Silicon compound, reactive material, resin composition, photosensitive resin composition, cured film, method for producing cured film, patterned cured film, and method for producing patterned cured film

Abstract

Provided is a silicon compound represented by general formula (x). Also provided is a reactive material comprising a silicon compound represented by general formula (x). In general formula (x), R1 represents or, when there are a plurality of the residues, independently represent a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, a linear alkenyl group having 2 to 10 carbon atoms, a branched alkenyl group having 3 to 10 carbon atoms, or a cyclic alkenyl group having 3 to 10 carbon atoms, wherein all or some of hydrogen atoms in the alkyl group or the alkenyl group may be substituted by fluorine atoms; R2 represents or, when there are a plurality of the residues, independently represent a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, wherein all or some of hydrogen atoms in the alkyl group may be substituted by fluorine atoms; RA represents an acid-labile group; a represents an integer of 1 to 3, b represents an integer of 0 to 2, and c represents an integer of 1 to 3, wherein a+b+c = 4; and n represents an integer of 1 to 5.

Description

[Technical field]

[0001] The present invention relates to a silicon compound, a reactive material, a resin composition, a photosensitive resin composition, a cured film, a method for producing a cured film, a patterned cured film, and a method for producing a patterned cured film. [Background technology]

[0002] Polymer compounds containing siloxane bonds have high heat resistance and transparency. Due to these properties, there are known attempts to apply polymer compounds containing siloxane bonds to, for example, coating materials for liquid crystal displays and organic electroluminescence displays, coating agents for image sensors, sealing materials in the semiconductor field, photosensitive resin compositions, and the like. Furthermore, polymer compounds containing siloxane bonds have high oxygen plasma resistance, and therefore polymer compounds containing siloxane bonds are being considered as materials for hard masks of multi-layer resists, for example.

[0003] Patent Document 1 describes a positive photosensitive resin composition containing a polysiloxane compound having a structure in which a group represented by -C(CF3)2OX (X is a hydrogen atom or an acid labile group) is substituted on a benzene ring. Paragraph 0106, Example 3-1 of Patent Document 1 describes a method for synthesizing a polysiloxane compound in which a polysiloxane compound (polymer) having a group represented by -C(CF3)2OH is reacted with di-tert-butyl dicarbonate to introduce an acid labile group (t-butoxycarbonyl group) into the polymer.

[0004] Patent Document 2 describes a method for producing a siloxane compound having a structure in which a group represented by -C(CF3)2OH is substituted on a benzene ring, the method comprising two specific steps. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 6323225 [Patent Document 2] International Publication No. 2019 / 167770 Summary of the Invention [Problem to be solved by the invention]

[0006] In the course of their investigations into fluorine-containing siloxane compounds, the present inventors have found that conventional fluorine-containing siloxane compounds have room for improvement, for example in terms of storage stability.

[0007] Therefore, the present inventors have carried out various investigations with the aim of providing a fluorine-containing siloxane compound having good storage stability. [Means for solving the problem]

[0008] As a result of investigations, the present inventors have completed the invention provided below and have solved the above-mentioned problems. The present invention is expressed as follows.

[0009] 1. A silicon compound represented by the following general formula (x):

[0010] [ka] In general formula (x), R 1 when there are multiple, each independently represents a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a linear alkenyl group having 2 to 10 carbon atoms, a branched alkenyl group having 3 to 10 carbon atoms, in which all or a part of the hydrogen atoms in the alkyl group or alkenyl group may be substituted with fluorine atoms, R 2 when there are multiple, each independently represents a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms, in which all or a part of the hydrogen atoms in the alkyl group may be substituted with fluorine atoms, R Ais an acid labile group, a is an integer from 1 to 3, b is an integer from 0 to 2, c is an integer from 1 to 3, and a+b+c=4; n is an integer from 1 to 5.

[0011] 2. 1. The silicon compound according to claim 1, R A is at least one selected from the group consisting of an alkyl group, an alkoxycarbonyl group, an acetal group, a silyl group and an acyl group.

[0012] 3. A reactive material comprising a silicon compound (X) represented by the following general formula (x):

[0013] [ka]

[0014] In general formula (x), R 1 when there are multiple, each independently represents a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a linear alkenyl group having 2 to 10 carbon atoms, a branched alkenyl group having 3 to 10 carbon atoms, in which all or a part of the hydrogen atoms in the alkyl group or alkenyl group may be substituted with fluorine atoms, R 2 when there are multiple, each independently represents a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms, in which all or a part of the hydrogen atoms in the alkyl group may be substituted with fluorine atoms, R A is an acid labile group, a is an integer from 1 to 3, b is an integer from 0 to 2, c is an integer from 1 to 3, and a+b+c=4; n is an integer from 1 to 5.

[0015] 4. 3. The reactive material according to claim 2, R Ais at least one reactive material selected from the group consisting of an alkyl group, an alkoxycarbonyl group, an acetal group, a silyl group and an acyl group.

[0016] 5. 3. or 4. The reactive material according to claim 1, Further, the composition contains a silicon compound (Y) represented by the following general formula (y): The mass of the silicon compound (X) contained in the reactive material is M X The mass of the silicon compound (Y) is M Y Then, {M Y / (M X +M Y )}×100, the ratio of silicon compound (Y) is 1×10 -4 ~12% by weight of reactive material.

[0017] [ka]

[0018] In general formula (y), R 1 , R 2 The definitions of a, b, c and n are the same as those in general formula (x). 6. A polysiloxane compound obtained by polycondensing the silicon compound according to 1. or 2. or the reactive material according to any one of 3. to 5. in the presence of an acidic catalyst or a basic catalyst.

[0019] 7. 6. The polysiloxane compound according to claim 6, A polysiloxane compound having a weight average molecular weight of 1,000 to 100,000.

[0020] 8. 8. A resin composition comprising the polysiloxane compound according to 6. or 7. above and a solvent.

[0021] 9. 8. The resin composition according to claim 8, The resin composition wherein the solvent contains at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, γ-butyrolactone, diacetone alcohol, diglyme, methyl isobutyl ketone, 3-methoxybutyl acetate, 2-heptanone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, glycols, glycol ethers, and glycol ether esters.

[0022] 10. 8. A photosensitive resin composition comprising the resin composition according to 8. or 9. and a photoacid generator.

[0023] 11. A cured film of the resin composition according to 8. or 9.

[0024] 12. A method for producing a cured film, comprising a heating step of applying the resin composition according to 8. or 9. onto a substrate and then heating the composition at a temperature of 100 to 350°C.

[0025] 13. 10. A patterned cured film of the photosensitive resin composition according to claim 10.

[0026] 14. A film-forming step of applying the photosensitive resin composition according to claim 10 onto a substrate to form a photosensitive resin film; an exposure step of exposing the photosensitive resin film to light; a developing step of developing the photosensitive resin film after exposure to form a patterned resin film; a curing step of heating the patterned resin film to convert the patterned resin film into a patterned cured film; A method for producing a patterned cured film comprising the steps of:

[0027] 15. 14. A method for producing a patterned cured film according to the present invention, comprising the steps of: The method for producing a patterned cured film, wherein the wavelength of light used for exposure in the exposure step is 100 to 600 nm. Effect of the Invention

[0028] According to the present invention, there is provided a fluorine-containing siloxane compound having good storage stability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0029] Hereinafter, an embodiment of the present invention will be described in detail.

[0030] In this specification, unless otherwise specified, the expression "X to Y" in the explanation of a numerical range means from X to Y. For example, "1 to 5% by mass" means "from 1% by mass to 5% by mass".

[0031] In the description of groups (atomic groups) in this specification, when a description is made without specifying whether the group is substituted or unsubstituted, the description includes both groups having no substituents and groups having a substituent. For example, an "alkyl group" includes not only an alkyl group having no substituents (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In this specification, the term "cyclic alkyl group" includes not only a single ring structure but also a polycyclic structure. The same applies to a "cycloalkyl group". In this specification, the term "(meth)acrylic" refers to a concept that includes both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate." In this specification, the term "organic group" means an atomic group obtained by removing one or more hydrogen atoms from an organic compound, unless otherwise specified. For example, a "monovalent organic group" refers to an atomic group obtained by removing one hydrogen atom from any organic compound.

[0032] In this specification, the group represented by -C(CF3)2OH may also be expressed as an "HFIP group", which is the abbreviation for hexafluoroisopropanol group.

[0033] <Silicon compounds and reactive materials> The silicon compound (silicon compound (X)) of this embodiment is represented by the following general formula (x). The reactive material of the present embodiment also contains a silicon compound (X) represented by the following general formula (x).

