Polysilsesquioxane compound, method for producing same, and composition

Abstract

The present invention addresses the problem of providing: a polysilsesquioxane compound having excellent film-forming properties; a method for producing the polysilsesquioxane compound; and a composition. The polysilsesquioxane compound has a polysilsesquioxane skeleton having a ladder-like structure, and contains three or more specific carbon number side chains that do not have a primary amino group or a salt structure thereof.

Description

Technical Field

[0001] The present invention relates to a polysilsesquioxane compound, a preparation method thereof, and a composition thereof. Background Art

[0002] Polysilsesquioxane compounds are inorganic compounds having an inorganic skeleton formed by siloxane bonds as the main skeleton and having an organic functional group in the side chain, and compounds with various structures such as a random structure, a cage structure, and a ladder structure are known. Polysilsesquioxane compounds have excellent properties such as heat resistance, and therefore have been tried to be used in various technical fields such as electronics and photonics (for example, see Patent Document 1 or Patent Document 2).

[0003] Patent Document 1 discloses a polysiloxane compound having a ladder-like polysiloxane skeleton and an amide structure containing a hydrophobic group in the side chain, wherein the amide structure containing a hydrophobic group includes a group represented by -N(H)-C(=O)-R (R is a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, a saturated alicyclic hydrocarbon group having 3 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms). In addition, Patent Document 2 discloses a polysiloxane compound having a ladder-like polysiloxane skeleton and an imide structure in the side chain, and having a number average molecular weight of 4,500 or more.

[0004] [Prior art literature]

[0005] [Patent Document]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2016-11340

[0007] [Patent Document 2] Japanese Patent Application Publication No. 2015-206030 Summary of the invention

[0008] [Problems to be solved by the invention]

[0009] As an example of a method for using a polysilsesquioxane compound, there is a method of applying a polymer solution obtained by dissolving the polysilsesquioxane compound in a solvent onto a substrate and forming a film. It is believed that if a film formed using a polysilsesquioxane compound can be patterned, the polysilsesquioxane compound can be applied to new uses or further high functionality can be achieved. Specifically, if a polysilsesquioxane compound can be used to form a film that can show a dissolution contrast (developability) in a developer, for example, development to resist applications or development to a cured film that requires patterning can be expected.

[0010] On the other hand, polysilsesquioxane compounds have relatively high crystallinity due to having an organic functional group in the side chain, and when formed into a film on a substrate, the surface smoothness is insufficient or cracks are easily generated, and the film forming property may be poor. Therefore, the application of polysilsesquioxane compounds in the above-mentioned applications is considered to be limited.

[0011] The present invention has been made in view of the above-mentioned problems, and a main object of the present invention is to provide a polysilsesquioxane compound having excellent film-forming properties and a method for producing the same.

[0012] [Technical means to solve the problem]

[0013] According to the present invention, the following means are provided.

[0014] [1] A polysilsesquioxane compound having a ladder-like polysilsesquioxane skeleton and containing three or more specific side chains having one or more carbon atoms and not having a primary amino group or a salt thereof.

[0015] [2] A method for producing a polysilsesquioxane compound, comprising a reaction step, wherein a hydrolysis condensation salt of an alkoxysilane compound having an amino group is reacted with a reactive compound having a functional group capable of reacting with the hydrolysis condensation salt, wherein the hydrolysis condensation salt has a ladder structure, and in the reaction step, the hydrolysis condensation salt is reacted with three or more of the reactive compounds simultaneously.

[0016] [3] A composition comprising the polysilsesquioxane compound of [1] and a solvent.

[0017] [Effects of the Invention]

[0018] According to the present invention, a polysilsesquioxane compound having excellent film-forming properties and capable of expressing developability can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a 29Si-NMR spectrum chart of the polymer (R-1) obtained in Synthesis Example 1.

[0020] Figure 2 This is a 1H-NMR spectrum of the polymer (P-1) obtained in Example 1.

[0021] Figure 3 This is a 1H-NMR spectrum chart of the polymer (Q-1) obtained in Comparative Example 1. DETAILED DESCRIPTION

[0022] Hereinafter, matters related to the embodiment will be described in detail. In addition, in this specification, the numerical range described using "to" means that the numerical values ​​described before and after "to" are included as the lower limit and the upper limit.

[0023] Here, in the present specification, "hydrocarbon group" means a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. "Chain hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched hydrocarbon group that do not contain a cyclic structure but only a chain structure. Among them, the chain hydrocarbon group may be saturated or unsaturated. "Alicyclic hydrocarbon group" refers to a hydrocarbon group that only contains the structure of alicyclic hydrocarbon as a ring structure and does not contain an aromatic ring structure. Among them, the alicyclic hydrocarbon group does not need to contain only the structure of alicyclic hydrocarbon, and also includes a group having a chain structure in a part thereof. "Aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as a ring structure. Among them, the aromatic hydrocarbon group does not need to contain only the aromatic ring structure, and may also contain a chain structure or an alicyclic hydrocarbon structure in a part thereof. "Aromatic ring group" refers to an n-valent group formed by removing n (where n is an integer greater than 1) hydrogen atoms from the ring part of a substituted or unsubstituted aromatic ring. "Aromatic heterocyclic group" refers to an n-valent group formed by removing n (where n is an integer greater than 1) hydrogen atoms from the ring part of a substituted or unsubstituted aromatic heterocyclic ring. "Organic group" refers to an atomic group formed by removing any hydrogen atom from a compound containing carbon (i.e., an organic compound). "Aromatic ring" means a term including an aromatic hydrocarbon ring and an aromatic heterocyclic ring. "(Meth)acryloyl-" means a term including "acryloyl-" and "methacryloyl-". "(Meth)acryloyloxy" means a term including "acryloyloxy" and "methacryloyloxy".

[0024] 《Polysilsesquioxane compounds》

[0025] The polysilsesquioxane compound (hereinafter also referred to as "polysilsesquioxane (P)") disclosed herein has a ladder-like polysilsesquioxane skeleton and contains three or more side chains having one or more carbon atoms and not having a primary amino group or a salt thereof (hereinafter also referred to as "specific side chains"). The polysilsesquioxane (P) can be represented by the following formula (1), for example. In the following formula (1), R a Equivalent to the side chain in ladder-like polysilsesquioxane compounds.

[0026] [Chemistry 1]

[0027]

[0028] (In formula (1), multiple R a are the same as or different from each other and are hydroxyl, protected hydroxyl or monovalent organic group with 1 or more carbon atoms; n is 1 or more; multiple R a Contains three or more specific side chains)

[0029] In the formula (1), R a In the case of a protected hydroxyl group, the group that replaces the hydrogen atom of the hydroxyl group is preferably a group that can be detached by at least one of heat, light, acid and base. Specifically, for example, a monovalent tertiary hydrocarbon group (tert-butyl, 1-alkylcyclooctyl, etc.), a carbamate-based detachable group (tert-butoxycarbonyl (Boc group), benzyloxycarbonyl, 9-fluorenylmethyloxycarbonyl, allyloxycarbonyl, etc.), a trialkylsilyl group, a benzyl group, a methoxymethyl group, an acetyl group, a benzoyl group, an alkoxymethyl group, etc.

