from the viewpoint of production efficiency.

[0292] The polymerization initiator may be added to the monomer solution and then fed to the reaction vessel. Alternatively, an initiator solution may be prepared separately from the monomer solution, and each may be fed to the reaction vessel independently. From the perspective of quality control, it is preferable to prepare the monomer solution and the initiator solution independently and then add them dropwise, since radicals generated from the initiator during the waiting time may cause the polymerization reaction to proceed, resulting in the formation of ultra-high molecular weight polymers. Furthermore, known chain transfer agents such as dodecyl mercaptan and 2-mercaptoethanol may be used in combination to adjust the molecular weight. In this case, the amount of the chain transfer agent added is preferably 0.01 to 20 mol % of the total amount of monomers to be polymerized.

[0293] The amount of each monomer in the monomer solution may be appropriately set so as to achieve the preferred content ratio of the repeating units described above.

[0294] (solvent) The resist composition contains a solvent. The solvent is not particularly limited as long as it can dissolve the hypervalent iodine compound, the carboxyl group-containing compound, and other components described below and can form a film. Such a solvent is preferably an organic solvent, and specific examples thereof include ketones such as cyclohexanone, methyl-2-n-pentyl ketone, and methyl isoamyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, diacetone alcohol, 4-methyl-2-pentanol, and methyl 2-hydroxyisobutyrate; propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether; Examples of suitable solvents include ethers such as propylene glycol dimethyl ether and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol mono tert-butyl ether acetate; carboxylic acids such as formic acid, acetic acid, and propionic acid; lactones such as γ-butyrolactone; and mixed solvents thereof.

[0295] The content of the solvent in the resist composition is preferably an amount such that the solids concentration in the resist composition is 0.1 to 20 mass%, more preferably 0.1 to 15 mass%, and even more preferably 0.1 to 10 mass%. In the present invention, the solids are a collective term for all components of the resist composition other than the solvent. The solvents may be used alone or in combination of two or more.

[0296] (surfactant) The resist composition may further contain a surfactant. The surfactant is preferably a fluorine-based and / or silicone-based surfactant. Examples of such surfactants include those described in paragraph

[0276] of U.S. Patent Application Publication No. 2008 / 0248425. Furthermore, surfactants other than the fluorine-based and / or silicone-based surfactants described in paragraph

[0280] of U.S. Patent Application Publication No. 2008 / 0248425 may also be used.

[0297] When the resist composition contains the surfactant, the content thereof is preferably 0.0001 to 2 mass % of the total solid content. The surfactant may be used alone or in combination of two or more.

[0298] (radical scavenger) The resist composition may further contain a radical scavenger, which can control photoreactions during photolithography and adjust sensitivity.

[0299] Examples of the radical scavenger include hindered phenols, quinones, hindered amines, and thiol compounds. Specific examples of hindered phenols include dibutylhydroxytoluene (BHT) and 2,2-methylenebis(4-methyl-6-tert-butylphenol). Examples of quinones include 4-methoxyphenol (methoquinone) and hydroquinone. Examples of hindered amines include 2,2,6,6-tetramethylpiperidine and 2,2,6,6-tetramethylpiperidine-N-oxy radical. Examples of thiols include dodecanethiol and hexadecanethiol.

[0300] When the resist composition contains the radical scavenger, the content thereof is preferably 0.01 to 10 mass % of the total solid content. The radical scavenger may be used alone or in combination of two or more.

[0301] (Crosslinking agent) The resist composition may further contain a crosslinking agent. Addition of the crosslinking agent promotes the crosslinking reaction during photolithography, improves the glass transition temperature of the pattern, and enables the formation of a pattern with excellent fine-line resolution.

[0302] Examples of the crosslinking agent include compounds having a carbon-carbon unsaturated bond as a functional group, such as a vinyl group, a (meth)acrylate group, an allyl group, an alkynyl group, or an aromatic ring. Specific examples of compounds having a vinyl group include linear alkenes, branched alkenes, and cyclic alkenes, which may have a substituent. Examples of compounds having a (meth)acrylate group include acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters, which may have a substituent. Examples of compounds having an allyl group include allyl alcohols, allyl ethers, allyl esters, allyl amides, allyl amines, and allyl group-containing isocyanurates, which may have a substituent. Examples of compounds having an alkynyl group include linear alkynes, branched alkynes, cyclic alkynes, alkynyl alcohols, alkynyl ethers, alkynyl esters, alkynyl amides, alkynyl amines, and alkynyl group-containing isocyanurates, which may have a substituent. Examples of compounds having an aromatic ring include arenes, heteroarenes, styrene, stilbene, phenylacetylene, acenaphthylene, chalcone, and the like, which may have a substituent. The crosslinking agent may have only one of the above functional groups, or may have a plurality of functional groups. The number of the above functional groups contained in the crosslinking agent is preferably 1 to 10, and more preferably 2 to 8.

[0303] When the resist composition contains the crosslinking agent, the content thereof is preferably 0.01 to 50 mass % of the total solid content. The crosslinking agents may be used alone or in combination of two or more.

[0304] (Photopolymerization initiator) When the resist composition contains the crosslinking agent, it may further contain a photopolymerization initiator. The photopolymerization initiator generates radicals when irradiated with high-energy rays, and can promote crosslinking of the crosslinking agent.

[0305] Specific examples of the photopolymerization initiator include benzophenone, methyl O-benzoylbenzoate, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives; 2,2-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino Acetophenone derivatives such as propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]-phenyl}-2-methylpropan-1-one, and methyl phenylglyoxylate; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, and diethylthioxanthone; benzil, benzil dimethyl ketal ... Benzyl derivatives such as dibenzoyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin, benzoin methyl ether, and 2-hydroxy-2-methyl-1-phenylpropan-1-one; 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2 -Oxime compounds such as propanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime-1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)]ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime);α-Hydroxyketone compounds such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methylpropane; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl) Examples of suitable compounds include α-aminoalkylphenone compounds such as butan-1-one; phosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; and titanocene compounds such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium.

[0306] When the resist composition contains the photopolymerization initiator, its content is preferably 0.1 to 10 mass %, more preferably 0.1 to 5 mass %, and most preferably 0.1 to 1 mass %, based on the total solid content. When the content is 0.1 mass % or more, a sufficient blending effect can be obtained.

[0307] As described above, the resist composition contains a hypervalent iodine compound and a carboxyl group-containing compound as main components, but does not contain an acid-labile group-containing polymer or a photoacid generator, which are contained in conventional chemically amplified resist compositions. However, the resist composition of the present invention can form a positive-tone pattern, in which the exposed portion becomes soluble in a developer, particularly upon exposure to EB or EUV. The mechanism behind this is not completely clear, but is presumed to be as follows.