[0034] [ka]

[0035] In general formula (x), R 1 when there are multiple, each independently represents a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a linear alkenyl group having 2 to 10 carbon atoms, a branched alkenyl group having 3 to 10 carbon atoms, in which all or a part of the hydrogen atoms in the alkyl group or alkenyl group may be substituted with fluorine atoms, R 2 when there are multiple, each independently represents a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms, in which all or a part of the hydrogen atoms in the alkyl group may be substituted with fluorine atoms, R A is an acid labile group, a is an integer from 1 to 3, b is an integer from 0 to 2, c is an integer from 1 to 3, and a+b+c=4; n is an integer from 1 to 5.

[0036] In the silicon compound (X), the hydrogen atom (which exhibits acidity) of the HFIP group is protected with an acid labile group. This results in -SiR 1 b (OR 2 ) c It is believed that partial hydrolysis and polycondensation are suppressed, resulting in good storage stability, which is a very desirable property for the industrial use of chemical materials.

[0037] The silicon compound (X) / reactive material of this embodiment will be described in more detail below.

[0038] (Regarding general formula (x)) In terms of availability and cost of raw materials, 1 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group. Similarly, in terms of availability and cost of raw materials, 2 is preferably a methyl group or an ethyl group. From the viewpoint of ease of synthesis, a is preferably 1. Similarly, in terms of ease of synthesis, n is preferably 1 or 2, and more preferably 1. c is preferably 2 or 3. OR of 2 or more 2 The presence of the above makes it possible to produce a polysiloxane compound (polymer or oligomer) using the silicon compound (X). Due to the reactivity (orientation) of the benzene ring, -C(CF3)2OR A is preferably -SiR 1 b (OR 2 ) c It is preferable that the moiety of the following group (2) in the general formula (x) is present at the meta position relative to the group represented by the following formula (2A) to formula (2D). Among them, the structure represented by the formula (2A) or formula (2D) is preferable.

[0039] [ka]

[0040] [ka]

[0041] In the group (2) and the formulae (2A) to (2D), the wavy lines indicate that the intersecting line segments are bonds.

[0042] R AThe acid labile group may be any group known in the field of photosensitive resin compositions without particular limitation, such as an alkyl group, an alkoxycarbonyl group, an acetal group, a silyl group, or an acyl group. Examples of the alkyl group include a tert-butyl group, a tert-amyl group, a 1,1-dimethylpropyl group, a 1-ethyl-1-methylpropyl group, a 1,1-dimethylbutyl group, an allyl group, a 1-pyrenylmethyl group, a 5-dibenzosuberyl group, a triphenylmethyl group, a 1-ethyl-1-methylbutyl group, a 1,1-diethylpropyl group, a 1,1-dimethyl-1-phenylmethyl group, a 1-methyl-1-ethyl-1-phenylmethyl group, a 1,1-diethyl-1-phenylmethyl group, a 1-methylcyclohexyl group, a 1-ethylcyclohexyl group, a 1-methylcyclopentyl group, a 1-ethylcyclopentyl group, a 1-isobornyl group, a 1-methyladamantyl group, a 1-ethyladamantyl group, a 1-isopropyladamantyl group, a 1-isopropylnorbornyl group, and a 1-isopropyl-(4-methylcyclohexyl) group. The alkyl group is preferably a tertiary alkyl group, more preferably -CR p R q R r (R p , R q and R r are each independently a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an aryl group, or an aralkyl group; R p , R q and R r Two of the groups may be bonded to form a ring structure. Examples of the alkoxycarbonyl group include a tert-butoxycarbonyl group, a tert-amyloxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, and an i-propoxycarbonyl group. Examples of the acetal group include a methoxymethyl group, an ethoxyethyl group, a butoxyethyl group, a cyclohexyloxyethyl group, a benzyloxyethyl group, a phenethyloxyethyl group, an ethoxypropyl group, a benzyloxypropyl group, a phenethyloxypropyl group, an ethoxybutyl group, and an ethoxyisobutyl group. Examples of the silyl group include a trimethylsilyl group, an ethyldimethylsilyl group, a methyldiethylsilyl group, a triethylsilyl group, an i-propyldimethylsilyl group, a methyldi-i-propylsilyl group, a tri-i-propylsilyl group, a tert-butyldimethylsilyl group, a methyldi-tert-butylsilyl group, a tri-tert-butylsilyl group, a phenyldimethylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a heptanoyl group, a hexanoyl group, a valeryl group, a pivaloyl group, an isovaleryl group, a lauryl group, a myristoyl group, a palmitoyl group, a stearoyl group, an oxalyl group, a malonyl group, a succinyl group, a glutaryl group, adipoyl group, a piperoyl group, a suberoyl group, an azelaoyl group, a sebacoyl group, a (meth)acryloyl group, a propioloyl group, a crotonoyl group, an oleoyl group, a maleoyl group, a fumaroyl group, a mesaconoyl group, a campholoyl group, a benzoyl group, a phthaloyl group, an isophthaloyl group, a terephthaloyl group, a naphthoyl group, a toluoyl group, a hydroatropoyl group, an atropoyl group, a cinnamoyl group, a furoyl group, a thenoyl group, a nicotinoyl group, and an isonicotinoyl group. Some or all of the hydrogen atoms of the acid labile group may be substituted with fluorine atoms.

[0043] Particularly preferred R A Examples of the structure include a structure represented by the following general formula (ALG-1) and a structure represented by the following general formula (ALG-2).

[0044] [ka]

[0045] In the general formula (ALG-1), R 11 represents a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 21 carbon atoms, R 12 is a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 21 carbon atoms.

[0046] In the general formula (ALG-2), R 13 , R 14 and R 15 each independently represents a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 21 carbon atoms, R 13 , R 14 and R 15 Two of these may be bonded to each other to form a ring structure.

[0047] In general formulae (ALG-1) and (ALG-2), * represents a bonding site with an oxygen atom.

[0048] In the general formula (x), when n is 2 or more, one molecule of the silicon compound (X) contains two or more R A In this case, there are two or more R A may be the same or different from each other. In addition, the reactive material of the present embodiment is made up of R A Of course, the reactive material of the present embodiment may contain substantially only one type of silicon compound (X).

[0049] Specific examples of the silicon compound (X) are listed below.

[0050] [ka]

[0051] In each of the above specific examples, R 1 , R 2 The combination of a, b and c is, for example, any one of combinations 1 to 6 shown in the following Table 1. In Table 1, Me represents a methyl group, and Et represents an ethyl group.

[0052] [Table 1]

[0053] (Silicon Compound (Y)) The reactive material of the present embodiment may further contain a silicon compound (Y) represented by the following general formula (y). In this case, the mass of the silicon compound (X) contained in the reactive material is M X , the mass of the silicon compound (Y) is M Y Then, {M Y / (M X +M Y The ratio (mass%) of the silicon compound (Y) represented by {(mass%)}×100 is preferably 1×10 -4 ~12%, more preferably 5×10 -4 The content is preferably from 0.001 to 10%, more preferably from 0.001 to 8%, and particularly preferably from 0.01 to 5%.

[0054] [ka]

[0055] In general formula (y), R 1 , R 2 The definitions and preferred embodiments of a, b, c and n are the same as those in formula (x).

[0056] The silicon compound (Y) has an HFIP group that is not protected by an acid labile group. This makes the silicon compound (Y) acidic. It is believed that the inclusion of an appropriate amount of the acidic silicon compound (Y) in the reactive material provides the effect of good reactivity while providing the effect of storage stability. It is considered that the silicon compound (Y) contributes to the reaction of the silicon compound (X), for example, polycondensation (formation of siloxane bond by dehydration), as an acid catalyst.Therefore, it is considered that the reactive material of this embodiment contains an appropriate amount of silicon compound (Y), and thus, for example, when the reactive material of this embodiment is used as a raw material monomer of a polysiloxane compound, it is possible to obtain good polymerizability while obtaining the effect of storage stability.In addition, for example, when the reactive material of this embodiment is used as a primer, it is possible to obtain good adhesion and curability while obtaining the effect of storage stability. Furthermore, for example, when the reactive material of this embodiment is used as a raw material monomer for a polysiloxane compound, the silicon compound (Y) is considered to be incorporated into the polysiloxane compound produced. This is considered to be advantageous in that it is not necessary to remove the catalyst after the synthesis of the polysiloxane compound.

[0057] (Method of producing silicon compound (X) / reactive material) The method for producing the silicon compound (X) / reactive material of this embodiment is not particularly limited. A typical method for producing the silicon compound (X) / reactive material is described below.