[0030] In R a In the case of a monovalent organic group having 1 or more carbon atoms, examples of the monovalent organic group include a monovalent hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group in which a portion of the methylene groups is substituted by -O-, -S-, -CO-, -CO-O-, -O-CO-O-, -NR 4 -、-CO-NR 4 -、-NR 4 -CO-NR 5 -、-O-CO-NR 4 -、-CO-NR 4 A monovalent group having 2 to 50 carbon atoms formed by substitution with -CO- or -SO2- (hereinafter also referred to as a "monovalent heteroatom-containing group"), a monovalent group having 1 to 50 carbon atoms formed by substitution with a substituent for one or more hydrogen atoms in a monovalent hydrocarbon group or a monovalent heteroatom-containing group, a monovalent group having a heterocycle, etc.

[0031] As R a Examples of the monovalent hydrocarbon group having 1 to 50 carbon atoms include a monovalent chain hydrocarbon group having 1 to 50 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 50 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 50 carbon atoms.

[0032] The monovalent chain hydrocarbon group having 1 to 50 carbon atoms may be saturated or unsaturated, and may be straight-chain or branched. The monovalent alicyclic hydrocarbon group having 3 to 50 carbon atoms may be saturated or unsaturated. In addition, the alicyclic ring in the alicyclic hydrocarbon group may have a monocyclic structure or a polycyclic structure. When the alicyclic ring in the alicyclic hydrocarbon group has a polycyclic structure, the alicyclic ring may have any one of a condensed ring structure, a bridged ring structure, and a spiro ring structure. The aromatic ring possessed by the monovalent aromatic hydrocarbon group having 6 to 50 carbon atoms may have a monocyclic structure or a condensed ring structure. In addition, the monovalent chain hydrocarbon group having 1 to 50 carbon atoms, the monovalent alicyclic hydrocarbon group having 3 to 50 carbon atoms, and the monovalent aromatic hydrocarbon group having 6 to 50 carbon atoms may also have a cross-linkable carbon-carbon unsaturated bond group.

[0033] In R aWhen there is a heterocyclic ring, the heterocyclic ring may be an aliphatic heterocyclic ring or an aromatic heterocyclic ring. In addition, the heterocyclic ring may be a monocyclic ring or a condensed ring.

[0034] As R a Specific examples of the aliphatic heterocycle that may be present include: cyclic ethers such as oxirane, oxetane, tetrahydrofuran, and tetrahydropyran; cyclic esters such as α-acetone, β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, and ε-caprolactone; cyclic acetals such as 1,3-dioxolane and 1,3-dioxane; ethylene carbonate, propylene carbonate, phthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 1,8-naphthalene-1,2-diol; Cyclic carbonates such as dicarboxylic anhydride and 2,3-naphthalene dicarboxylic anhydride; cyclic imides such as succinimide, glutarimide, phthalimide, 1,8-naphthalene dicarboximide, 2,3-naphthalene dicarboximide, hexahydro-4-methylphthalimide and 5-norbornene-2,3-dicarboxylic imide; nitrogen-containing aliphatic heterocycles such as piperidine, piperazine, morpholine and hexamethyleneimine; sulfur-containing aliphatic heterocycles such as ethylene sulfide, tetrahydrothiophene and cyclopentane sulfone, etc.

[0035] Examples of the aromatic heterocycle include nitrogen-containing aromatic heterocycles such as pyrrole ring, imidazole ring, pyrazole ring, triazole ring, pyridine ring, pyrimidine ring, pyridazine ring, quinoline ring, benzimidazole ring, carbazole ring and pyrazine ring; oxygen-containing aromatic heterocycles such as furan; and sulfur-containing aromatic heterocycles such as thiophene.

[0036] In R a When having a substituent, examples of the substituent include a hydroxyl group, a protected hydroxyl group, a protected primary amino group, a carboxyl group, a protected carboxyl group, a thiol group, a protected thiol group, a (meth)acryloyl group, an isocyanate group, a protected isocyanate group, an oxirane group, an oxetane group, a halogen atom, a cyano group, a nitro group, an alkyl group, an alkoxy group, and the like.

[0037] The degree of polymerization of the polysilsesquioxane (P) (ie, n in the formula (1)) is preferably 10 to 1,500, more preferably 15 to 1,000, and still more preferably 20 to 800.

[0038] The polysilsesquioxane (P) has three or more specific side chains. The three or more specific side chains possessed by the polysilsesquioxane (P) are not particularly limited as long as the structures are different from each other. That is, the polysilsesquioxane (P) has a first side chain, a second side chain, and a third side chain having different structures as specific side chains. The polysilsesquioxane (P) having the first side chain, the second side chain, and the third side chain may further have a fourth side chain, a fifth side chain, etc. having different structures from the first to third side chains as specific side chains.

[0039] In terms of improving film forming properties by reducing crystallinity or facilitating adjustment of solubility in a developer, the polysilsesquioxane (P) preferably has three or more side chains having different types of functional groups in the side chains, or three or more side chains having different types of functional groups. In terms of film forming properties and a balance between solubility contrast in a developer and ease of synthesis, the number of types of specific side chains possessed by the polysilsesquioxane (P) is preferably 3 to 12, more preferably 3 to 6, and even more preferably 4 to 6.

[0040] From the viewpoint of improving the ease of production of the polysilsesquioxane compound having a specific side chain, the specific side chain preferably has a partial structure represented by the following formula (2).

[0041] [Chemistry 2]

[0042] *-X 1 -R 1 (2)

[0043] (In formula (2), X 1 For-NR 2 -CO-、-NR 2 -、-NR 2 -CO-NR 3 -、-CO-NR 2 -CO- or a group represented by the following formula (n);

[0044] [Chemistry 3]

[0045]

[0046] (In formula (n), R 7 is a monovalent organic group; m is an integer from 0 to 3; when m is 2 or 3, multiple R 7 Same or different; "* 1 " represents the same as R in the formula (2) 1 The bond of the

[0047] R 2 and R 3 are independently a hydrogen atom or a monovalent hydrocarbon group; R 1 is a monovalent organic group; "*" indicates a bonding bond)

[0048] In the formula (2), R 2 or R 3 In the case of a monovalent hydrocarbon group, examples of the monovalent hydrocarbon group include a monovalent chain hydrocarbon group having 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms. Among these, an alkyl group having 1 to 6 carbon atoms is preferred, and an alkyl group having 1 to 3 carbon atoms is more preferred.

[0049] As R in the formula (n) 7 Examples of the group include a monovalent hydrocarbon group having 1 to 10 carbon atoms and a monovalent hydrocarbon group having 2 to 10 carbon atoms containing -O- between carbon-carbon bonds of the hydrocarbon group.

[0050] As R 1 Specific examples of the monovalent organic group represented by include the following as R a In the case of a monovalent organic group having 1 or more carbon atoms, the groups are the same as those shown in the specific examples.