[0308] The hypervalent iodine compounds represented by formulas (7), (8), and (9) are tricoordinate compounds containing an aryl group and a carboxylate ligand. When such tricoordinate iodine compounds are mixed with a carboxylate-containing compound, an exchange of the carboxylate ligand is thought to occur via an equilibrium reaction. If the original carboxylate ligand can be removed in some way, a hypervalent iodine compound with a new ligand is generated. For example, by mixing 1-iodonaphthylene diacetate as the hypervalent iodine compound with a carboxylate-containing compound and removing the resulting low-boiling acetic acid, the ligand exchange is completed. The carboxylate-containing compound then becomes a crosslinked polymer formed by the hypervalent iodine compound.

[0309] Polymers crosslinked with hypervalent iodine compounds are generated during film formation. This is because even if such crosslinked polymers are synthesized in advance, they are insoluble in most organic solvents, making it impossible to prepare a solution. This is presumably because hypervalent iodine compounds, which have low solvent solubility due to their inherent high polarization, become even less soluble when a carboxyl group-containing compound is used as a ligand. Therefore, it is desirable to complete the ligand exchange reaction and form a resist film by removing the original low-molecular-weight carboxylic acid component during film formation and the subsequent baking process.

[0310] The resist film obtained from the resist composition undergoes a change in polarity due to the decomposition of the hypervalent iodine compound, which is the main component, by light, and a pattern is formed by a development step. The mechanism by which this occurs is not completely clear, but is presumed to be as follows, for example.

[0311] The resist film obtained from the resist composition contains a polymer to which a hypervalent iodine compound is bonded during film formation. However, when this polymer is decomposed by light, it becomes a monovalent iodine compound, and at the same time, the bond between the carboxyl group-containing compound and the hypervalent iodine compound is released, resulting in a decrease in molecular weight. As a result, a positive pattern is formed in which the exposed areas are removed by an organic solvent.

[0312] Based on the above assumption, the resist composition can be said to be a non-chemically amplified resist composition. The resist composition does not require an acid-labile group-containing polymer or a photoacid generator, as in conventional chemically amplified resist compositions. Therefore, adverse effects due to acid diffusion (e.g., image blurring) do not occur, and fine patterns can be resolved.

[0313] The resist composition is particularly effective in EUV lithography because it contains iodine atoms with high absorption capacity for EUV light, which reduces shot noise and enables higher resolution and lower LWR.

[0314] Metal resists containing metal tin compounds as their main component, which have a high absorption capacity for EUV light similar to that of iodine atoms, have been reported as EUV resist compositions capable of forming fine patterns (e.g., Patent Document 2). However, as mentioned above, such metal resists have many problems, such as insufficient solubility in solvents, poor storage stability, and defects due to post-etching residues caused by the presence of metal elements. On the other hand, the resist composition of the present invention is advantageous over metal resists in terms of defects because it does not contain metal elements, and it also has no issues with solubility in solvents. Furthermore, the resist composition of the present invention can be applied to positive resists, and therefore has a wide range of uses. For example, in the contact hole formation process, metal resists developed using negative tone development require a reversal process step after pillar pattern formation, whereas positive tone resists do not require such a step. Therefore, from the perspective of process simplicity, the resist composition of the present invention can be said to be more useful than metal resists.

[0315] The resist film preferably has a thickness of 10 to 70 nm, more preferably 20 to 50 nm.

[0316] [Resist Underlayer Film] The laminate of the present invention provides a laminate comprising a resist underlayer film between the substrate and the silicon-containing resist underlayer film.

[0317] The resist underlayer film may be a known film used in a fine patterning process using a multilayer resist method. Specific examples of the resist underlayer film include spin-on carbon ODL-301 (carbon content: 88% by mass) manufactured by Shin-Etsu Chemical Co., Ltd.

[0318] The resist underlayer film preferably has a thickness of 40 to 200 nm, more preferably 40 to 150 nm.

[0319] The resist underlayer film is preferably a resist underlayer film obtained using a solution-type composition for forming a resist underlayer film, or a resist underlayer film formed by a CVD method or an ALD method. [Method of manufacturing laminate] The present invention provides the following method for producing a laminate. forming a resist underlayer film on a substrate; forming a silicon-containing resist underlayer film on the resist underlayer film from a silicon-containing resist underlayer film composition containing a thermally crosslinkable polysiloxane comprising one or more repeating units represented by the above-described general formulas (1) to (3) and one or more repeating units represented by the above-described general formulas (4) to (6); A method for producing a laminate, comprising the steps of: applying a resist composition onto the silicon-containing resist underlayer film; the resist composition comprising at least one hypervalent iodine compound selected from the group consisting of a hypervalent iodine compound represented by formula (7) above, a hypervalent iodine compound represented by formula (8) below, and a hypervalent iodine compound represented by formula (9) above; a carboxy group-containing compound; and a solvent; and then performing a heat treatment to form a resist film.

[0320] The method for producing a laminate of the present invention, which is used in a two-layer resist process, includes the steps of applying the silicon-containing resist underlayer film composition onto a substrate and heat-treating the composition to form an adhesion film, and applying the resist composition onto the silicon-containing resist underlayer film and heat-treating the composition to form a resist film.

[0321] The present invention provides a method for producing the above-described laminate, characterized in that the resist underlayer film is formed by applying an underlayer film-forming material onto a substrate and then heat-treating the applied material.

[0322] The silicon-containing resist underlayer film can be formed by applying the silicon-containing resist underlayer film composition to a substrate by spin coating or the like, evaporating the solvent, and baking to promote the crosslinking reaction. The baking temperature is preferably 100 to 400°C, more preferably 150 to 300°C. The baking time is preferably 10 to 600 seconds, more preferably 10 to 300 seconds.

[0323] Alternatively, the silicon-containing resist underlayer film can be formed by applying the silicon-containing resist underlayer film composition to a substrate by spin coating or the like, as described above, and then baking and curing the silicon-containing resist underlayer film composition in an atmosphere with an oxygen concentration of 0.1 to 21%. By baking the silicon-containing resist underlayer film composition in such an oxygen atmosphere, a sufficiently cured film can be obtained. In this case, the baking temperature and time can be the same as those described above.

[0324] The atmosphere during baking may be air or may contain an inert gas such as N2, Ar, or He. The atmosphere may have an oxygen concentration of less than 0.1%. The baking temperature and time may be the same as those described above. Even if the substrate contains a material that is unstable when heated in an oxygen atmosphere, the crosslinking reaction during the formation of the silicon-containing resist underlayer film can be promoted without causing deterioration of the substrate.

[0325] The resist film can be formed by applying the resist film onto the silicon-containing resist underlayer film by an appropriate application method such as spin coating, roll coating, flow coating, dip coating, spray coating, or doctor coating, and then pre-baking the applied resist film on a hot plate, preferably at 60 to 200°C for 10 seconds to 30 minutes, more preferably at 80 to 180°C for 30 seconds to 20 minutes.