[0058] First, in the general formula (x), R A Such compounds are known and can be synthesized by referring to the method described in the above-mentioned Patent Document 2, for example.

[0059] Next, in the general formula (x), R A An acid labile group is introduced into a compound in which R is a hydrogen atom. As a method for introducing an acid labile group, a known method for introducing an acid labile group into an alcohol compound can be used.

[0060] For example, a dialkyl dicarbonate compound or an alkoxycarbonyl alkyl halide and a compound represented by the general formula (x), R A An acid labile group can be introduced by reacting a compound in which is a hydrogen atom in a solvent in the presence of a base.

[0061] As an example of a method for introducing an acid labile group, a tert-butoxycarbonyl group (R 13 , R 14 and R 15 A method for introducing a group (wherein is a methyl group) will be explained. In the general formula (x), R A Di-tert-butyl dicarbonate is added in an amount equal to or greater than the amount of HFIP groups present in the molecule of a compound in which R is a hydrogen atom, and the compound is dissolved in a solvent in the presence of a base such as pyridine, triethylamine, or N,N-dimethylaminopyridine and reacted. In this manner, a tert-butoxycarbonyl group can be introduced. The solvent that can be used is not particularly limited as long as it can dissolve the compound put into the reaction system and does not adversely affect the reaction. Specifically, toluene, xylene, pyridine, etc. are preferred. The reaction temperature and reaction time vary depending on the type of base used, but the reaction temperature is usually from room temperature to 180° C., and the reaction time is 1 to 24 hours. After the reaction is completed, the solvent, base, and di-tert-butyl dicarbonate, if added in excess, are distilled off to obtain the compound represented by the general formula (x) R A is a tert-butoxycarbonyl group.

[0062] As another example of a method for introducing an acid labile group, a methoxymethyl group (R 11 is a methyl group, R 12 A method for introducing a group (wherein is a hydrogen atom) will be explained. In the general formula (x), R AA strong base (such as NaH) and a chloromethyl methyl ether in an amount equal to or greater than the amount of HFIP groups present in the molecule of a compound in which the is a hydrogen atom are added and reacted. In this manner, a methoxymethyl group can be introduced. The solvent that can be used at this time is not particularly limited, and any solvent that can dissolve the compound to be added to the reaction system and does not adversely affect the reaction can be used. A preferred solvent is tetrahydrofuran, etc. The reaction proceeds even at room temperature. After the reaction is completed, it is preferable to carry out post-treatment such as adding a solvent (toluene, diisopropyl ether, etc.) for separating into two layers during water washing, washing with water, washing with saline, and simple distillation (pressure of about 2.5 kPa, temperature of about 200 to 220°C).

[0063] As yet another example of the method for introducing an acid labile group, a method for introducing an acid labile group using vinyl acetal will be described. In the general formula (x), R A The amount of vinyl acetal (R 11 Compounds represented by -O-CH=CH2, R 11 The definition of is the same as that of general formula (ALG-1)) is reacted in the presence of an acid catalyst (e.g., paratoluenesulfonic acid). 12 An acid labile group, in which the aryl group is a methyl group, can be introduced. The solvent that can be used in this case is not particularly limited, and any solvent that can dissolve the compound to be added to the reaction system and does not adversely affect the reaction can be used. The reaction proceeds even at room temperature. After the reaction is completed, post-treatment such as washing and distillation may be performed.

[0064] <Polysiloxane compound and its manufacturing method> The polysiloxane compound of the present embodiment is produced by polycondensing the above silicon compound (silicon compound (X)) or the above reactive material in the presence of an acidic or basic catalyst. The silicon compound (X) is produced by polycondensing the above silicon compound (silicon compound (X)) or the above reactive material in the presence of an acidic or basic catalyst. 2The " part is hydrolyzed, which generates silanol groups. Two or more of the generated silanol groups undergo dehydration condensation to obtain a polysiloxane compound. Alternatively, the generated silanol groups and "Si-OR 2 Polysiloxane compounds can also be obtained by a condensation reaction of the " moiety. During polycondensation, a reactive material (monomer) other than the silicon compound (X) or the silicon compound (Y) may be present in the reaction system. This allows a copolymer to be obtained. This will be explained later.

[0065] Methods for producing a polysiloxane compound having a structure in which an HFIP group is protected with an acid labile group can be broadly classified into the following two production methods. Production method 1: A reactive material having an unprotected HFIP group (e.g., in the general formula (x), R A A polymer or oligomer is obtained by polycondensation of a compound in which R is a hydrogen atom, and then an acid labile group is introduced into the polymer or oligomer. Production method 2: A reactive material, such as a silicon compound (X), in which the HFIP group has been protected with an acid labile group in advance, is polycondensed.

[0066] In Example 3-1 of the above-mentioned Patent Document 1, a polysiloxane compound having an acid labile group is produced by the above-mentioned "production method 1." However, according to the knowledge of the present inventors, when a polysiloxane compound is produced by the production method 1, problems such as the production of undesirable by-products, coloration of the final product, and difficulty in producing a polysiloxane compound with a large weight average molecular weight can occur. The present inventors have conducted various studies to solve the above problems. Through the studies, they have unexpectedly found that when a polysiloxane compound is produced according to Production Method 2, the above problems are unlikely to occur.

[0067] It is not necessarily clear how the polysiloxane compound produced by Production Method 1 differs from the polysiloxane compound produced by Production Method 2. However, the present inventors have found that the polysiloxane compound produced by Production Method 1 and the polysiloxane compound produced by Production Method 2 appear to differ, for example, in terms of transparency.

[0068] Although it is merely speculation, the reasons why the polysiloxane compounds produced by Production Method 1 and those produced by Production Method 2 are different in nature are thought to be related to (1) the fact that the unprotected HFIP group in Production Method 1 deactivates the polymerization catalyst (particularly the basic catalyst), and (2) the fact that Production Method 1 is more likely to produce unintended by-products and that the by-products may be difficult to remove. To supplement the above (2), introducing an acid labile group into the raw material monomer before producing a polysiloxane compound, as in Production Method 2, makes it easier to remove impurities (unreacted materials, etc.) than in Production Method 1, which is thought to lead to increased transparency of the final polysiloxane compound. In other words, a highly transparent polysiloxane compound can be easily obtained by polycondensing the above silicon compound (silicon compound (X)) or the above reactive material in the presence of an acidic or basic catalyst.

[0069] The present inventors have found that the polysiloxane compound produced by Production Method 2 tends to have a higher weight-average molecular weight than the polysiloxane compound produced by Production Method 1. In other words, the reactive material containing the silicon compound (X) of this embodiment has good storage stability and good reactivity in that it can produce a polysiloxane compound with a higher weight-average molecular weight.

[0070] The weight average molecular weight of the polysiloxane compound of the present embodiment is preferably 1,000 to 100,000, and more preferably 1,500 to 50,000. As described above, by using the reactive material of the present embodiment as a raw material and subjecting the raw material to polycondensation in the presence of an acidic catalyst or a basic catalyst, a polysiloxane compound having a relatively large weight average molecular weight tends to be obtained.

[0071] Regarding the procedure and reaction conditions of polycondensation in producing the polysiloxane compound of the present embodiment, known techniques in hydrolysis and condensation reaction of alkoxysilanes can be appropriately applied. As an example, the polysiloxane compound of the present embodiment can be produced by the following procedures and conditions (1) to (4).

[0072] (1) First, a predetermined amount of the reactive material is placed in a reaction vessel at room temperature (which refers to the ambient temperature without heating or cooling, usually about 15 to 30° C.). (2) Water for hydrolysis, a catalyst for promoting the polycondensation reaction, and optionally a reaction solvent are added to a reaction vessel and stirred appropriately to prepare a reaction solution. The order of addition of these is not particularly limited, and the reaction solution can be prepared by adding them in any order. At this time, a siloxane compound (monomer) that does not fall under the silicon compound (X) or silicon compound (Y) may be added to the reaction vessel. In this way, a polysiloxane compound that is a copolymer can be produced. (3) The reaction solution prepared in (2) is stirred while the hydrolysis and condensation reactions proceed. Although it depends on the type of catalyst, the time required for the reaction is usually 3 to 24 hours, and the reaction temperature is usually room temperature (25°C) to 200°C. When heating, it is preferable to reflux the reaction system by making the reaction vessel a closed system or by attaching a reflux device such as a condenser to prevent unreacted raw materials, water, reaction solvent and / or catalyst in the reaction system from being distilled out of the reaction system. (4) After the reaction is completed, it is preferable to remove the water remaining in the reaction system, the produced alcohol, the catalyst, etc. The water, alcohol, and catalyst may be removed by extraction, or by azeotropic removal using a Dean-Stark apparatus after adding a solvent that does not adversely affect the reaction, such as toluene, to the reaction system.