[0051] The group represented by the formula (2) may be directly bonded to the silicon atom (more specifically, the silicon atom forming the siloxane bond), or may be bonded to the silicon atom via a divalent linking group. From the viewpoint of the ease of synthesis of the polysilsesquioxane (P), the group represented by the formula (2) is preferably bonded to the silicon atom via a divalent linking group. Examples of the divalent linking group include: an alkanediyl group having 1 to 6 carbon atoms, an alkanediyl group having a carbon-carbon bond containing -NR 6 -(where R 6 The divalent linking group is preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, a divalent group having 2 to 12 carbon atoms, etc. Among these, an alkanediyl group having 1 to 6 carbon atoms is preferred.

[0052] In addition, the polysilsesquioxane (P) may also have three or more specific side chains and a side chain having a carbon number of 1 or more and having a primary amino group. In addition, the polysilsesquioxane (P) may also have a side chain having a carbon number of 1 or more and having a salt structure of a primary amino group. The salt structure of the primary amino group is composed of "-NH3 + X - ” (wherein X- is a counter anion).

[0053] Polysilsesquioxane (P) has three or more specific side chains and exhibits good film-forming properties, so it is useful as a film-forming material. In addition, according to the polysilsesquioxane (P), by introducing a variety of functional groups into the side chains, the dissolution rate in the developer (e.g., an alkaline solution or an organic solvent) can be made different by applying heat or light, thereby obtaining a film with pattern-forming ability or a film with various functions such as liquid crystal orientation, heat resistance, biocompatibility, and substrate adhesion. That is, polysilsesquioxane (P) is useful in obtaining a polymer that exhibits the desired function and has excellent film-forming properties.

[0054] From the viewpoint of obtaining a film exhibiting pattern forming ability, the polysilsesquioxane (P) preferably has at least one of the first side chain, the second side chain, and the third side chain as specific side chains, the first functional group shown below, the second functional group, or the first and second functional groups.

[0055] The first functional group: one selected from the group consisting of a carboxyl group, a hydroxyl group, a protected carboxyl group and a protected hydroxyl group

[0056] Second functional group: cross-linking carbon-carbon unsaturated bond group

[0057] ·First functional group

[0058] The first functional group is introduced into the side chain of the polysilsesquioxane (P) for the purpose of imparting easy solubility or poor solubility in a developer by the properties of the functional group, thereby making the pattern forming ability manifest. The side chain having the first functional group may have a carboxyl group, a hydroxyl group, a protected carboxyl group or a protected hydroxyl group at the end of the side chain, or may have these groups in the middle of the side chain. In addition, in the side chain having the first functional group, the number of the first functional groups (the total number when there are two or more) is not particularly limited. The total number of carboxyl groups, hydroxyl groups, protected carboxyl groups and protected hydroxyl groups is, for example, 1 to 5 per side chain.

[0059] In the protected carboxyl group, as a group that replaces the hydrogen atom of the carboxyl group, it is preferably a group that can be detached by at least any one of heat, light, acid and base. Specifically, for example, a monovalent tertiary hydrocarbon group, a group having an acetal structure, etc. can be listed. As a monovalent tertiary hydrocarbon group, for example, tert-butyl, 3-methyl-3-pentyl, 1-alkylcycloalkyl, etc. can be listed. As a group having an acetal structure, for example, 1-methoxyethyl, 1-cyclohexyloxyethyl, 2-tetrahydropyranyl, 1-methyl-1-methoxyethyl, 1-methyl-1-cyclohexyloxyethyl, 2-(2-methyltetrahydropyranyl) group, etc. can be listed.

[0060] Specific examples of protected hydroxyl groups include: a The groups are the same as the groups exemplified as the protected hydroxyl groups in the description of .

[0061] Second functional group

[0062] The second functional group is introduced into the side chain of the polysilsesquioxane (P) for the purpose of imparting easy solubility or poor solubility to the developer by a curing reaction, thereby making the pattern forming ability manifest. As a cross-linkable carbon-carbon unsaturated bond group, it is preferably a functional group that can form a bond (preferably a covalent bond) between or within molecules by light or heat. Specific examples of cross-linkable carbon-carbon unsaturated bond groups include, for example, vinyl, (meth)acryloyl, vinylphenyl, vinyl ether, cinnamate, etc. The side chain having the second functional group may have a cross-linkable carbon-carbon unsaturated bond group at the end of the side chain, or may have the group in the middle of the side chain.

[0063] From the viewpoint of ensuring good film forming properties and exhibiting pattern forming ability, the polysilsesquioxane (P) preferably has at least one of the first functional group and the second functional group, and more preferably has the first functional group and the second functional group in the side chain. In addition, the side chain having the first functional group and the side chain having the second functional group preferably each have a group represented by the formula (2), and more preferably the group represented by the formula (2) is bonded to the silicon atom via a divalent linking group.

[0064] When the polysilsesquioxane (P) has a first functional group and a second functional group, the first functional group and the second functional group may be present in the same side chain, or a side chain having the first functional group and a side chain having the second functional group but not having the first functional group may be contained in one molecule. That is, the polysilsesquioxane (P) only needs to have at least one of the first side chain, the second side chain, and the third side chain as a specific side chain having the first functional group, and at least one of the first side chain, the second side chain, and the third side chain as a specific side chain having the second functional group. From the viewpoint of making the film forming property and the pattern forming ability good, it is preferred that the polysilsesquioxane (P) has the first functional group and the second functional group in the specific side chain, and two or more of the first side chain, the second side chain, and the third side chain as the specific side chain have at least one of the first functional group and the second functional group.

[0065] In the polysilsesquioxane (P), the content ratio of the first functional group is preferably 2 mol% or more, more preferably 5 mol% or more, and further preferably 10 mol% or more, relative to the silicon atoms possessed by the polysilsesquioxane (P). In addition, the content ratio of the first functional group is preferably 90 mol% or less, more preferably 80 mol% or less, and further preferably 75 mol% or less, relative to the silicon atoms possessed by the polysilsesquioxane (P). The first functional group possessed by the polysilsesquioxane (P) may be only one type, or may be two or more types.

[0066] In addition, the content ratio of the second functional group relative to the silicon atoms possessed by the polysilsesquioxane (P) is preferably 1 mol% or more, more preferably 2 mol% or more, and further preferably 5 mol% or more. In addition, the content ratio of the second functional group relative to the silicon atoms possessed by the polysilsesquioxane (P) is preferably 90 mol% or less, more preferably 80 mol% or less, and further preferably 70 mol% or less. The second functional group possessed by the polysilsesquioxane (P) may be only one type or may be two or more types.

[0067] In addition, the so-called "content ratio of the first functional group" refers to the ratio of the total amount of the first functional groups in the polysilsesquioxane (P) to the amount of silicon atoms possessed by the polysilsesquioxane (P). Therefore, for example, when the polysilsesquioxane (P) contains a side chain having a first functional group but not a second functional group, and a side chain having a first functional group and a second functional group, the first functional group possessed by the side chain of the former is compared with the total amount of the first functional group possessed by the side chain of the latter, and the amount of silicon atoms possessed by the polysilsesquioxane (P), and the content ratio of the first functional group is calculated. The same is true for the content ratio of the second functional group, and the content ratios of the third functional group and the fourth functional group shown below.