[0326] The method for producing a laminate of the present invention, which is used in a three-layer resist process, includes the steps of applying a resist underlayer film-forming material onto a substrate and heat treating it to form a resist underlayer film, applying a silicon-containing resist underlayer film composition onto the resist underlayer film and heat treating it to form a silicon-containing resist underlayer film, and applying the resist composition onto the silicon-containing resist underlayer film and heat treating it to form a resist film.

[0327] The resist underlayer film can be formed by applying a resist underlayer film-forming composition to a substrate by spin coating or the like, evaporating the solvent, and baking the resulting film. The baking temperature can be set appropriately depending on the type of resist underlayer film to be formed, but is typically about 100 to 400° C., and preferably about 150 to 300° C. The baking time can be set appropriately depending on the type of resist underlayer film to be formed, but is typically about 10 to 600 seconds, and preferably about 10 to 300 seconds.

[0328] The resist underlayer film is preferably formed by a CVD method or an ALD method.

[0329] In the three-layer resist process, the silicon-containing resist underlayer film can be formed by applying the silicon-containing resist underlayer film composition onto the resist underlayer film by spin coating or the like, evaporating the solvent, and baking to promote the crosslinking reaction. In this case, the baking time and temperature can be the same as those in the method for forming the silicon-containing resist underlayer film in the two-layer resist process.

[0330] In the three-layer resist process, the resist film can be formed by the same method as the method for forming the resist film in the two-layer resist process.

[0331] [Pattern formation method] The present invention provides a pattern forming method comprising the steps of exposing a resist film of the above-described laminate to i-line, KrF excimer laser, ArF excimer laser, electron beam or extreme ultraviolet light, and developing the exposed resist film using a developer.

[0332] When exposing using i-line, KrF excimer laser light, ArF excimer laser light, or EUV, the exposure dose is preferably about 1 to 300 mJ / cm2, more preferably about 10 to 200 mJ / cm2, either directly or using a mask for forming the desired pattern. When exposing using EB, the exposure dose is preferably about 0.1 to 8000 μC / cm2, more preferably about 0.5 to 5000 μC / cm2, either directly or using a mask for forming the desired pattern. The pattern forming method of the present invention is particularly suitable for fine patterning using EB or EUV, among high-energy beams.

[0333] After exposure, PEB is performed as needed, preferably on a hot plate or in an oven at 30 to 200°C for 10 seconds to 30 minutes, more preferably at 60 to 120°C for 30 seconds to 20 minutes.

[0334] After exposure or PEB, the film is developed with a developer as needed to perform patterning. The developer used in this case is preferably an organic solvent. After exposure or PEB, the film is developed with a developer as needed to perform patterning. The developer used in this case may be 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, 5-methyl-2-hexanone, methylcyclohexanone, acetophenone, methylacetophenone, isopropyl alcohol, isoamyl alcohol, n-butanol, tert-butyl alcohol, tert-pentyl alcohol, n-pentanol, cyclohexanol, formic acid, acetic acid, propionic acid, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, cyclohexyl acetate, 4-tert-butylcyclohexyl acetate, octyl acetate, isobornyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, Examples of organic solvents include ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, ethyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, 2-phenylethyl acetate, 2-propanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 3-methyl-1-butanol, diacetone alcohol, 4-methyl-2-pentanol, 3-methylcyclohexanol, 3,5,5-trimethylhexyl alcohol, 2,6-dimethyl-4-heptanol, toluene, anisole, and ε-caprolactone. These developers may be used alone or in combination of two or more.

[0335] After development, rinsing is performed as necessary. A preferred rinsing solution is a solvent that is miscible with the developer but does not dissolve the resist film. Preferred examples of such solvents include alcohols having 3 to 10 carbon atoms, ether compounds having 8 to 12 carbon atoms, alkanes, alkenes, alkynes, and aromatic solvents having 6 to 12 carbon atoms.

[0336] Rinsing can reduce the occurrence of resist pattern collapse and defects. Rinsing is not always necessary, and not performing rinsing can reduce the amount of solvent used. [Example]

[0337] The present invention will be specifically explained below with reference to Synthesis Examples, Comparative Synthesis Examples, Preparation Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples. The molecular weight was measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) or N,N-dimethylformamide (DMF) as an eluent to determine the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in terms of polystyrene, from which the polydispersity (Mw / Mn) was calculated.

[0338] [1] Synthesis of polymers for silicon-containing resist underlayer film compositions [Synthesis Example 1-1] A mixture of 30.6 g of compound (101), 11.4 g of compound (102), and 4.3 g of compound (103) (molar ratio: 67 / 28 / 5) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and the mixture was maintained at 25°C for 24 hours to allow hydrolysis and condensation. After completion of the reaction, 450 g of propylene glycol monoethyl ether (PGEE) and 1.1 g of 24% aqueous maleic acid solution were added, and the water and by-product alcohol used in the hydrolysis and condensation were distilled off under reduced pressure to obtain 240 g of a PGEE solution of polysiloxane compound 1 (compound concentration: 10%). The polystyrene-equivalent molecular weight of polysiloxane compound 1 was measured to be Mw = 2,750.

[0339] [Synthesis Example 1-2] A mixture of 30.6 g of compound (101), 9.4 g of compound (102), and 8.5 g of compound (103) (molar ratio: 67 / 23 / 10) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and the mixture was maintained at 25°C for 24 hours to allow hydrolysis and condensation. After completion of the reaction, 450 g of propylene glycol monoethyl ether (PGEE) and 1.1 g of 24% aqueous maleic acid solution were added, and the water and by-product alcohol used in the hydrolysis and condensation were distilled off under reduced pressure to obtain 270 g of a PGEE solution of polysiloxane compound 2 (compound concentration: 10%). The polystyrene-equivalent molecular weight of polysiloxane compound 2 was measured and found to be Mw = 2,650.

[0340] [Synthesis Example 1-3] A mixture of 30.6 g of compound (101), 5.3 g of compound (102), and 17.1 g of compound (103) (molar ratio: 67 / 13 / 20) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and the mixture was maintained at 25°C for 24 hours to allow hydrolysis and condensation. After completion of the reaction, 450 g of propylene glycol monoethyl ether (PGEE) and 1.4 g of 24% aqueous maleic acid solution were added, and the water and by-product alcohol used in the hydrolysis and condensation were distilled off under reduced pressure to obtain 280 g of a PGEE solution of polysiloxane compound 3 (compound concentration 10%). The polystyrene-equivalent molecular weight of polysiloxane compound 3 was measured and found to be Mw = 2,700.

[0341] [Synthesis Example 1-4] A mixture of 30.6 g of compound (101), 1.2 g of compound (102), and 25.6 g of compound (103) (molar ratio: 67 / 3 / 30) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and the mixture was maintained at 25°C for 24 hours to allow hydrolysis and condensation. After completion of the reaction, 450 g of propylene glycol monoethyl ether (PGEE) and 1.6 g of 24% aqueous maleic acid solution were added, and the water and by-product alcohol used in the hydrolysis and condensation were distilled off under reduced pressure to obtain 280 g of a PGEE solution of polysiloxane compound 4 (compound concentration: 10%). The polystyrene-equivalent molecular weight of polysiloxane compound 4 was measured and found to be Mw = 2,700.