[0073] The amount of water used in the hydrolysis and condensation reactions is not particularly limited. From the viewpoint of reaction efficiency, the amount of water used in the hydrolyzable group (OR in the general formula (x)) contained in the raw material is preferably 100 to 2000. 2 The amount is preferably 0.5 to 5 times the total number of moles of the above-mentioned compounds.

[0074] There is no particular limitation on the catalyst for promoting polycondensation, and any known acid catalyst or base catalyst can be appropriately used. Examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, oxalic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, benzenesulfonic acid, tosylic acid, formic acid, polycarboxylic acids, and anhydrides thereof. Examples of the base catalyst include tetramethylammonium hydroxide, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, and sodium carbonate. The amount of catalyst used is determined by the ratio of the hydrolyzable group (OR in the general formula (x)) contained in the raw material. 2 etc.) for the total number of moles, 1.0 x 10 -5 ~1.0×10 -1 Preferably, it is twice as large.

[0075] In producing the polysiloxane compound, a reaction solvent may or may not be used. When a reaction solvent is used, the type is not particularly limited. From the viewpoint of solubility in the raw material compound, water, and catalyst, a polar solvent is preferable, and an alcohol solvent is more preferable. Specific examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, diacetone alcohol, and propylene glycol monomethyl ether. The reaction solvent may be a single solvent or a mixed solvent. When a reaction solvent is used, the amount used may be an amount necessary for the reaction to proceed in a homogeneous system.

[0076] (Copolymer component (silicon compound (Z)) As described above, during polycondensation, one or more reactive materials (monomers) other than the silicon compound (X) or silicon compound (Y) may be present in the reaction system to obtain a copolymer. Specifically, in the above step (2), a siloxane compound or silane compound monomer that does not fall under the category of the silicon compound (X) or silicon compound (Y) is added to the reaction vessel to obtain a copolymer. Hereinafter, "siloxane compounds or silane compound monomers that do not fall under the category of silicon compounds (X) or silicon compounds (Y)" will be collectively referred to as "silicon compounds (Z)."

[0077] A preferred example of the silicon compound (Z) is a compound having, in one molecule, (i) a hydrolyzable alkoxysilyl group and (ii) at least one group selected from the group consisting of an epoxy group, an oxetane group, and a (meth)acryloyl group (hereinafter, this compound is also referred to as silicon compound (Z1)). By incorporating a structural unit derived from the silicon compound (Z1) into the polysiloxane compound of this embodiment, the polysiloxane compound of this embodiment can be preferably used in, for example, a thermosetting resin composition.

[0078] More specifically, the silicon compound (Z1) is represented by the following general formula (z1).

[0079] [ka]

[0080] In general formula (z1), R 1 , R 2 The definitions and preferred embodiments of a, b and c are the same as those of general formula (x), R y is a monovalent organic group having 2 to 30 carbon atoms that contains an epoxy group, an oxetane group, or a (meth)acryloyl group. R y By including an epoxy group or an oxetane group, for example, when the polysiloxane compound of the present embodiment is applied to a resin composition or the like described below, the adhesion to various substrates such as silicon, glass, and resin can be improved. y In the case where contains a (meth)acryloyl group, for example, when the polysiloxane compound of the present embodiment is formed into a cured film as described below, good solvent resistance can be obtained.

[0081] R y If contains an epoxy group or an oxetane group, R y is preferably a group represented by the following formula (2a), (2b) or (2c).

[0082] [ka]

[0083] In the above formula, R g , R h and R i Each independently represents a single bond or a divalent organic group. The dashed line represents a bond. R g , R h and R iWhen is a divalent organic group, the divalent organic group may be, for example, an alkylene group having 1 to 20 carbon atoms. This alkylene group may contain one or more moieties forming an ether bond. When the number of carbon atoms is 3 or more, the alkylene group may be branched, or distant carbon atoms may be linked to form a ring. When there are two or more alkylene groups, oxygen may be inserted between carbon atoms to contain one or more moieties forming an ether bond.

[0084] R y When R contains a (meth)acryloyl group, y is preferably a group selected from the following formula (3a) or (4a).

[0085] [ka]

[0086] In the above formula, R j and R k each independently represents a single bond or a divalent organic group. A dashed line represents a bond. R j and R k Preferred examples of the divalent organic group include R g , R h and R i Examples of the preferred groups include those mentioned above.

[0087] Specific examples of the silicon compound (Z1) include 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM-403), 3-glycidoxypropyltriethoxysilane (same company, product name: KBE-403), 3-glycidoxypropylmethyldiethoxysilane (same company, product name: KBE-402), 3-glycidoxypropylmethyldimethoxysilane (same company, product name: KBM-402), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (same company, product name: KBM-303), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (same company, product name: KBM-303), and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (same company, product name: KBM-403). Examples of the silane include ethyltriethoxysilane, 8-glycidoxyoctyltrimethoxysilane (product name: KBM-4803), [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, and [(3-ethyl-3-oxetanyl)methoxy]propyltriethoxysilane. Specific examples of the silicon compound (Z1) include 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name: KBM-503), 3-methacryloxypropyltriethoxysilane (same company, product name: KBE-503), 3-methacryloxypropylmethyldimethoxysilane (same company, product name: KBM-502), 3-methacryloxypropylmethyldiethoxysilane (same company, product name: KBE-502), 3-acryloxypropyltrimethoxysilane (same company, product name: KBM-5103), and 8-methacryloxyoctyltrimethoxysilane (same company, product name: KBM-5803).

[0088] Other examples of silicon compounds (Z) include tetraalkoxysilane, tetrahalosilane, and their oligomers. Examples of oligomers include silicate 40 (average pentamer, manufactured by Tama Chemical Industry Co., Ltd.), ethyl silicate 40 (average pentamer, manufactured by Colcoat Co., Ltd.), silicate 45 (average heptamer, manufactured by Tama Chemical Industry Co., Ltd.), M silicate 51 (average tetramer, manufactured by Tama Chemical Industry Co., Ltd.), methyl silicate 51 (average tetramer, manufactured by Colcoat Co., Ltd.), methyl silicate 53A (average heptamer, manufactured by Colcoat Co., Ltd.), ethyl silicate 48 (average decamer, manufactured by Colcoat Co., Ltd.), and EMS-485 (mixture of ethyl silicate and methyl silicate, manufactured by Colcoat Co., Ltd.).

[0089] Further examples of the silicon compound (Z) include various alkoxysilanes. Specifically, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldiphenoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiphenoxysilane, bis(3,3,3-trifluoropropyl)dimethoxysilane, methyl(3,3,3-trifluoropropyl)dimethoxysilane, methyltrimethoxysilane, methylphenyldimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxy ... Silane, methylphenyldiethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, isopropyltriethoxysilane, phenyltriethoxysilane, methyltripropoxysilane, ethyltripropoxysilane, propyltripropoxysilane, isopropyltripropoxysilane, phenyltripropoxysilane, methyltriisopropoxysilane, ethyltriisopropoxysilane, propyltriisopropoxysilane, isopropyltriisopropoxysilane, phenyltriisopropoxysilane, trifluoromethyltrimethoxysilane, pentafluoroethyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, and the like.

[0090] Among the above examples, in terms of heat resistance and transparency when the polysiloxane compound is made into a cured film, phenyltrimethoxysilane, phenyltriethoxysilane, methylphenyldimethoxysilane, and methylphenyldiethoxysilane are preferred. In addition, in terms of increasing flexibility and preventing cracks when the polysiloxane compound is made into a cured film, dimethyldimethoxysilane and dimethyldiethoxysilane are preferred.

[0091] When the silicon compound (Z) is used, only one type may be used, or two or more types may be used. When the silicon compound (Z) is used, its amount may be appropriately adjusted depending on the desired performance, etc. Specifically, when the silicon compound (Z) is used, its amount is, for example, 1 to 50 mol%, preferably 5 to 40 mol%, in all the polymerizable components (silicon compounds (X), (Y) and (Z)) used in the polycondensation. When the silicon compound (Z1) is used, the amount thereof is preferably 1 to 50 mol %, more preferably 5 to 40 mol %, of all the polymerizable components used in the polycondensation, taking into consideration the balance between curability and other properties. In general, the ratio of the silicon compounds (X), (Y) and (Z) to the ratio of the structural units in the polysiloxane compound corresponding to the silicon compounds (X), (Y) and (Z) can be considered to be roughly the same.