[0068] At least any one of the specific side chains in the polysilsesquioxane (P) may further have a group shown below as a functional group different from the first functional group and the second functional group.

[0069] Third functional group: a monovalent hydrophobic group having 1 to 50 carbon atoms (excluding the second functional group)

[0070] The fourth functional group: heterocyclic group

[0071] ·The third functional group

[0072] In order to adjust the fat solubility of the polysilsesquioxane (P) and thereby adjust the film-forming property or solubility in the developer, a third functional group may be introduced into the side chain of the polysilsesquioxane (P). The side chain having the third functional group may further have at least one of the first functional group and the second functional group. From the viewpoint of the ease of synthesis of the polysilsesquioxane (P) or the viewpoint of making the film-forming property good, the side chain having the third functional group is preferably a side chain different from the side chain having at least one of the first functional group and the second functional group (that is, a side chain having no one of the first functional group and the second functional group).

[0073] Examples of the monovalent hydrophobic group having 1 to 50 carbon atoms include: a monovalent chain hydrocarbon group having 1 to 50 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 50 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 50 carbon atoms, a monovalent oxy hydrocarbon group having 1 to 50 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 50 carbon atoms, a group having a structure in which two or more rings are bonded directly or via a divalent linking group (e.g., -O-, -CO-, -COO-, -(CH2)2-O-, etc.). Specific examples of the hydrocarbon group include: a The groups are the same as the groups exemplified in the description of the monovalent hydrocarbon group.

[0074] The side chain having the third functional group preferably has a group represented by the formula (2), and more preferably the group represented by the formula (2) is bonded to the silicon atom via a divalent linking group.1 It is preferably a monovalent chain hydrocarbon group having 1 to 50 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 50 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 50 carbon atoms, and more preferably a monovalent chain hydrocarbon group having 3 to 50 carbon atoms, a monovalent alicyclic hydrocarbon group having 5 to 50 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 50 carbon atoms.

[0075] From the viewpoint of exhibiting good pattern forming ability and achieving better film forming properties, the polysilsesquioxane (P) preferably has a first functional group or a second functional group and a third functional group, and more preferably has a first functional group, a second functional group and a third functional group.

[0076] When the polysilsesquioxane (P) has a third functional group, the content ratio of the third functional group is preferably 1 mol% or more, more preferably 2 mol% or more, and further preferably 5 mol% or more relative to the silicon atoms possessed by the polysilsesquioxane (P). In addition, the content ratio of the third functional group is preferably 90 mol% or less, more preferably 70 mol% or less, and further preferably 50 mol% or less relative to the silicon atoms possessed by the polysilsesquioxane (P). The third functional group possessed by the polysilsesquioxane (P) may be only one type or may be two or more types.

[0077] ·The fourth functional group

[0078] For example, the fourth functional group (heterocyclic group) is introduced into the side chain of the polysilsesquioxane (P) for the purpose of improving the dispersibility of inorganic particles, improving the adhesion to the substrate, adjusting the electrical characteristics in the application of liquid crystal alignment film, conductivity, adsorption of ionic low molecules, etc. Examples of the heterocyclic group possessed by the fourth functional group include a The side chain having the fourth functional group may also have a group represented by the formula (2). When the side chain having the fourth functional group has a group represented by the formula (2), the group represented by the formula (2) is preferably bonded to the silicon atom via a divalent linking group.

[0079] The fourth functional group may be introduced into a side chain having at least any one of the first functional group, the second functional group and the third functional group, or may be introduced into a side chain different therefrom. From the viewpoint of ease of synthesis of the polysilsesquioxane (P) or the viewpoint of making film forming properties good, it is preferred to introduce the fourth functional group into a side chain different from a side chain having at least any one of the first functional group and the second functional group (i.e., a side chain having no first functional group and no second functional group).

[0080] When the polysilsesquioxane (P) has a fourth functional group, from the viewpoint of ensuring good film-forming properties and exhibiting pattern forming ability, the polysilsesquioxane (P) preferably further has at least one of the first functional group and the second functional group, more preferably further has the first functional group and the second functional group, and more preferably has the first functional group, the second functional group and the third functional group.

[0081] When the polysilsesquioxane (P) has a fourth functional group, the content ratio of the fourth functional group is preferably 1 mol% or more, and more preferably 2 mol% or more, relative to the silicon atoms possessed by the polysilsesquioxane (P). In addition, the content ratio of the fourth functional group is preferably 30 mol% or less, and more preferably 25 mol% or less, relative to the silicon atoms possessed by the polysilsesquioxane (P). The fourth functional group possessed by the polysilsesquioxane (P) may be only one type, or may be two or more types.

[0082] From the viewpoint of film forming properties, the weight average molecular weight (Mw) of the polysilsesquioxane (P) is preferably 10,000 or more, more preferably 15,000 or more, and further preferably 20,000 or more. In addition, from the viewpoint of the handleability of the polysilsesquioxane (P), the Mw of the polysilsesquioxane (P) is preferably 400,000 or less, and more preferably 150,000 or less. In addition, in the present specification, the Mw of the polysilsesquioxane compound is a polystyrene conversion value measured by gel permeation chromatography (GPC).

[0083] <Synthesis of polysilsesquioxane (P)>

[0084] The method for synthesizing polysilsesquioxane (P) is not particularly limited as long as a compound having a polysilsesquioxane skeleton having a ladder structure and containing three or more specific side chains can be obtained. Polysilsesquioxane (P) can be obtained, for example, by using a compound having an alkoxysilyl group (hereinafter, also referred to as an "alkoxysilane compound") as a raw material and performing a hydrolysis-condensation reaction of the alkoxysilane compound.

[0085] More specifically, it is preferred to use a method including a reaction step of reacting a hydrolysis condensate salt of an alkoxysilane compound having an amino group with a reactive compound having a functional group capable of reacting with the hydrolysis condensate salt, and in the reaction step, the hydrolysis condensate salt having a ladder structure is reacted with three or more reactive compounds simultaneously to obtain polysilsesquioxane (P). According to the method, a ladder-structured polysilsesquioxane compound having three or more specific side chains can be obtained simply and with high yield.

[0086] When synthesizing the hydrolysis condensate salt, as the alkoxysilane compound, a nitrogen-containing alkoxysilane compound can be preferably used. As the nitrogen-containing alkoxysilane compound, for example, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl methoxydiethoxysilane, 3-aminopropyl ethoxydimethoxysilane, 3-aminopropyl tripropoxysilane, 3-aminopropyl tri(isopropoxy)silane, 3-aminopropyl tributoxysilane, N-(3-cyclohexylamino)propyl trimethoxysilane, etc. can be cited. Among these, an alkoxysilane compound with a primary amino group can be preferably used. As the nitrogen-containing alkoxysilane compound, one can be used alone, or two or more can be used in combination.