[0342] [Synthesis Example 1-5] A mixture of 22.8 g of compound (101) and 42.7 g of compound (103) (molar ratio: 50 / 50) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and the mixture was maintained at 25°C for 24 hours to allow hydrolysis and condensation. After completion of the reaction, 450 g of propylene glycol monoethyl ether (PGEE) and 2.0 g of 24% aqueous maleic acid solution were added, and the water and by-product alcohol used in the hydrolysis and condensation were distilled off under reduced pressure to obtain 300 g of a PGEE solution of polysiloxane compound 5 (compound concentration: 10%). The polystyrene-equivalent molecular weight of polysiloxane compound 5 was measured and found to be Mw = 2,650.

[0343] [Synthesis Example 1-6] A mixture of 30.6 g of compound (101), 9.4 g of compound (102), and 9.1 g of compound (104) (molar ratio: 67 / 23 / 10) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and the mixture was maintained at 25°C for 24 hours to allow hydrolysis and condensation. After completion of the reaction, 450 g of propylene glycol monoethyl ether (PGEE) and 1.2 g of 24% aqueous maleic acid solution were added, and the water and by-product alcohol used in the hydrolysis and condensation were distilled off under reduced pressure to obtain 240 g of a PGEE solution of polysiloxane compound 6 (compound concentration: 10%). The polystyrene-equivalent molecular weight of polysiloxane compound 6 was measured to be Mw = 2,650.

[0344] [Synthesis Example 1-7] A mixture of 30.6 g of compound (101), 9.4 g of compound (102), and 9.8 g of compound (105) (molar ratio: 67 / 23 / 10) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and the mixture was maintained at 25°C for 24 hours to allow hydrolysis and condensation. After completion of the reaction, 450 g of propylene glycol monoethyl ether (PGEE) and 1.2 g of 24% aqueous maleic acid solution were added, and the water and by-product alcohol used in the hydrolysis and condensation were distilled off under reduced pressure to obtain 250 g of a PGEE solution of polysiloxane compound 7 (compound concentration 10%). The polystyrene-equivalent molecular weight of polysiloxane compound 7 was measured and found to be Mw = 2,700.

[0345] [Synthesis Example 1-8] A mixture of 30.6 g of compound (101), 9.4 g of compound (102), and 9.8 g of compound (106) (molar ratio: 67 / 23 / 10) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and the mixture was maintained at 25°C for 24 hours to allow hydrolysis and condensation. After completion of the reaction, 450 g of propylene glycol monoethyl ether (PGEE) and 1.2 g of 24% aqueous maleic acid solution were added, and the water and by-product alcohol used in the hydrolysis and condensation were distilled off under reduced pressure to obtain 255 g of a PGEE solution of polysiloxane compound 8 (compound concentration 10%). The polystyrene-equivalent molecular weight of polysiloxane compound 8 was measured and found to be Mw = 2,730.

[0346] [Synthesis Example 1-9] A mixture of 30.6 g of compound (101), 9.4 g of compound (102), and 6.3 g of compound (107) (molar ratio: 67 / 23 / 10) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and the mixture was maintained at 25°C for 24 hours to allow hydrolysis and condensation. After completion of the reaction, 450 g of propylene glycol monoethyl ether (PGEE) and 1.0 g of 24% aqueous maleic acid solution were added, and the water and by-product alcohol used in the hydrolysis and condensation were distilled off under reduced pressure to obtain 220 g of a PGEE solution of polysiloxane compound 9 (compound concentration 10%). The polystyrene-equivalent molecular weight of polysiloxane compound 9 was measured to be Mw = 2,550.

[0347] [Synthesis Example 1-10] A mixture of 30.6 g of compound (101), 9.4 g of compound (102), and 6.9 g of compound (108) (molar ratio: 67 / 23 / 10) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and the mixture was maintained at 25°C for 24 hours to allow hydrolysis and condensation. After completion of the reaction, 450 g of propylene glycol monoethyl ether (PGEE) and 1.1 g of 24% aqueous maleic acid solution were added, and the water and by-product alcohol used in the hydrolysis and condensation were distilled off under reduced pressure to obtain 255 g of a PGEE solution of polysiloxane compound 10 (compound concentration 10%). The polystyrene-equivalent molecular weight of polysiloxane compound 10 was measured to be Mw = 3,600.

[0348] [Synthesis Example 1-11] A mixture of 30.6 g of compound (101), 5.3 g of compound (102), and 13.8 g of compound (108) (molar ratio: 67 / 13 / 20) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and the mixture was maintained at 25°C for 24 hours to allow hydrolysis and condensation. After completion of the reaction, 450 g of propylene glycol monoethyl ether (PGEE) and 1.1 g of 24% aqueous maleic acid solution were added, and the water and by-product alcohol used in the hydrolysis and condensation were distilled off under reduced pressure to obtain 270 g of a PGEE solution of polysiloxane compound 11 (compound concentration: 10%). The polystyrene-equivalent molecular weight of polysiloxane compound 11 was measured to be Mw = 3,600.

[0349] [Synthesis Example 1-12] A mixture of 30.6 g of compound (101), 1.2 g of compound (102), and 20.7 g of compound (108) (molar ratio: 67 / 3 / 30) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and the mixture was maintained at 25°C for 24 hours to allow hydrolysis and condensation. After completion of the reaction, 450 g of propylene glycol monoethyl ether (PGEE) and 1.2 g of 24% aqueous maleic acid solution were added, and the water and by-product alcohol used in the hydrolysis and condensation were distilled off under reduced pressure to obtain 310 g of a PGEE solution of polysiloxane compound 12 (compound concentration: 10%). The polystyrene-equivalent molecular weight of polysiloxane compound 12 was measured to be Mw = 7,000.

[0350] [Comparative Synthesis Example 1-13] A mixture of 30.6 g of compound (101), 9.4 g of compound (102), and 5.9 g of compound (109) (molar ratio: 67 / 23 / 10) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and the mixture was maintained at 25°C for 24 hours to allow hydrolysis and condensation. After completion of the reaction, 450 g of propylene glycol monoethyl ether (PGEE) and 1.0 g of 24% aqueous maleic acid solution were added, and the water and by-product alcohol used in the hydrolysis and condensation were distilled off under reduced pressure to obtain 210 g of a PGEE solution of polysiloxane compound 13 (compound concentration: 10%). The polystyrene-equivalent molecular weight of polysiloxane compound 13 was measured and found to be Mw = 2,600.