[0092] <Resin composition, cured film of resin composition, and method for producing the cured film> The resin composition of this embodiment includes the above-mentioned polysiloxane compound and a solvent. In other words, the resin composition of this embodiment is a composition in which the above-mentioned polysiloxane compound is dissolved and / or dispersed in a solvent. The polysiloxane compound is dissolved and / or dispersed in a solvent to form a resin composition, and the resin composition is applied onto a substrate, and the solvent is dried to form a resin film. In addition, a cured film can be produced by heating the resin film.

[0093] The solvent typically includes an organic solvent. Preferred usable solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, γ-butyrolactone, diacetone alcohol, diglyme, methyl isobutyl ketone, 3-methoxybutyl acetate, 2-heptanone, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0094] In addition, glycols, glycol ethers, glycol ether esters, etc. can also be used as solvents. Specific examples include Cellutol (registered trademark) manufactured by Daicel Corporation and Hisorb (registered trademark) manufactured by Toho Chemical Industry Co., Ltd. More specific examples include cyclohexanol acetate, dipropylene glycol dimethyl ether, propylene glycol diacetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, 3-methoxybutyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin ... Examples of the ethylene glycol ether include ethylene glycol, propylene glycol-n-propyl ether, propylene glycol-n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol-n-propyl ether, dipropylene glycol-n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol-n-butyl ether, triethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, and triethylene glycol dimethyl ether.

[0095] The solvent may be a single solvent or a mixed solvent. The amount of the solvent used is not particularly limited, but is used so that the total solid content (components other than the volatile solvent) in the resin composition is usually 5 to 60 mass %, preferably 10 to 50 mass %. By appropriately adjusting the total solid content concentration, the ease of forming a thin film and the uniformity of the film thickness tend to improve.

[0096] The resin composition of the present embodiment may contain one or more additive components in addition to the polysiloxane compound and the solvent. For example, additives such as surfactants can be blended for the purpose of improving coating properties, leveling properties, film-forming properties, storage stability, defoaming properties, etc. Specific examples of commercially available surfactants include MEGAFAC (trade name), product numbers F142D, F172, F173, and F183, manufactured by DIC Corporation, Fluorad (trade name), product numbers FC-135, FC-170C, FC-430, and FC-431, manufactured by Sumitomo 3M Limited, Surflon (trade name), product numbers S-112, S-113, S-131, S-141, and S-145, manufactured by AGC Seimi Chemical Co., Ltd., and SH-28PA, SH-190, SH-193, SZ-6032, and SF-8428, manufactured by Toray Dow Corning Silicone Co., Ltd. ("Megafac," "Florald," and "Surflon" are registered trademarks of their respective companies.)

[0097] When a surfactant is used, only one surfactant may be used, or two or more surfactants may be used. When a surfactant is used, the amount thereof is usually 0.001 to 10 parts by mass based on 100 parts by mass of the polysiloxane compound.

[0098] As another additive component, a curing agent can be used for the purpose of improving the resistance to chemical solutions when the cured film is formed. Examples of the curing agent include a melamine curing agent, a urea resin curing agent, a polybasic acid curing agent, an isocyanate curing agent, and an epoxy curing agent.

[0099] Specific examples include isocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, and diphenylmethane diisocyanate, and their isocyanurates, blocked isocyanates, and biuret derivatives; amino compounds such as melamine resins such as alkylated melamine, methylol melamine, and imino melamine, and urea resins; and epoxy curing agents having two or more epoxy groups obtained by reacting a polyhydric phenol such as bisphenol A with epichlorohydrin.

[0100] When a curing agent is used, only one curing agent may be used, or two or more curing agents may be used. When a curing agent is used, the amount thereof is usually 0.001 to 10 parts by mass based on 100 parts by mass of the polysiloxane compound.

[0101] A method for producing a cured film using the resin composition of the present embodiment includes, for example, A film forming step of applying the resin composition of the present embodiment onto a substrate to form a resin film; a curing step of heating the resin film to form a cured film; may include. The film-forming step and the curing step will be specifically described below.

[0102] ·Film formation process In the film-forming step, the substrate to which the resin composition is applied is not particularly limited and may be selected from silicon wafers, metals, glass, ceramics, and plastic substrates depending on the application of the cured film to be formed. The coating method and coating device used for forming the film are not particularly limited, and any known coating method / device such as spin coating, dip coating, spray coating, bar coating, applicator, inkjet, roll coating, etc. can be used.

[0103] The substrate coated with the resin composition is heated, for example, at 80 to 120° C. for 30 seconds to 5 minutes to volatilize the solvent in the resin composition, thereby obtaining a resin film.

[0104] ·Curing process A cured film can be obtained by further heating the resin film formed in the film formation process. The temperature of the heat treatment is usually 100 to 350°C. Although it depends on the boiling point of the solvent, a more preferable temperature is 150 to 280°C. By heating at a moderately high temperature, the processing speed can be increased. On the other hand, by not using an excessively high heating temperature, the uniformity of the cured film can be improved.

[0105] <Photosensitive resin composition, patterned cured film, and method for producing patterned cured film> The photosensitive resin composition of the present embodiment includes the polysiloxane compound, a photoacid generator, and a solvent. In other words, the photosensitive resin composition of the present embodiment can be produced by further adding a photoacid generator to the above-mentioned resin composition.

[0106] The photoacid generator is not particularly limited as long as it is a compound that generates an acid when irradiated with light such as ultraviolet light. The acid generated by light irradiation acts on the acid labile group in the polysiloxane compound, and the acid labile group is eliminated to generate an HFIP group. This makes the polysiloxane compound soluble in an alkaline developer. On the other hand, without light irradiation, the polysiloxane compound remains insoluble in an alkaline developer. By utilizing such a change in solubility in an alkaline developer caused by light irradiation, a patterned resin film can be produced from the photosensitive resin composition. In addition, a patterned cured film can be obtained by curing the pattern.

[0107] Specific examples of the photoacid generator include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, and oxime-O-sulfonate. The photoacid generator is not particularly limited as long as it generates an acid capable of eliminating an acid labile group. The photoacid generator may be used alone or in combination of two or more kinds.

[0108] Commercially available photoacid generators include trade names: Irgacure PAG121, Irgacure PAG103, Irgacure CGI1380, and Irgacure CGI725 (all manufactured by BASF), trade names: PAI-101, PAI-106, NAI-105, NAI-106, TAZ-110, TAZ-204 (all manufactured by Midori Chemical Co., Ltd.), trade names: CPI-200K, CPI-210S, CPI-101A, CPI-110A, CPI-100P, CPI-110P, CPI-100TF, CPI-110TF, HS-1, HS-1A, HS-1P, HS-1N, HS-1TF, HS-1NF, HS-1MS, HS-1CS, LW-S1, LW-S1NF (all manufactured by San-Apro Co., Ltd.), trade names: TFE-triazine, TME-triazine or MP-triazine (all manufactured by Sanwa Chemical Co., Ltd.). Of course, the photoacid generator that can be used is not limited to these.

[0109] When a photoacid generator is used, only one photoacid generator may be used, or two or more photoacid generators may be used. The amount of the photoacid generator is, for example, 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the polysiloxane compound. By using an appropriate amount of the photoacid generator, it is possible to achieve both sufficient sensitivity and resolution and storage stability of the composition.

[0110] The photosensitive resin composition of the present embodiment may contain one or more additive components, as in the above-mentioned resin composition. Examples of the additive components that can be added are also as described above.

[0111] In terms of "photosensitivity", a sensitizer may be used as an added component. The sensitizer preferably has light absorption at the exposure wavelength in the exposure process (e.g., 365 nm (i-line), 405 nm (h-line), 436 nm (g-line)). However, if the sensitizer remains in the cured film as is, a problem of reduced transparency may occur. Therefore, the sensitizer is preferably a compound that vaporizes during heat treatment such as thermal curing, or a compound that fades when exposed to light such as bleaching exposure.