[0087] When synthesizing the hydrolysis condensate salt, a compound different from the nitrogen-containing alkoxysilane compound may be further used as the alkoxysilane compound. Examples of such alkoxysilane compounds include alkoxysilane compounds such as tetramethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and dimethyldiethoxysilane; sulfur-containing alkoxysilane compounds such as 3-mercaptopropyltriethoxysilane and mercaptomethyltriethoxysilane; epoxy-containing silane compounds such as 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane; unsaturated bond-containing alkoxysilane compounds such as 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, vinyltriethoxysilane, and p-phenylenetrimethoxysilane; trimethoxysilylpropylsuccinic anhydride, and the like.

[0088] As a method for obtaining a hydrolysis condensate salt, the following methods can be cited: a method of obtaining a hydrolysis condensate having a ladder structure with a primary or secondary amino group by a hydrolysis-condensation reaction of an alkoxysilane compound, and then reacting the obtained hydrolysis condensate with an acid to obtain an ammonium salt, i.e., a hydrolysis condensate salt; a method of reacting an alkoxysilane compound having a primary or secondary amino group with an acid to form a salt, and then performing a hydrolysis-condensation reaction of the alkoxysilyl group to obtain an ammonium salt, i.e., a hydrolysis condensate salt. Among these, the latter method is preferred in terms of being able to obtain a ladder structure polysilsesquioxane compound with a high yield.

[0089] The acid is not particularly limited, and examples thereof include hydrogen halides, oxygen-containing acids, etc. Specific examples of hydrogen halides include hydrogen chloride, hydrogen fluoride, hydrogen bromide, hydrogen iodide, etc. Specific examples of oxygen-containing acids include nitric acid, sulfuric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.

[0090] The hydrolysis-condensation reaction can be carried out by reacting one or more of the alkoxysilane compounds in the presence of water. During the reaction, the proportion of water used is preferably 10 to 2,000 parts by mass, more preferably 20 to 1,000 parts by mass, relative to 100 parts by mass of the alkoxysilane compound (total amount). The hydrolysis-condensation reaction is preferably carried out by heating, for example, in an oil bath. At this time, the heating temperature is preferably set to 130° C. or less, and the heating time is preferably set to 0.5 to 12 hours.

[0091] Then, the hydrolysis-condensation product salt having a ladder-like structure obtained by the hydrolysis-condensation reaction and three or more reactive compounds having functional groups capable of reacting with the hydrolysis-condensation product salt (hereinafter, also referred to as "reactive compounds") are reacted simultaneously (reaction step). By reacting the hydrolysis-condensation product salt with three or more reactive compounds simultaneously, the -NH3 + (X - ) or -NH2 + (X - )-as a reaction site, an organic group derived from each of the three reactive compounds is introduced into the hydrolysis condensate.

[0092] The functional group of the reactive compound that is capable of reacting with the hydrolysis condensation product salt (hereinafter also referred to as a "specific functional group") is not particularly limited as long as it is a functional group that can form a bond (preferably a covalent bond) by reacting with the ammonium salt structure of the hydrolysis condensation product salt or an amino group derived from the ammonium salt structure. From the viewpoint of reactivity, the specific functional group is preferably selected from -COX 2 (Where X 2 is a halogen atom), a cyclic ether group, an isocyanate group, an anhydride group, and an active ester group. 2 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Examples of the active ester group include an N-hydroxyester group, etc.

[0093] In addition, by using a reactive compound having a cyclic ether group as a specific functional group and reacting with a hydrolysis condensation salt, a polysilsesquioxane (P) having a hydroxyl group in the side chain can be obtained. In addition, by using a reactive compound having an acid anhydride group as a specific functional group and reacting with a hydrolysis condensation salt, a polysilsesquioxane (P) having a carboxyl group in the side chain can be obtained.

[0094] In the reactive compound, the structure other than the specific functional group can be appropriately selected according to the structure of the specific side chain introduced into the polysilsesquioxane compound. For example, as a reactive compound for introducing a side chain having a first functional group into a polysilsesquioxane compound (hereinafter, also referred to as the "first compound"), there can be cited compounds having at least one selected from the group consisting of an anhydride group, a cyclic ether group, a protected carboxyl group, and a protected hydroxyl group. In addition, as a reactive compound for obtaining a polysilsesquioxane compound having a second side chain (hereinafter, also referred to as the "second compound"), there can be cited compounds having a cross-linkable carbon-carbon unsaturated bond group and a specific functional group and being different from the first compound.

[0095] In addition, when synthesizing polysilsesquioxane (P), when the first compound and the second compound are used as reactive compounds, the second compound may have at least one selected from the group consisting of an anhydride group, a cyclic ether group, a protected carboxyl group, and a protected hydroxyl group in addition to having a cross-linkable carbon-carbon unsaturated bond group, as long as the second compound is a compound having a different structure from the first compound. In addition, the first compound may have at least one selected from the group consisting of an anhydride group, a cyclic ether group, a protected carboxyl group, and a protected hydroxyl group, as long as the first compound is a compound having a different structure from the second compound, and may have a cross-linkable carbon-carbon unsaturated bond group. That is, a compound having a cross-linkable carbon-carbon unsaturated bond group, an anhydride group, a cyclic ether group, a protected carboxyl group, or a protected hydroxyl group is both the first compound and the second compound.

[0096] Specific examples of the first compound include compounds represented by the following formula (1-1) to formula (1-19), and the like.

[0097] [Chemistry 4]

[0098]

[0099] (Where Y 1 For the detached base)

[0100] Specific examples of the second compound include compounds represented by the following formula (2-1) to formula (2-8), and the like.

[0101] [Chemistry 5]

[0102]

[0103] From the viewpoint of obtaining a polysilsesquioxane (P) having better film-forming properties and pattern-forming ability, the three or more reactive compounds used in the synthesis of the polysilsesquioxane (P) are preferably compounds containing at least one selected from the group consisting of an acid anhydride group, a cyclic ether group, a protected carboxyl group and a protected hydroxyl group and a cross-linkable carbon-carbon unsaturated bond group in different molecules, or compounds containing at least one selected from the group consisting of an acid anhydride group, a cyclic ether group, a protected carboxyl group and a protected hydroxyl group and a cross-linkable carbon-carbon unsaturated bond group in the same molecule.

[0104] When the hydrolysis condensation product salt reacts with the reactive compound, the ratio of the first compound used is preferably more than 2 mol %, more preferably more than 5 mol %, and more preferably more than 10 mol % relative to the silicon atom possessed by the hydrolysis condensation product salt. In addition, the ratio of the first compound used is preferably less than 90 mol %, more preferably less than 80 mol %, and more preferably less than 75 mol % relative to the silicon atom possessed by the hydrolysis condensation product salt. The first compound can be used alone or in combination of two or more.

[0105] In addition, relative to the silicon atoms possessed by the hydrolysis condensation product salt, the usage ratio of the second compound is preferably 1 mol% or more, more preferably 2 mol% or more, and further preferably 5 mol% or more. In addition, relative to the silicon atoms possessed by the hydrolysis condensation product salt, the usage ratio of the second compound is preferably 90 mol% or less, more preferably 80 mol% or less, and further preferably 70 mol% or less. The second compound can be used alone or in combination of two or more.