[0351] Using the monomers shown in Table 1, the target polysiloxane compounds 1 to 13 were obtained by the methods of [Synthesis Example 1-1] to [Synthesis Example 1-12] and [Comparative Synthesis Example 1-13].

[0352] [Table 1] [ka]

[0353] [2] Preparation of silicon-containing resist underlayer film composition Polysiloxane compounds 1 to 13 obtained in the above Synthesis Examples 1-1 to 1-13, a crosslinking catalyst, an acid, a solvent, and water were mixed in the proportions shown in Table 2, and the mixture was filtered through a 0.1 μm fluororesin filter to prepare polysiloxane underlayer film composition solutions, designated Sol. 1 to 13, respectively.

[0354] [Table 2]

[0355] TPSNO3: Triphenylsulfonium nitrate QBANO3: Tetrabutylammonium nitrate PGEE: Propylene glycol monoethyl ether

[0356] [3] Synthesis of polymers for resist compositions The compounds shown below were used to synthesize the polymers P-1 to P-5 for resist compositions. [ka]

[0357] [ka]

[0358] [ka]

[0359] [Synthesis Example 2-1] Synthesis of Polymer P-1 A monomer-polymerization initiator solution was prepared by placing 56 g of monomer b-1, 36 g of monomer c-1, 5.4 g of V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.), and 180 g of MEK in a flask under a nitrogen atmosphere. 55 g of MEK was placed in a separate flask under a nitrogen atmosphere and heated to 80°C with stirring. The monomer-polymerization initiator solution was then added dropwise over 4 hours. After the addition, the polymerization solution was stirred for 2 hours while maintaining the temperature at 80°C, and then cooled to room temperature. The resulting polymerization solution was added dropwise to 4,000 g of vigorously stirred hexane, and the precipitated polymer was filtered. The resulting polymer was washed twice with 1,200 g of hexane and then vacuum-dried at 50°C for 20 hours to obtain polymer P-1 as a white powder (yield: 90 g, 98%). The Mw of polymer P-1 was 8,000, and the Mw / Mn ratio was 1.42. The Mw is a polystyrene-equivalent value measured by GPC using THF as a solvent. [ka]

[0360] [Synthesis Examples 2-2 to 2-5] Synthesis of Polymers P-2 to P-5 The polymers shown in Table 3 below were synthesized in the same manner as in Synthesis Example 2-1, except that the types and blending ratios of the respective monomers were changed.

[0361] [Table 3]

[0362] [4] Preparation of resist composition [Preparation Examples 2-1 to 2-10, Comparative Preparation Examples 1-1 to 1-2] Resist compositions (R-01 to R-10) were prepared by dissolving a hypervalent iodine compound and a carboxyl group-containing compound in a solvent containing 0.01% by mass of a surfactant (PF-636, Omnova) according to the compositions shown in Table 4 below, and filtering the resulting solution through a 0.2 μm Teflon (registered trademark) filter. Resist compositions (CR-01 and CR-02) were prepared by dissolving a polymer, a photoacid generator, and a sensitivity adjuster in a solvent containing 0.01% by mass of a surfactant (PF-636, Omnova) according to the compositions shown in Table 5 below, and filtering the resulting solution through a 0.2 μm Teflon (registered trademark) filter.

[0363] [Table 4]

[0364] [Table 5]

[0365] In Tables 4 and 5, the hypervalent iodine compounds I-1 to I-3, carboxy group-containing compounds m-1 to m-3, photoacid generator PAG-1, sensitivity adjuster Q-1 and solvents are as follows. [ka]

[0366] [ka]

[0367] [ka]

[0368] [ka]

[0369] Solvent: AcOH (acetic acid) GBL (γ-butyrolactone)

[0370] [5] Fabrication of laminate and EUV lithography evaluation (two-layer resist process, line and space pattern) [Examples 1-1 to 1-21, Comparative Examples 1-1 to 1-4] Each silicon-containing resist underlayer film composition (Sol. 1 to Sol. 13) was spin-coated onto a silicon substrate and baked for 60 seconds using a hot plate at the temperature shown in Table 6 to form a silicon-containing resist underlayer film with a thickness of 40 nm. Next, each resist composition (R-01 to R-10, CR-01 to CR-02) was spin-coated onto the film and pre-baked (PAB) for 60 seconds using a hot plate at the temperature listed in Table 6 to produce a 40 nm thick resist film. The resist film was exposed to a 36 nm line and space (LS) 1:1 pattern using an ASML EUV scanner NXE3400 (NA 0.33, σ 0.9, 90-degree dipole illumination), and then PEB was performed on a hot plate at the temperature listed in Table 6 for 60 seconds. Development was then performed for 30 seconds using the developer listed in Table 5 to form an LS pattern with a space width of 18 nm and a pitch of 36 nm.

[0371] The resulting resist patterns were evaluated as follows, and the results are shown in Table 6.

[0372] [Sensitivity evaluation] The LS pattern was observed using a critical dimension SEM (CG-6300) manufactured by Hitachi High-Tech Corporation, and the optimum exposure dose Eop (mJ / cm2) for obtaining an LS pattern with a space width of 18 nm and a pitch of 36 nm was determined, and this was taken as the sensitivity.

[0373] [LWR rating] The LS pattern obtained by irradiation with the optimum exposure dose was measured at 10 points in the longitudinal direction of the space width using a critical dimension SEM (CG-6300) manufactured by Hitachi High-Tech Corporation, and the LWR was calculated as three times the standard deviation (σ) (3σ). The smaller this value, the less roughness and the more uniform the space width pattern obtained.

[0374] [Limiting resolution evaluation] The limiting line width (nm) that can be resolved when forming a pattern by gradually increasing the exposure dose from the optimum exposure dose at which the LS pattern is formed was determined using a critical dimension SEM (CG-6300) manufactured by Hitachi High-Technologies Corporation, and this was taken as the limiting resolution (nm). The smaller this value, the better the limiting resolution, indicating that a finer pattern can be formed.

[0375] [Table 6]

[0376] Developer: nBA (butyl acetate) TMAH (2.38% by mass tetramethylammonium hydroxide aqueous solution)

[0377] From the results shown in Table 6, when comparing Comparative Examples 1-1 and 1-2 with the Examples, it was found that excellent resolution could be obtained by using the silicon-containing resist underlayer film composition in a two-layer resist process. Furthermore, it was also found to have excellent sensitivity, resolution, and LWR, even compared to Comparative Examples 1-3 and 1-4, which used chemically amplified resist compositions using an acid-catalyzed reaction. Therefore, it was found that the two-layer resist process using the laminate of the present invention provided excellent resolution in LS pattern formation by EUV exposure. [6] Stack manufacturing and EUV lithography evaluation (3-layer resist process, contact hole pattern) [Examples 2-1 to 2-21, Comparative Examples 2-1 to 2-4] A silicon substrate was coated with spin-on carbon ODL-301 (carbon content: 88% by mass) manufactured by Shin-Etsu Chemical Co., Ltd., and baked at 350°C for 60 seconds to form a resist underlayer film with a thickness of 200 nm. Each silicon-containing resist underlayer film composition (Sol. 1 to Sol. 13) was spin-coated thereon, and baked using a hot plate at the temperature listed in Table 7 for 60 seconds to form a silicon-containing resist underlayer film with a thickness of 40 nm. Next, each resist composition (R-01 to R-10, CR-01 to CR-02) was spin-coated onto the film and pre-baked (PAB) for 60 seconds using a hot plate at the temperature listed in Table 7 to produce a resist film with a thickness of 50 nm. Next, the resist film was exposed using an ASML EUV scanner NXE3400 (NA 0.33, σ 0.9 / 0.6, quadruple pole illumination, wafer dimensions 64 nm pitch, +20% bias hole pattern mask), and PEB was performed on a hot plate at the temperature listed in Table 6 for 60 seconds. Development was performed for 30 seconds using the developer listed in Table 7 to obtain a hole pattern with a dimension of 32 nm.