[0112] Specific examples of sensitizers include coumarins such as 3,3'-carbonylbis(diethylaminocoumarin), anthraquinones such as 9,10-anthraquinone, aromatic ketones such as benzophenone, 4,4'-dimethoxybenzophenone, acetophenone, 4-methoxyacetophenone, and benzaldehyde, biphenyl, 1,4-dimethylnaphthalene, 9-fluorenone, fluorene, phenanthrene, triphenylene, pyrene, anthracene, 9-phenylanthracene, 9-methoxyanthracene, and 9-phenylanthracene. Condensed aromatic compounds such as 9,10-diphenylanthracene, 9,10-bis(4-methoxyphenyl)anthracene, 9,10-bis(triphenylsilyl)anthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentaoxyanthracene, 2-t-butyl-9,10-dibutoxyanthracene, and 9,10-bis(trimethylsilylethynyl)anthracene are also included. Commercially available compounds include Anthracure (manufactured by Kawasaki Chemical Industries, Ltd.).

[0113] When a sensitizer is used, only one type may be used, or two or more types may be used. When a sensitizer is used, the amount thereof is usually 0.001 to 10 parts by mass based on 100 parts by mass of the polysiloxane compound.

[0114] Further, examples of the additive components include organic basic compounds (amine compounds, nitrogen-containing heterocyclic compounds) commonly used in photosensitive resin compositions containing an acid labile group.

[0115] In the photosensitive resin composition of this embodiment, the amount of the solvent used can be the same as in the above-mentioned resin composition.

[0116] A patterned cured film can be produced using the photosensitive resin composition of the present embodiment. The patterned cured film can be produced, for example, a film forming step of applying the photosensitive resin composition onto a substrate to form a photosensitive resin film; an exposure step of exposing the photosensitive resin film to light; a developing step of developing the exposed photosensitive resin film to form a patterned resin film; a curing step of heating the patterned resin film to convert the patterned resin film into a patterned cured film; It can be produced by a series of steps including the steps of:

[0117] Below, an explanation will be given for each of the above steps.

[0118] ·Film formation process The substrate to which the photosensitive resin composition is applied is selected from, for example, silicon wafers, metals, glass, ceramics, and plastic substrates depending on the application of the cured film to be formed. As the coating method, a known coating method such as spin coating, dip coating, spray coating, bar coating, applicator, ink jet or roll coater can be used without any particular limitation.

[0119] The substrate coated with the photosensitive resin composition is heated, for example, at 80 to 120° C. for about 30 seconds to 5 minutes to dry off the solvent, thereby obtaining a photosensitive resin film.

[0120] Exposure process For example, the photosensitive resin film obtained in the film formation step is irradiated with light through a photomask for forming a desired pattern.

[0121] For the exposure, known methods and devices can be used. As the light source, a light source having a wavelength in the range of 100 to 600 nm can be used. Specific examples that can be used include a low pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a KrF excimer laser (wavelength 248 nm), and an ArF excimer laser (wavelength 193 nm). The exposure dose is usually 1 to 10,000 mJ / cm. 2 Approximately, preferably 10 to 5000 mJ / cm 2 That's about it.

[0122] After the exposure, post-exposure baking may be carried out before the development step, if necessary. The post-exposure baking temperature is preferably 60 to 180° C., and the post-exposure baking time is preferably 0.5 to 10 minutes.

[0123] ·Development process Next, the exposed photosensitive resin film obtained in the exposure step is developed to form a film having a pattern shape (hereinafter, also referred to as a "patterned resin film"). By using an alkaline aqueous solution as a developer, the exposed parts of the exposed photosensitive resin film are dissolved, and a patterned resin film is formed.

[0124] The developer is not particularly limited as long as it can remove the photosensitive resin film in the exposed area. Specific examples include aqueous alkali solutions in which inorganic alkali, primary amines, secondary amines, tertiary amines, alcohol amines, quaternary ammonium salts, and mixtures thereof are dissolved. More specifically, examples of the aqueous alkali solution include potassium hydroxide, sodium hydroxide, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide (abbreviation: TMAH), etc. Among these, it is preferable to use an aqueous TMAH solution, and it is particularly preferable to use an aqueous TMAH solution having a concentration of 0.1% by mass or more and 5% by mass or less, more preferably 2% by mass or more and 3% by mass or less.

[0125] As the developing method, a known method such as a dipping method, a paddle method, a spray method, etc. can be used. The developing time is usually 0.1 to 3 minutes, preferably 0.5 to 2 minutes. Thereafter, washing, rinsing, drying, etc. are performed as necessary, and a desired patterned film (patterned resin film) can be formed on the substrate.

[0126] ·Curing process The patterned resin film obtained in the development step is subjected to a heat treatment to obtain a final patterned cured film. The heat treatment can condense the alkoxy groups and silanol groups remaining as unreactive groups in the polysiloxane compound. In addition, when the photosensitive resin composition contains an epoxy group, an oxetane group, a methacryloyl group, an acryloyl group, or the like, the epoxy group, the oxetane group, the methacryloyl group, the acryloyl group, or the like, they can be sufficiently cured. The heating temperature is preferably 80 to 400°C, more preferably 100 to 350°C. The heating time is usually 1 to 90 minutes, preferably 5 to 60 minutes. By appropriately adjusting the heating temperature and time, it is possible to sufficiently harden the resin film while suppressing decomposition of the components contained in the resin film. In addition, it is easy to obtain a cured film that has good chemical resistance, high transparency, and suppresses the occurrence of cracks.

[0127] <Reference form> In the above section <Silicon Compound and Reactive Material>, it was stated that the reactive material of this embodiment can further contain a silicon compound (Y) represented by the following general formula (y). In this regard, some of the embodiments of the present invention can be considered as "compositions" as follows.

[0128] "A composition comprising a silicon compound (X) represented by general formula (x) and a silicon compound (Y) represented by general formula (y), The mass of the silicon compound (X) contained in this composition is M X , the mass of the silicon compound (Y) is M Y Then, {M Y / (M X +M Y The ratio (mass%) of the silicon compound (Y) represented by {(mass%)}×100 is preferably 1×10 -4 ~12%, more preferably 5×10 -4 The composition is preferably 0.001 to 5% by weight, more preferably 0.001 to 10%, even more preferably 0.001 to 8%, and particularly preferably 0.01 to 5% by weight."

[0129] In this composition, the definitions and preferred embodiments of the silicon compound (X) represented by the general formula (x) and the silicon compound (Y) represented by the general formula (y) are as described above. This composition may or may not contain optional components other than the silicon compound (X) and the silicon compound (Y). The optional components include solvents (such as organic solvents), stabilizers, and unavoidably contained water and impurities.

[0130] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of the present invention are included in the present invention. EXAMPLES

[0131] The embodiments of the present invention will be described in detail based on Examples and Comparative Examples. It should be noted that the present invention is not limited to the Examples.

[0132] In the examples, unless otherwise specified, some compounds are represented as follows:

[0133] THF: tetrahydrofuran MOMCl: Chloromethyl methyl ether Boc2O: Di-tert-butyl dicarbonate TBAI: Tetrabutylammonium iodide TMAH: Tetramethylammonium hydroxide Ph-Si: Phenyltriethoxysilane KBM-303: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. KBM-5103: Shin-Etsu Chemical Co., Ltd., 3-acryloxypropyltrimethoxysilane Ethyl polysilicate: Tama Chemical Industry Co., Ltd., silicate 40

[0134] HFA-Si: A compound represented by the following chemical formula

[0135] [ka]

[0136] HFA-Si-MOM: A compound represented by the following chemical formula

[0137] [ka]

[0138] HFA-Si-BOC: A compound represented by the following chemical formula

[0139] [ka]

[0140] The devices and conditions used for the various measurements will be described in advance.

[0141] (Nuclear magnetic resonance (NMR)) A nuclear magnetic resonance apparatus with a resonance frequency of 400 MHz (manufactured by JEOL Ltd., equipment name JNM-ECA-400) was used. 1 H-NMR and 19 F-NMR was measured.

[0142] (Gas Chromatography (GC)) The gas chromatograph used was Shimadzu GC-2010 manufactured by Shimadzu Corporation, and the capillary column used was Agilent Model DB5 (length 30 mm x inner diameter 0.25 mm x film thickness 0.25 μm).

[0143] (Gel Permeation Chromatography (GPC)) The weight average molecular weight in terms of polystyrene was measured using a high-speed GPC apparatus manufactured by Tosoh Corporation, with the device name HLC-8320GPC.