[0106] In addition, the "ratio of the first compound used" is calculated based on the total amount of the two or more first compounds used when two or more compounds are used as the first compound. Therefore, for example, when a compound having an acid anhydride group, a cyclic ether group, a protected carboxyl group or a protected hydroxyl group and a compound having a cross-linkable carbon-carbon unsaturated bond group and an acid anhydride group, a cyclic ether group, a protected carboxyl group or a protected hydroxyl group are used as reactive compounds, the ratio of the first compound used is calculated based on the total amount of the former compound and the latter compound. The same is true for the blending ratio of the second compound and the blending ratio of the third compound and the fourth compound shown below.

[0107] In addition, as polysilsesquioxane (P), when a compound having a third functional group in a side chain is obtained, as a reactive compound for obtaining the compound (hereinafter also referred to as a "third compound"), a compound having a monovalent hydrophobic group and a specific functional group and different from the first compound and the second compound can be cited. As specific examples of the third compound, for example, compounds represented by the following formulas (3-1) to (3-14) can be cited.

[0108] [Chemistry 6]

[0109]

[0110] When the reaction of the hydrolysis condensation product salt and the reactive compound, relative to the silicon atom possessed by the hydrolysis condensation product salt, the usage ratio of the third compound is preferably more than 1 mol %, more preferably more than 2 mol %, and then preferably more than 5 mol %. In addition, relative to the silicon atom possessed by the hydrolysis condensation product salt, the usage ratio of the third compound is preferably less than 90 mol %, more preferably less than 70 mol %, and then preferably less than 50 mol %. The third compound can be used alone or in combination of two or more.

[0111] Furthermore, when obtaining a compound having a fourth functional group in a side chain as a polysilsesquioxane (P), the following methods can be cited as methods thereof: (1) a method of using a compound having a heterocyclic ring and a specific functional group (hereinafter also referred to as a "fourth compound") as a reactive compound; (2) a method of using a carboxylic acid anhydride as a reactive compound and hydrolyzing -NH3 + X - Alternatively, a method of obtaining a polysilsesquioxane having a cyclic imide in a side chain by reacting a primary amino group generated by neutralization of a hydrolysis condensate salt with a carboxylic anhydride and then imidizing the reactant.

[0112] Specific examples of the fourth compound include compounds represented by the following formula (4-1) to formula (4-5), and the like.

[0113] [Chemistry 7]

[0114]

[0115] When the fourth compound is used in the reaction of the hydrolysis condensation product salt and the reactive compound, the fourth compound is preferably used at a ratio of 1 mol % or more, more preferably 2 mol % or more, and then preferably 5 mol % or more relative to the silicon atom possessed by the hydrolysis condensation product salt. In addition, the fourth compound is preferably used at a ratio of 60 mol % or less, more preferably 50 mol % or less relative to the silicon atom possessed by the hydrolysis condensation product salt. The fourth compound can be used alone or in combination of two or more.

[0116] The reaction of the hydrolysis condensate salt and the reactive compound is preferably carried out in a solvent in the presence of a base. As reaction solvents, water, organic solvents and mixed solvents thereof can be cited. As organic solvents, for example, N-methyl-2-pyrrolidone, N,N'-dimethylformamide (DMF), N,N'-dimethylacetamide, γ-butyrolactone, dimethyl sulfoxide (DMSO), cyclopentane sulfone, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, cyclohexanone, cyclopentanone, etc. can be cited.

[0117] As the base used, organic bases can be cited, and tertiary amines and quaternary ammonium can be preferably used. The amount of the base used varies depending on the type of the base or reaction conditions such as temperature, and can be appropriately set, for example, preferably 1 to 600 mol parts relative to 100 mol parts of silicon atoms possessed by the hydrolysis condensate salt. The proportion of the reaction solvent used is preferably 10 to 10,000 mol parts relative to a total of 100 parts by mass of the hydrolysis condensate salt.

[0118] In the reaction of the hydrolysis condensate salt and the reactive compound, the reaction temperature is preferably 0° C. to 250° C., more preferably 10° C. to 130° C. The reaction time is preferably 0.5 hour to 24 hours.

[0119] When the reaction of hydrolysis condensation product salt and reactive compound, use three or more compounds as reactive compound, and make hydrolysis condensation product salt and three or more reactive compounds react simultaneously.The method that makes hydrolysis condensation product salt and three or more reactive compounds react simultaneously is not particularly limited.For example, three or more reactive compounds can be mixed with solvent, prepare the mixed solution comprising three or more reactive compounds, and the mixed solution of described preparation is mixed with hydrolysis condensation product salt.At this moment, hydrolysis condensation product salt can be solid, and can also be the liquid containing hydrolysis condensation product salt formed by being dissolved in solvent.Or, can also prepare the solution comprising each reactive compound by three or more reactive compounds are mixed with solvent respectively, and the solution of described preparation is mixed with hydrolysis condensation product salt simultaneously.With regard to the aspect that operation is easier, it is preferably the method for using the former among these.

[0120] After the reaction is completed, the solid separated from the reaction solution is preferably washed with water and then dried using an appropriate drying agent as necessary to obtain the target polysilsesquioxane (P).

[0121] Composition

[0122] The composition disclosed herein is a polymer composition containing the polysilsesquioxane (P) and a solvent. As the solvent, a solvent capable of dissolving or dispersing the polysilsesquioxane (P) can be suitably used. Specific examples of the solvent include water, an organic solvent, and a mixed solvent thereof.

[0123] Examples of the organic solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,2-dimethyl-2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone, phenol, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, diacetone alcohol, 1-hexanol, 2-hexanol, propane-1,2-diol, 3-methoxy-1-butanol, ethylene glycol monomethyl ether, methyl lactate, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl acetoacetate. Ester, ethyl acetoacetate, ethyl propionate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate, propylene glycol monomethyl ether (propyleneglycol monomethyl ether, PGME), diethylene glycol diethyl ether acetate, propylene glycol monomethyl ether acetate (propylene glycol monomethyl ether acetate, PGMEA), propylene glycol diacetate, cyclopentanone, cyclohexanone, etc.

[0124] The composition of the present disclosure may further contain components (other components) other than polysilsesquioxane (P) and solvent. Other components may be appropriately set according to the purpose of the film formed by the composition of the present disclosure, and for example, polymers different from polysilsesquioxane (P), crosslinking agents, thermal polymerization initiators, photopolymerization initiators, antioxidants, metal chelate compounds, hardening accelerators, surfactants, fillers, dispersants, photosensitizers, colorants, softeners, plasticizers, bonding aids, ultraviolet absorbers, etc. may be listed. The proportion of other components may be appropriately selected according to each compound within the range that does not damage the effect of the present disclosure.

[0125] The solid content concentration of the composition of the present disclosure (the ratio of the total mass of the components other than the solvent to the total mass of the composition) can be appropriately selected in consideration of the viscosity of the composition, the volatility of the solvent, the use of the composition, etc. From the viewpoint of film forming properties, the solid content concentration of the composition of the present disclosure is, for example, 1% by mass to 60% by mass. The temperature when preparing the composition is, for example, 0°C to 60°C.