[0378] The resulting resist patterns were evaluated as follows, and the results are shown in Table 7.

[0379] [Sensitivity evaluation] The contact hole pattern was observed using a critical dimension SEM (CG-6300) manufactured by Hitachi High-Tech Corporation, and the optimum exposure dose Eop (mJ / cm 2 ) required to obtain a hole pattern with a dimension of 22 nm was determined and used as the sensitivity.

[0380] [CDU Rating] The dimensions of 50 hole patterns obtained by irradiation with the optimal exposure dose were measured, and the CDU was calculated as three times the standard deviation (σ). The smaller this value, the more uniform the hole diameter pattern obtained.

[0381] [Limiting resolution evaluation] The limiting hole diameter (nm) that can be resolved when forming a hole pattern by gradually decreasing the exposure dose from the optimum exposure dose required to form the hole pattern was determined using a critical dimension SEM (CG-6300) manufactured by Hitachi High-Technologies Corporation, and this was taken as the limiting resolution (nm). The smaller this value, the better the limiting resolution, indicating that a pattern with a finer hole diameter can be formed.

[0382] [Table 7]

[0383] The results shown in Table 7 show that, when Comparative Examples 2-1 and 2-2 are compared with the Examples, excellent CDU patterns can be obtained in a three-layer resist process by using the silicon-containing resist underlayer film composition. Furthermore, even when compared with Comparative Examples 2-3 and 2-4, which used chemically amplified resist compositions using an acid catalyst reaction, excellent sensitivity, resolution, and LWR were observed. Therefore, it was found that the three-layer resist process using the laminate of the present invention provides excellent CDU in contact hole pattern formation by EUV exposure.

[0384] This specification includes the following inventions.