[0144] <Production of reactive materials> (Synthesis Example 1-1: Production of reactive material containing HFA-Si-MOM) To a mixture of THF (150 g) and NaH (16.2 g, 0.41 mol) in a three-neck flask placed in an ice bath, HFA-Si (150 g, 0.37 mol) was added dropwise, followed by MOMCl (32.6 g, 0.38 mol), and then the mixture was stirred at room temperature for 20 hours. After the above stirring, the reaction solution was concentrated with an evaporator. 300 g of toluene and 150 g of water were added to the concentrated reaction solution and stirred. After stirring, the mixture was left to stand for a while to separate into two layers, and the lower aqueous layer was removed. 150 g of water was further added to the obtained upper organic layer, and the same operation was repeated. The finally obtained upper organic layer was concentrated with an evaporator to obtain 180 g of crude product. The obtained crude product was subjected to simple distillation (vacuum degree 2.5 kPa, bath temperature 200 to 220° C., top temperature 170° C.) to obtain 145 g of a reactive material (liquid) containing HFA-Si-MOM. In the above, the yield of HFA-Si-MOM was 84.3%, and the GC purity was 97%. The reactive material obtained contained a small amount of HFA-Si, and the ratio of HFA-Si calculated by {amount of HFA-Si / (amount of HFA-Si-MOM+amount of HFA-Si)}×100 was 0.1% by mass.

[0145] The signals obtained by NMR measurement are shown below. 1 H-NMR (solvent CDCl3, TMS): δ7.92(s,1H), 7.79-7.76(m,1H), 7.68-7.67(m,1H), 7.49-7.45(m,1H), 4.83(s,2H), 3.86(q,6H), 3.55(s,3H), 1.23(t,9H) 19 F-NMR (solvent CDCl3, C6F6): δ-71.4(s,6F)

[0146] (Synthesis Example 1-2: Production of HFA-Si-BOC) THF (10 g), NaH (1.2 g, 0.03 mol), and HFA-Si (10 g, 0.025 mol) were added to a three-neck flask placed in an ice bath and stirred for 30 minutes. Then, BocO (5.2 g, 0.027 mol) and TBAI (0.3 g, 0.001 mol) were added to the flask and stirred at room temperature for 18 hours. Diisopropyl ether (20 g) and water (10 g) were added to the obtained reaction product, stirred, and then allowed to stand for a while. After standing to separate into two layers, the lower aqueous layer was removed. The upper organic layer obtained was dried over magnesium sulfate, and then concentrated with an evaporator to obtain 10 g of HFA-Si-BOC (yield 83%, GC purity 95%).

[0147] The signals obtained by NMR measurement are shown below. 1 H-NMR (solvent CDCl3, TMS): δ7.78-7.75(m,2H), 7.52-7.43(m,2H), 3.84(q,6H), 1.46(s,9H), 1.22(t,9H) 19 F-NMR (solvent CDCl3, C6F6): δ-70.2(s,6F)

[0148] <Preparation of comparative compounds> HFA-Si was synthesized according to the procedure described in paragraph 0124, Example 5 of WO 2019 / 167770.

[0149] <Evaluation of storage stability> As an evaluation sample, the reactive material (containing 0.1 mass% of HFA-Si corresponding to the silicon compound (Y)) produced in Synthesis Example 1-1 was prepared (referred to as "Sample 1"). Samples 2 to 5 were prepared by adding HFA-Si to the reactive material of Sample 1. For each sample, {M Y / (M X +M Y The ratio of the silicon compound (Y) represented by {(Y) / (Y)}×100 is shown in the table below.

[0150] For each sample, 5 parts by mass of water was added to 100 parts by mass of the total amount of HFA-Si-MOM and HFA-Si, and the sample was stored in a refrigerator for 24 hours. GPC and GC measurements were performed before and after storage to evaluate the storage stability. Table 2 below shows the evaluation results based on the following evaluation criteria.

[0151] GPC measurement: The weight average molecular weight Mw after 24 hours of storage in a refrigerator is compared to the Mw at the start of storage. No change: Mw value change is within ±20 Changed: Mw value increased by 200 or more

[0152] GC measurement: GC purity after 24 hours of storage in refrigerator compared to the GC purity at the start of storage. No change: Change in GC purity is within ±1.5% Changed: GC purity decreased by 10% or more ("GC purity" refers to the purity of HFA-Si-MOM in a sample, calculated from the area of ​​the chart obtained by gas chromatographic measurement.)

[0153] The evaluation results for each sample are shown below.

[0154] [Table 2]

[0155] From Table 2, {M Y / (M X +M Y It was shown that the storage stability of reactive materials having a small ratio of the silicon compound (Y) represented by {Y x 100} was particularly good.

[0156] <Production of polysiloxane compound> (Synthesis Example 2-1: Synthesis of polysiloxane compound under basic conditions) A reactive material containing HFA-Si-MOM obtained in Synthesis Example 1-1 (1.0 g, 2.2 mmol), EtOH (0.5 g), water (0.13 g, 7.0 mmol), and a 25 mass% TMAH aqueous solution (0.002 g, 0.02 mmol as TMAH) were placed in a reaction vessel, and the reaction was carried out at 60° C. for 4 hours with stirring. Toluene (5 g) was then added to the reaction mixture, and the mixture was refluxed at 105° C. for 20 hours with a Dean-Stark apparatus to remove water and EtOH. The mixture was then washed three times with water (2 g each time), and the organic layer was concentrated using an evaporator (conditions: 30 hPa, 60° C., 30 min). As a result of the above, 0.8 g of the target polysiloxane compound was obtained. The weight average molecular weight Mw measured by GPC was 2,100.

[0157] (Comparative Synthesis Example 2-1: Synthesis of polysiloxane compound under basic conditions) Into a reaction vessel were added HFA-Si (1 g, 2.5 mmol), EtOH (1 g), water (0.14 g, 7.8 mmol), and a 25 mass % TMAH aqueous solution (0.002 g, 0.02 mmol as TMAH), and the mixture was reacted at 60° C. for 4 hours with stirring. Toluene (5 g) was then added to the reaction mixture, and the mixture was refluxed at 105° C. for 20 hours with a Dean-Stark apparatus to remove water and EtOH. The mixture was then washed three times with water (2 g each time), and the organic layer was concentrated using an evaporator (conditions: 30 hPa, 60° C., 30 min). As a result of the above, 0.8 g of a polysiloxane compound was obtained. The weight average molecular weight Mw was 1,000 as measured by GPC.

[0158] (Comparative Synthesis Example 2-2: Synthesis of polysiloxane compound under basic conditions) HFA-Si (1 g, 2.5 mmol), NaOH (0.4 g, 3.0 mmol), water (0.14 g, 7.8 mmol), and EtOH (1 g) were placed in a reaction vessel and reacted at 60°C for 4 hours with stirring. This produced a polysiloxane compound. The weight average molecular weight Mw measured by GPC was 1300.

[0159] In Synthesis Example 2-1, a polysiloxane compound with a relatively large Mw was obtained, but the Mw of the polysiloxane compounds obtained in Comparative Synthesis Example 2-1 and Comparative Synthesis Example 2-2 was significantly smaller than that of Synthesis Example 2-1. From this, it can be said that the reactivity of the reactive material of this embodiment is good, at least from the viewpoint of polymerizability. In addition, taken together with the above-mentioned evaluation results of the storage stability of the reactive material (which was good), it was shown that the reactive material of this embodiment has good storage stability as well as good reactivity.

[0160] (Synthesis Example 2-2: Synthesis of polysiloxane compound under acidic conditions) Into a reaction vessel were added reactive materials (1.0 g, 2.2 mmol) containing HFA-Si-MOM obtained in Synthesis Example 1-1, acetone (2 g), water (4.13 g, 7.0 mmol), and acetic acid (0.02 g, 0.1 mmol), and the mixture was reacted at 60° C. for 20 hours. After that, the acetone and water were distilled off from the reaction solution using an evaporator, and 0.8 g of polymer was obtained (yield 100%). The weight average molecular weight Mw measured by GPC was 1600. In addition, 19 F-NMR analysis showed that the methoxymethyl group had not been eliminated. From the above, it was demonstrated that the reactive material of the present embodiment can be preferably used as a raw material for polysiloxane compounds, even under acidic conditions.

[0161] (Synthesis Example 2-1' and Synthesis Examples 2-3 to 2-9: Synthesis of polysiloxane compound and preparation of solution composition) A polysiloxane compound (Synthesis Example 2-1') was obtained in the same manner as in Synthesis Example 2-1, except that KOH was used as the polymerization catalyst instead of TMAH. Moreover, a polysiloxane compound (Synthesis Example 2-3) was obtained in the same manner as in Synthesis Example 2-2, except that hydrochloric acid was used as the polymerization catalyst instead of acetic acid. Furthermore, polysiloxane compounds were obtained in the same manner as in Synthesis Example 2-1, except that the types and charging ratios of raw materials were changed as shown in the table below (Synthesis Examples 2-4 to 2-9).