[0126] When forming a film using the present composition, it can be carried out according to a known method. For example, a pattern can be formed by exposing a portion of a film formed from the present composition and dissolving the unexposed portion in a developer.

[0127] The polysilsesquioxane (P) disclosed in the present invention is excellent in film forming properties and developability and can be used in various applications. Specifically, it is useful as a material for various applications such as optical applications, display applications, and semiconductor applications.

[0128] According to the present disclosure, the following means are provided.

[0129] [Means 1] A polysilsesquioxane compound having a ladder-like polysilsesquioxane skeleton and containing three or more specific side chains having one or more carbon atoms and not having a primary amino group or a salt thereof.

[0130] [Means 2] The polysilsesquioxane compound according to [Means 1], wherein the specific side chain has a partial structure represented by the formula (2).

[0131] [Means 3] The polysilsesquioxane compound according to [Means 1] or [Means 2], wherein at least one of the specific side chains has one or more selected from the group consisting of a carboxyl group, a hydroxyl group, a protected carboxyl group, and a protected hydroxyl group.

[0132] [Means 4] The polysilsesquioxane compound according to any one of [Means 1] to [Means 3], wherein at least one of the specific side chains has a crosslinkable carbon-carbon unsaturated bond group.

[0133] [Means 5] A polysilsesquioxane compound according to any one of [Means 1] to [Means 4], wherein as the specific side chain, there are a first side chain, a second side chain and a third side chain having structures different from each other, at least any one of the first side chain, the second side chain and the third side chain has one or more selected from the group consisting of a carboxyl group, a hydroxyl group, a protected carboxyl group and a protected hydroxyl group, and at least any one of the first side chain, the second side chain and the third side chain has a cross-linkable carbon-carbon unsaturated bond group.

[0134] [Means 6] The polysilsesquioxane compound according to any one of [Means 1] to [Means 5], wherein at least one of the specific side chains has a monovalent hydrophobic group having 1 to 50 carbon atoms (excluding crosslinkable carbon-carbon unsaturated bond groups).

[0135] [Means 7] The polysilsesquioxane compound according to any one of [Means 1] to [Means 6], wherein at least one of the specific side chains has a heterocyclic ring.

[0136] [Means 8] The polysilsesquioxane compound according to any one of [Means 1] to [Means 7], wherein the weight average molecular weight is 10,000 or more.

[0137] [Means 9] A method for producing a polysilsesquioxane compound, comprising a reaction step, wherein the hydrolysis condensation salt of an alkoxysilane compound having an amino group and a reactive compound having a functional group capable of reacting with the hydrolysis condensation salt are reacted, wherein the hydrolysis condensation salt has a ladder structure, and in the reaction step, the hydrolysis condensation salt is reacted with three or more of the reactive compounds simultaneously.

[0138] [Means 10] A method for producing a polysilsesquioxane compound according to [Means 9], wherein three or more of the reactive compounds have at least one selected from the group consisting of anhydride groups, cyclic ether groups, protected carboxyl groups and protected hydroxyl groups, and a cross-linkable carbon-carbon unsaturated bond group in different molecules, or have at least one selected from the group consisting of anhydride groups, cyclic ether groups, protected carboxyl groups and protected hydroxyl groups, and a cross-linkable carbon-carbon unsaturated bond group in the same molecule.

[0139] [Means 11] The method for producing a polysilsesquioxane compound according to [Means 9] or [Means 10], wherein the reactive compound has a 2 (Where X 2 is a halogen atom), at least one of the group consisting of a cyclic ether group, an isocyanate group, an anhydride group and an active ester group.

[0140] [Means 12] A composition comprising the polysilsesquioxane compound according to any one of [Means 1] to [Means 8], and a solvent.

[0141] [Example]

[0142] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples. In addition, "parts" and "%" in the following examples are based on mass unless otherwise specified.

[0143] In the following examples, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polysilsesquioxane compound were measured by the following methods.

[0144] <Mw and Mn of polysilsesquioxane compound>

[0145] The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) under the following conditions.

[0146] Device: Showa Denko Co., Ltd.'s "GPC-101"

[0147] GPC column: A combination of GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 manufactured by Shimadzu GLC Co., Ltd.

[0148] Mobile phase: tetrahydrofuran (THF)

[0149] Column temperature: 40℃

[0150] Flow rate: 1.0mL / min

[0151] Sample concentration: 1.0 mass%

[0152] Sample injection volume: 100μL

[0153] Detector: Differential refractometer

[0154] Standard material: monodisperse polystyrene

[0155] 1. Synthesis of polysilsesquioxane compounds

[0156] [Synthesis Example 1] Synthesis of Ladder Poly(3-aminopropyl)Silsesquioxane Hydrochloride (Polymer (R-1))

[0157] In a 500mL flask, add 24.000g of 3-aminopropyltrimethoxysilane and 200mL of 1.0mol / L hydrochloric acid, and stir at room temperature for 2 hours while circulating nitrogen. Afterwards, immerse the flask in an oil bath, heat and stir at 100°C to evaporate hydrogen chloride, water and by-product methanol. Next, dissolve the obtained solid component in 300mL of ultrapure water, and put the solution into 3000mL of acetone to precipitate a white solid, which is recovered by suction filtration. Furthermore, add 300mL of methanol to the recovered product for washing, and finally wash the recovered product with 300mL of acetone, and dry the obtained product under reduced pressure to obtain 14.573g of polymer (R-1). The composition of polymer (R-1) 29Si-NMR ( 29 Si-NuclearMagnetic Resonance, 29 The analytical results obtained by Si-NMR ( Figure 1 ) is consistent with the identification result of the non-patent literature "Kaneko et al., International Journal of Polymer Science, 2012, Article ID 684278", confirming that polymer (R-1) is ladder-like poly (3-aminopropyl) silsesquioxane hydrochloride.

[0158] [Example 1] Synthesis of Ladder-Shaped Polysilsesquioxane Compound (Polymer (P-1))

[0159] In a 50 mL eggplant-shaped flask, 0.2910 g (2 mmol) of the polymer (R-1) obtained by Synthesis Example 1 was completely dissolved in 6.0 mL of distilled water, and then 4.0 mL of N,N-dimethylformamide (DMF) and 0.608 g of triethylamine were added. Then, 0.1120 g of benzoyl chloride (compound (C-1)), 0.0800 g of succinic anhydride (compound (A-1)), and 0.0420 g of methacryloyl chloride (compound (C-2)) as reactive compounds were added to the solution, and stirred at room temperature for 10 minutes using a magnetic stirrer. Thereafter, 6 mL of 1N HCl was added, and stirring was continued for 5 minutes. The turbid solution was filtered, and the white solid was washed with distilled water and dried to obtain 0.40 g of polymer (P-1). The molecular weight of the polymer (P-1) was measured by GPC, and the weight average molecular weight was 38,000.