[0385] [1] A substrate; a silicon-containing resist underlayer film obtained from a silicon-containing resist underlayer film composition containing a thermally crosslinkable polysiloxane including at least one repeating unit represented by the following general formulas (1) to (3) and at least one repeating unit represented by the following general formulas (4) to (6); a resist film obtained from a resist composition containing at least one hypervalent iodine compound selected from the group consisting of a hypervalent iodine compound represented by the following formula (7), a hypervalent iodine compound represented by the following formula (8), and a hypervalent iodine compound represented by the following formula (9), a carboxy group-containing compound, and a solvent; A laminate comprising the above in this order. [ka] (In the formula, R 1 is an organic group having a carboxyl group or an organic group having a carboxyl group substituted with an acid labile group, and R 2 , R 3 and R 4 are each a monovalent organic group having 1 to 30 carbon atoms, which may be the same or different. [ka] (In the formula, m is 0, 1, or 2. When m is 0, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, or 5, and 1≦n1+n2≦6. When m is 1, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1≦n1+n2≦8. When m is 2, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, or 5. , 5, 6, 7, 8, or 9, and 1≦n1+n2≦10. n3 is 1 or 2. n4 is 0, 1, 2, 3, or 4, provided that 1≦n3+n4≦5. n5 is 1 or 2. n6 is 0, 1, 2, 3, or 4, provided that 1≦n5+n6≦5. n7 is 0, 1, 2, 3, or 4. n8 is 1, 2, 3, or 4. R 11 ~R 18 are each independently a halogen atom or a hydrocarbyl group having 1 to 10 carbon atoms which may contain a heteroatom. 11 and R 12 , R 13 and R 14 , R 15 and R 16 , or R 17 and R 18 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms. R 21 ~R 24 are each independently a hydrocarbyl group having 1 to 40 carbon atoms which may contain a halogen atom or a heteroatom. When n2 is 2 or more, each R 21 may be the same or different, and multiple R 21 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n4 is 2 or more, each R 22 may be the same or different, and multiple R 22 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n6 is 2 or more, each R 23 may be the same or different, and multiple R 23 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n7 is 2 or more, each R24 may be the same or different, and multiple R 24 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are attached. R 25 is an (n8)-valent hydrocarbon group having 1 to 40 carbon atoms or an (n8)-valent heterocyclic group having 2 to 40 carbon atoms, and when n8 is 2, R 25 may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, a sulfonyl group, or a thioketone bond. In addition, some or all of the hydrogen atoms of the (n8)-valent hydrocarbon group or the (n8)-valent heterocyclic group may be substituted with a group containing a hetero atom, and some of the -CH2- of the (n8)-valent hydrocarbon group may be substituted with a group containing a hetero atom, and R 24 and R 25 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms. [2]: The laminate according to [1], characterized in that a resist underlayer film is provided between the substrate and the silicon-containing resist underlayer film. [3]: The laminate according to [1] or [2], wherein the silicon-containing resist underlayer film composition contains a siloxane polymerization crosslinking catalyst (Xc), an alcohol-based organic solvent, and water. [4]: The laminate according to any one of [1] to [3], wherein the carboxy group-containing compound in the resist composition is a polymer containing a repeating unit represented by the following formula (10) or a compound represented by the following formula (11): [ka] (In the formula, R A is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. X A is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OX A1 -X A1is a saturated hydrocarbylene group having 1 to 10 carbon atoms, a phenylene group, or a naphthylene group, and the saturated hydrocarbylene group may contain a hydroxy group, an ether bond, an ester bond, or a lactone ring. * represents a bond to a carbon atom in the main chain. p is 1, 2, 3 or 4. R 31 is a p-valent hydrocarbon group having 1 to 40 carbon atoms or a p-valent heterocyclic group having 2 to 40 carbon atoms, and when p is 2, R 31 may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, or a sulfonyl group. Some or all of the hydrogen atoms of the p-valent hydrocarbon group or p-valent heterocyclic group may be substituted with a group containing a heteroatom, and some of the -CH2- groups of the p-valent hydrocarbon group may be substituted with a group containing a heteroatom. R 32 is a single bond or a hydrocarbylene group having 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing a hetero atom, or some of the -CH2- of the hydrocarbylene group may be substituted with a group containing a hetero atom. 32 may be the same as or different from each other.) [5]: forming a resist underlayer film on a substrate; forming a silicon-containing resist underlayer film on the resist underlayer film from a silicon-containing resist underlayer film composition containing a thermally crosslinkable polysiloxane containing one or more repeating units represented by the following general formulas (1) to (3) and one or more repeating units represented by the following general formulas (4) to (6); A method for producing a laminate, comprising the steps of: applying a resist composition onto the silicon-containing resist underlayer film, the resist composition comprising at least one hypervalent iodine compound selected from the group consisting of a hypervalent iodine compound represented by the following formula (7), a hypervalent iodine compound represented by the following formula (8), and a hypervalent iodine compound represented by the following formula (9); a carboxy group-containing compound; and a solvent; and then performing a heat treatment to form a resist film. [ka] (In the formula, R 1 is an organic group having a carboxyl group or an organic group having a carboxyl group substituted with an acid labile group, and R 2 , R 3 and R 4 are each a monovalent organic group having 1 to 30 carbon atoms, which may be the same or different. [ka] (In the formula, m is 0, 1, or 2. When m is 0, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, or 5, and 1≦n1+n2≦6. When m is 1, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1≦n1+n2≦8. When m is 2, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, or 5. , 5, 6, 7, 8, or 9, and 1≦n1+n2≦10. n3 is 1 or 2. n4 is 0, 1, 2, 3, or 4, provided that 1≦n3+n4≦5. n5 is 1 or 2. n6 is 0, 1, 2, 3, or 4, provided that 1≦n5+n6≦5. n7 is 0, 1, 2, 3, or 4. n8 is 1, 2, 3, or 4. R 11 ~R 18 are each independently a halogen atom or a hydrocarbyl group having 1 to 10 carbon atoms which may contain a heteroatom. 11 and R 12 , R 13 and R 14 , R 15 and R 16 , or R 17 and R 18 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms. R 21 ~R 24 are each independently a hydrocarbyl group having 1 to 40 carbon atoms which may contain a halogen atom or a heteroatom. When n2 is 2 or more, each R 21 may be the same or different, and multiple R 21may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n4 is 2 or more, each R 22 may be the same or different, and multiple R 22 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n6 is 2 or more, each R 23 may be the same or different, and multiple R 23 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n7 is 2 or more, each R 24 may be the same or different, and multiple R 24 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are attached. R 25 is an (n8)-valent hydrocarbon group having 1 to 40 carbon atoms or an (n8)-valent heterocyclic group having 2 to 40 carbon atoms, and when n8 is 2, R 25 may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, a sulfonyl group, or a thioketone bond. In addition, some or all of the hydrogen atoms of the (n8)-valent hydrocarbon group or the (n8)-valent heterocyclic group may be substituted with a group containing a hetero atom, and some of the -CH2- of the (n8)-valent hydrocarbon group may be substituted with a group containing a hetero atom, and R 24 and R 25 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms. [6]: The method for producing a laminate according to [5], wherein the resist underlayer film is formed by applying an underlayer film-forming material onto a substrate and performing a heat treatment. [7]: The method for producing a laminate according to [5], wherein the resist underlayer film is formed by a CVD method or an ALD method. [8]: The method for producing a laminate according to any one of [5] to [7], wherein the carboxy group-containing compound is a polymer containing a repeating unit represented by the following formula (10) or a compound represented by the following formula (11): [ka] (In the formula, R A is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. X A is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OX A1 -X A1 is a saturated hydrocarbylene group having 1 to 10 carbon atoms, a phenylene group, or a naphthylene group, and the saturated hydrocarbylene group may contain a hydroxy group, an ether bond, an ester bond, or a lactone ring. * represents a bond to a carbon atom in the main chain. p is 1, 2, 3 or 4. R 31 is a p-valent hydrocarbon group having 1 to 40 carbon atoms or a p-valent heterocyclic group having 2 to 40 carbon atoms, and when p is 2, R 31 may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, or a sulfonyl group. Some or all of the hydrogen atoms of the p-valent hydrocarbon group or p-valent heterocyclic group may be substituted with a group containing a heteroatom, and some of the -CH2- groups of the p-valent hydrocarbon group may be substituted with a group containing a heteroatom. R 32 is a single bond or a hydrocarbylene group having 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing a hetero atom, or some of the -CH2- of the hydrocarbylene group may be substituted with a group containing a hetero atom. 32 may be the same as or different from each other.) [9]: A pattern forming method comprising the steps of: exposing a resist film of the laminate according to any one of [1] to [4] to i-line, KrF excimer laser, ArF excimer laser, electron beam, or extreme ultraviolet light; and developing the exposed resist film using a developer.

[10] : The pattern forming method according to [9], wherein the developer is an organic solvent.

[0386] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention.

Claims

1. A substrate; a silicon-containing resist underlayer film obtained from a silicon-containing resist underlayer film composition containing a thermally crosslinkable polysiloxane comprising one or more repeating units represented by the following general formulas (1) to (3) and one or more repeating units represented by the following general formulas (4) to (6); a resist film obtained from a resist composition containing at least one hypervalent iodine compound selected from the group consisting of a hypervalent iodine compound represented by the following formula (7), a hypervalent iodine compound represented by the following formula (8), and a hypervalent iodine compound represented by the following formula (9), a carboxy group-containing compound, and a solvent; A laminate comprising the above in this order. 【Chemistry 1】 (In the formula, R １ is an organic group having a carboxy group or an organic group having a carboxyl group substituted with an acid labile group, and R ２ , R ３ and R ４ are each a monovalent organic group having 1 to 30 carbon atoms, which may be the same or different. 【Chemistry 2】 (In the formula, m is 0, 1, or 2. When m is 0, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, or 5, and 1≦n1+n2≦6. When m is 1, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1≦n1+n2≦8. When m is 2, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, and 1≦n1+n2≦10. n3 is 1 or 2. n4 is 0, 1, 2, 3, or 4, provided that 1≦n3+n4≦5. n5 is 1 or 2. n6 is 0, 1, 2, 3, or 4, provided that 1≦n5+n6≦5. n7 is 0, 1, 2, 3, or 4. n8 is 1, 2, 3, or 4. R １１ ~R １８ are each independently a halogen atom or a hydrocarbyl group having 1 to 10 carbon atoms which may contain a heteroatom. １１ and R １２ , R １３ and R １４ , R １５ and R １６ , or R １７ and R １８ may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms. R ２１ ~R ２４ are each independently a halogen atom or a hydrocarbyl group having 1 to 40 carbon atoms which may contain a heteroatom. When n2 is 2 or more, each R ２１ may be the same or different, and multiple R ２１ may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. ２２ may be the same or different, and multiple R ２２ may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. ２３ may be the same or different, and multiple R ２３ may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. ２４ may be the same or different, and multiple R ２４ may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are attached. R ２５ is an (n8)-valent hydrocarbon group having 1 to 40 carbon atoms or an (n8)-valent heterocyclic group having 2 to 40 carbon atoms, and when n8 is 2, R ２５ may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, a sulfonyl group, or a thioketone bond. In addition, some or all of the hydrogen atoms of the (n8)-valent hydrocarbon group or the (n8)-valent heterocyclic group may be substituted with a group containing a hetero atom, and the —CH ２ A part of - may be substituted with a group containing a hetero atom, ２４ and R ２５ may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms.)