[0162] The polysiloxane compounds obtained in Synthesis Examples 2-1, 2-1', and 2-2 to 2-9 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to obtain solution compositions (resin compositions) P-1, P-1', and P-2 to P-9 each having a concentration of 25% by mass.

[0163] The above matters are summarized in the table below. In the table below, "HFA-Si-MOM" represents the reactive material containing HFA-Si-MOM obtained in Synthesis Example 1-1.

[0164] [Table 3]

[0165] <Film formation from solution composition and evaluation of tackiness> Solution compositions P-1, P-1', and P-2 to P-9 were each spin-coated at 500 rpm onto a silicon wafer having a diameter of 4 inches and a thickness of 525 μm manufactured by SUMCO Corporation. The silicon wafer was then dried on a hot plate at 100° C. for 3 minutes, and then baked at 230° C. for 1 hour. In this way, a cured polysiloxane film having a thickness of 1 to 2 μm was obtained. When the presence or absence of tackiness was confirmed by touching with a finger, no tackiness was observed in any of the films. In other words, it was confirmed that the polysiloxane compound obtained by polycondensing the reactive material of this embodiment in the presence of an acid catalyst or a base catalyst does not pose any significant problem in application to film formation, etc.

[0166] <Transparency assessment> Using solution compositions P-1, P-1', and P-2 to P-9, and in the same manner as above, except that a 4-inch glass substrate was used instead of a 4-inch silicon wafer, a polysiloxane cured film having a thickness of 1 to 2 μm was obtained. Then, the transmission spectrum of the cured film was measured. The transmittance of the cured films obtained from solution compositions P-1, P-1', and P-2 to P-9 at a wavelength of 400 nm, calculated as a film thickness of 2 μm, was all greater than 90%. Also, the transmittance of the cured films obtained from P-1, P-1', P-2 to P-4, and P-9 at a wavelength of 350 nm, calculated as a film thickness of 2 μm, was all greater than 90%. Due to such favorable light transmittance at wavelengths of 350 to 400 nm, the polysiloxane compound obtained by polycondensing the reactive material of this embodiment in the presence of an acidic catalyst or a basic catalyst can be preferably used, for example, as a photosensitive resin composition applied to i-line exposure, and as a coating material for organic electroluminescence (EL) and liquid crystal displays, CMOS image sensors, and the like.

[0167] <Preparation of photosensitive resin composition and evaluation of patterning properties> To 3 g of each of solution compositions P-1, P-1′, and P-2 to P-4, 0.04 g of a photoacid generator, CPI-100TF (manufactured by San-Apro Co., Ltd.), was added and stirred to prepare homogeneous photosensitive resin compositions (five types). Each photosensitive resin composition was applied by spin coating at 500 rpm onto a silicon wafer having a diameter of 4 inches and a thickness of 525 μm manufactured by SUMCO Corp. The silicon wafer was then heat-treated on a hot plate at 100° C. for 3 minutes to obtain a photosensitive resin film having a thickness of 1 to 2 μm.

[0168] Next, using an exposure device equipped with a high-pressure mercury lamp, the photosensitive resin film was exposed to 108 mJ / cm 2 through a photomask. 2 The sample was then irradiated with light of 10000 W. Then, it was heated on a hot plate at 150°C for 1 minute. After the heat treatment, it was developed by immersing in a 2.38% by mass TMAH aqueous solution for 1 minute, and then washed by immersing in water for 30 seconds. After washing, it was baked in an oven at 230°C for 1 hour in the atmosphere. As a result, a patterned cured film with a positive pattern was obtained. In all five types of photosensitive resin compositions, a line and space pattern of 10 to 20 μm could be resolved. In other words, the polysiloxane compound obtained by polycondensing this reactive material can be preferably applied to a photosensitive resin composition. [Industrial Applicability]

[0169] The silicon compound and reactive material of the present embodiment are useful not only as raw materials for polymer synthesis, but also as polymer modifiers, surface treatment agents for inorganic compounds, coupling agents for various materials, intermediate raw materials for organic synthesis, and the like. Furthermore, by adding a photosensitizer to a resin composition containing the polysiloxane compound obtained by polycondensing the silicon compound or reactive material of this embodiment, it is possible to obtain a photosensitive resin composition that can be patterned by alkaline development. Furthermore, the cured film obtained from the resin composition or photosensitive resin composition of this embodiment has excellent transparency. For this reason, the resin composition or photosensitive resin composition of this embodiment is preferably used as a protective film for semiconductors, a protective film for organic EL or liquid crystal displays, a coating material for image sensors, a planarizing material, a microlens material, an insulating protective film material for touch panels, a liquid crystal display TFT planarizing material, a material for forming cores or clads of optical waveguides, an electron beam resist, an intermediate film for multilayer resists, an underlayer film, an anti-reflection film, etc. Among these applications, when used in optical components such as displays and image sensors, fine particles such as polytetrafluoroethylene, silica, titanium oxide, zirconium oxide, and magnesium fluoride can be mixed at any ratio for the purpose of adjusting the refractive index.

[0170] This application claims priority based on Japanese Patent Application No. 2019-195382, filed on October 28, 2019, the disclosure of which is incorporated herein in its entirety.

Claims

1. A silicon compound represented by the following general formula (x): 【Chemistry 1】 In general formula (x), R １ when there are a plurality of, each independently represents a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a linear alkenyl group having 2 to 10 carbon atoms, a branched alkenyl group having 3 to 10 carbon atoms, in which all or a part of the hydrogen atoms in the alkyl group or alkenyl group may be substituted with fluorine atoms, R ２ when there are a plurality of, each independently represents a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms, in which all or a part of the hydrogen atoms in the alkyl group may be substituted with fluorine atoms, R Ａ is an acetal group which is an acid labile group, a is an integer from 1 to 3, b is an integer from 0 to 2, c is an integer from 1 to 3, and a+b+c=4; n is an integer from 1 to 5.

2. A reactive material comprising a silicon compound (X) represented by the following general formula (x): 【Chemistry 2】 In general formula (x), R １ when there are a plurality of, each independently represents a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a linear alkenyl group having 2 to 10 carbon atoms, a branched alkenyl group having 3 to 10 carbon atoms, in which all or a part of the hydrogen atoms in the alkyl group or alkenyl group may be substituted with fluorine atoms, R ２ when there are a plurality of, each independently represents a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms, in which all or a part of the hydrogen atoms in the alkyl group may be substituted with fluorine atoms, R Ａ is an acetal group which is an acid labile group, a is an integer from 1 to 3, b is an integer from 0 to 2, c is an integer from 1 to 3, and a+b+c=4; n is an integer from 1 to 5.

3. 3. The reactive material of claim 2, Further, the composition contains a silicon compound (Y) represented by the following general formula (y): The mass of the silicon compound (X) contained in the reactive material is M Ｘ The mass of the silicon compound (Y) is M Ｙ Then, {M Ｙ / (M Ｘ +M Ｙ )} × 100, the ratio of the silicon compound (Y) is 1 × 10 －４ % by weight of reactive material. 【Chemistry 3】 In general formula (y), R １ , R ２ The definitions of a, b, c and n are the same as those in general formula (x).

4. A method for producing a polysiloxane compound, comprising polycondensing the silicon compound according to claim 1 or the reactive material according to claim 2 in the presence of an acidic or basic catalyst.

5. A method for producing the polysiloxane compound according to claim 4, comprising the steps of: A method for producing a polysiloxane compound having a weight average molecular weight of 1,000 to 100,000.

6. A step of obtaining a polysiloxane compound by the method for producing a polysiloxane compound according to claim 4 or 5; A step of mixing the polysiloxane compound obtained in the above step with a solvent to obtain a resin composition; a heating step of applying the resin composition onto a substrate and then heating the substrate at a temperature of 100 to 350° C.; A method for producing a cured film comprising the steps of:

7. A step of obtaining a polysiloxane compound by the method for producing a polysiloxane compound according to claim 4 or 5; A step of mixing the polysiloxane compound obtained in the above step with a photoacid generator and a solvent to obtain a photosensitive resin composition; a film forming step of applying the photosensitive resin composition onto a substrate to form a photosensitive resin film; an exposure step of exposing the photosensitive resin film to light; a developing step of developing the photosensitive resin film after exposure to form a patterned resin film; a curing step of heating the patterned resin film to convert the patterned resin film into a patterned cured film; A method for producing a patterned cured film comprising the steps of:

8. A method for producing the patterned cured film according to claim 7, comprising the steps of: The method for producing a patterned cured film, wherein the wavelength of light used for exposure in the exposure step is 100 to 600 nm.

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