2. 2. The laminate according to claim 1, further comprising a resist underlayer film between the substrate and the silicon-containing resist underlayer film.

3. 2. The laminate according to claim 1, wherein the silicon-containing resist underlayer film composition comprises a siloxane polymerization crosslinking catalyst (Xc), an alcohol-based organic solvent, and water.

4. 2. The laminate according to claim 1, wherein the carboxy group-containing compound in the resist composition is a polymer containing a repeating unit represented by the following formula (10) or a compound represented by the following formula (11): 【Transformation 3】 (In the formula, R Ａ is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. X Ａ represents a single bond, a phenylene group, a naphthylene group, or *-C(=O)-O-X Ａ１ - is. X Ａ１ is a saturated hydrocarbylene group having 1 to 10 carbon atoms, a phenylene group, or a naphthylene group, and the saturated hydrocarbylene group may contain a hydroxy group, an ether bond, an ester bond, or a lactone ring. * represents a bond to a carbon atom in the main chain. p is 1, 2, 3 or 4. R ３１ is a p-valent hydrocarbon group having 1 to 40 carbon atoms or a p-valent heterocyclic group having 2 to 40 carbon atoms, and when p is 2, R ３１ may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, or a sulfonyl group. In addition, some or all of the hydrogen atoms of the p-valent hydrocarbon group or the p-valent heterocyclic group may be substituted with a group containing a hetero atom, and the -CH ２ A portion of - may be substituted with a group containing a hetero atom. R ３２ represents a single bond or a hydrocarbylene group having 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing a hetero atom, and the —CH ２ When p is 2 to 4, each R ３２ may be the same as or different from each other.)

5. forming a resist underlayer film on a substrate; forming a silicon-containing resist underlayer film on the resist underlayer film from a silicon-containing resist underlayer film composition containing a thermally crosslinkable polysiloxane containing one or more repeating units represented by the following general formulas (1) to (3) and one or more repeating units represented by the following general formulas (4) to (6); A method for producing a laminate, comprising the steps of: applying a resist composition onto the silicon-containing resist underlayer film, the resist composition comprising at least one hypervalent iodine compound selected from the group consisting of a hypervalent iodine compound represented by the following formula (7), a hypervalent iodine compound represented by the following formula (8), and a hypervalent iodine compound represented by the following formula (9); a carboxy group-containing compound; and a solvent; and then performing a heat treatment to form a resist film. 【Chemistry 4】 (In the formula, R １ is an organic group having a carboxy group or an organic group having a carboxyl group substituted with an acid labile group, and R ２ , R ３ and R ４ are each a monovalent organic group having 1 to 30 carbon atoms, which may be the same or different. 【Transformation 5】 (In the formula, m is 0, 1, or 2. When m is 0, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, or 5, and 1≦n1+n2≦6. When m is 1, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1≦n1+n2≦8. When m is 2, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, and 1≦n1+n2≦10. n3 is 1 or 2. n4 is 0, 1, 2, 3, or 4, provided that 1≦n3+n4≦5. n5 is 1 or 2. n6 is 0, 1, 2, 3, or 4, provided that 1≦n5+n6≦5. n7 is 0, 1, 2, 3, or 4. n8 is 1, 2, 3, or 4. R １１ ~R １８ are each independently a halogen atom or a hydrocarbyl group having 1 to 10 carbon atoms which may contain a heteroatom. １１ and R １２ , R １３ and R １４ , R １５ and R １６ , or R １７ and R １８ may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms. R ２１ ~R ２４ are each independently a halogen atom or a hydrocarbyl group having 1 to 40 carbon atoms which may contain a heteroatom. When n2 is 2 or more, each R ２１ may be the same or different, and multiple R ２１ may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. ２２ may be the same or different, and multiple R ２２ may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. ２３ may be the same or different, and multiple R ２３ may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. ２４ may be the same or different, and multiple R ２４ may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are attached. R ２５ is an (n8)-valent hydrocarbon group having 1 to 40 carbon atoms or an (n8)-valent heterocyclic group having 2 to 40 carbon atoms, and when n8 is 2, R ２５ may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, a sulfonyl group, or a thioketone bond. In addition, some or all of the hydrogen atoms of the (n8)-valent hydrocarbon group or the (n8)-valent heterocyclic group may be substituted with a group containing a hetero atom, and the —CH ２ A part of - may be substituted with a group containing a hetero atom, ２４ and R ２５ may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms.)

6. 6. The method for producing a laminate according to claim 5, wherein the resist underlayer film is formed by applying an underlayer film forming material onto a substrate and then heat treating the applied material.

7. 6. The method for producing a laminate according to claim 5, wherein the resist underlayer film is formed by a CVD method or an ALD method.

8. The method for producing a laminate according to any one of claims 5 to 7, wherein the carboxy group-containing compound is a polymer containing a repeating unit represented by the following formula (10) or a compound represented by the following formula (11): 【Transformation 6】 (In the formula, R Ａ is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. X Ａ represents a single bond, a phenylene group, a naphthylene group, or *-C(=O)-O-X Ａ１ - is. X Ａ１ is a saturated hydrocarbylene group having 1 to 10 carbon atoms, a phenylene group, or a naphthylene group, and the saturated hydrocarbylene group may contain a hydroxy group, an ether bond, an ester bond, or a lactone ring. * represents a bond to a carbon atom in the main chain. p is 1, 2, 3 or 4. R ３１ is a p-valent hydrocarbon group having 1 to 40 carbon atoms or a p-valent heterocyclic group having 2 to 40 carbon atoms, and when p is 2, R ３１ may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, or a sulfonyl group. In addition, some or all of the hydrogen atoms of the p-valent hydrocarbon group or the p-valent heterocyclic group may be substituted with a group containing a hetero atom, and the -CH ２ A portion of - may be substituted with a group containing a hetero atom. R ３２ represents a single bond or a hydrocarbylene group having 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing a hetero atom, and the —CH ２ When p is 2 to 4, each R ３２ may be the same as or different from each other.)

9. A pattern forming method comprising the steps of: exposing a resist film of the laminate according to any one of claims 1 to 4 to i-line, KrF excimer laser, ArF excimer laser, electron beam, or extreme ultraviolet light; and developing the exposed resist film using a developer.

10. 10. The pattern forming method according to claim 9, wherein the developer is an organic solvent.

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