[0160] The polymer (P-1) was added to an alkaline solution (4 wt% NaOH heavy aqueous solution) to hydrolyze the siloxane main chain. 1 H-NMR measurement. The results are shown in Figure 2 In. Figure 2In the NMR spectrum, a peak derived from compound (C-1) was seen near 7.31ppm-7.73ppm, a peak derived from compound (A-1) was seen near 2.30ppm, and a peak derived from compound (C-2) was seen near 5.27ppm and 5.53ppm. In addition, in terms of the integral ratio of each peak, the introduction ratio of compound (C-1), compound (A-1) and compound (C-2) is roughly the same as the blending ratio of these three compounds, C-1: A-1: ​​C-2 = 4: 4: 2 (molar ratio). Based on the results, it can be said that in polymer (P-1), partial structures derived from each of compound (C-1), compound (A-1) and compound (C-2) are introduced into the side chain of the siloxane skeleton.

[0161] [Examples 2 to 6, Examples 9 to 11 and Comparative Example 2]

[0162] The same operation as in Example 1 was carried out except that the type and amount of the organic compound were changed as shown in Table 1, thereby obtaining polymers (P-2) to (P-6) and polymers (P-9) to (P-11), respectively.

[0163] [Example 7]

[0164] In a 50 mL eggplant flask, 0.2910 g (2 mmol) of polymer (R-1) was completely dissolved in 6.0 mL of distilled water, and then 4.0 mL of DMF and 0.608 g of triethylamine were added. The following three solutions (Solution 1 to Solution 3) were added to the solution being stirred at room temperature using a magnetic stirrer.

[0165] Solution 1: A solution prepared by dissolving 0.084 g of compound (A-2) in 1.5 mL of DMF

[0166] Solution 2: A solution prepared by dissolving 0.124 g of compound (I-1) in 1.5 mL of DMF

[0167] Solution 3: A solution prepared by dissolving 0.097 g of compound (C-8) in 1.5 mL of DMF

[0168] Thereafter, stirring was continued at room temperature for 10 minutes. Subsequently, 6 mL of 1N HCl was added, and stirring was continued for 5 minutes. The turbid solution was filtered, and the white solid was washed with distilled water and dried to obtain 0.480 g of a polymer (P-7).

[0169] [Example 8]

[0170] Except for changing the type and amount of the organic compound as shown in Table 1, the same operation as in Example 1 was performed to obtain a solid of the polymer (P-8). Then, in a 20 mL eggplant flask, 0.40 g of the polymer (P-8) and 3.6 g of N-methyl-2-pyrrolidone (NMP) were added and dissolved. Then, the temperature was raised to 180°C and stirred for 4 hours to carry out the imidization reaction. After the reaction was completed, the reaction solution was cooled to room temperature, added dropwise to 100 mL of methanol, the precipitate was filtered and recovered, and dried under reduced pressure to obtain 0.37 g of polymer (P-8A).

[0171] [Comparative Example 1]

[0172] In a 50 mL eggplant-shaped flask, 0.2910 g (2 mmol) of the polymer (R-1) obtained in Synthesis Example 1 was completely dissolved in 6.0 mL of distilled water, and then 4.0 mL of DMF and 0.608 g of triethylamine were added. Subsequently, the following three solutions were added dropwise to the solution stirred by a magnetic stirrer at room temperature in the order of solution 1, solution 2, and solution 3. When adding solutions 1 to 3 dropwise, the addition of solution 2 was started after the addition of solution 1 was completed, and the addition of solution 3 was started after the addition of solution 2 was completed.

[0173] Solution 1: A solution prepared by dissolving 0.1120 g of compound (C-1) in 1.5 mL of DMF

[0174] Solution 2: A solution prepared by dissolving 0.0420 g of compound (C-2) in 1.5 mL of DMF

[0175] Solution 3: A solution prepared by dissolving 0.0800 g of compound (A-1) in 1.5 mL of DMF

[0176] After all the solution was added, stirring was continued at room temperature for 10 minutes. Then, 6 mL of 1N HCl was added and stirring was continued for 5 minutes. The turbid solution was filtered, and the white solid was washed with distilled water and dried to obtain 0.20 g of polymer (Q-1).

[0177] For polymer (Q-1), the same treatment as in Example 1 was performed 1 H-NMR measurement. The results are shown in Figure 3 In. Figure 3In the NMR spectrum of , peaks derived from compound (C-1) were observed near 7.32ppm-7.73ppm, peaks derived from compound (C-2) were observed near 5.27ppm and 5.52ppm, but no peak derived from compound (A-1) was observed near 2.30ppm. On the other hand, in polymer (Q-1), a peak derived from a methylene group adjacent to a primary amino group was observed near 2.35ppm. According to the results, it is known that no partial structure derived from compound (A-1) is introduced into polymer (Q-1).

[0178] [Comparative Example 3]

[0179] In a 100 mL three-necked flask, 10.00 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 50.00 g of methyl isobutyl ketone, and 1.00 g of triethylamine were added and mixed at room temperature. Then, 10.00 g of pure water was added dropwise, and the mixture was reacted at 80° C. for 8 hours. After the reaction was completed, the organic layer was taken out and washed with a 0.2% by mass aqueous solution of ammonium nitrate until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure. An appropriate amount of methyl isobutyl ketone was added to obtain a 50% by mass solution of a polymer (ESSQ-1) having an epoxy group.

[0180] In a 100 mL three-necked flask, 2.00 g of a solution containing the polymer (ESSQ-1), 50 mol% of the compound (K-1) based on the total amount of silicon atoms in the polymer (ESSQ-1), 50 mol% of the compound (K-2) based on the total amount of silicon atoms in the polymer (ESSQ-1), 0.10 g of tetrabutylammonium bromide, and 29.00 g of methyl isobutyl ketone were added, and the mixture was stirred at 90° C. for 24 hours. After cooling to room temperature, liquid separation and washing with distilled water were repeated 5 times. Thereafter, the organic layer was recovered, and concentration and NMP dilution were repeated twice using a rotary evaporator, and then NMP was used to adjust the solid content concentration to 35% by mass to obtain an NMP solution of the polymer (Q-3).

[0181]

[0182] In Table 1, the numerical values ​​of the reactive compound and the base represent the ratio (mol %) to the total amount of silicon atoms possessed by the polymer (precursor). The abbreviations of the reactive compounds in Table 1 are shown below. In Table 1, "Compound 1" is a compound capable of introducing a first functional group into the side chain of polysilsesquioxane, and "Compound 2" is a compound capable of introducing a second functional group into the side chain of polysilsesquioxane. A-2 and E-1 are compounds capable of introducing a first functional group and a second functional group into the side chain of polysilsesquioxane.

[0183] [Chemistry 8]

[0184]

[0185] 2. Evaluation

[0186] [Example 12]

[0187] (1) Film-forming properties

[0188] The polymer (P-1) was dissolved in a mixed solvent of N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) (NMP / BC=80 / 20 (mass ratio)) to prepare a solution having a solid content concentration of 4 mass%. The solution was filtered using a filter having a pore size of 0.45 μm to prepare a polymer solution. The obtained polymer solution was applied to a silicon wafer using a spinner, pre-baked using a hot plate at 100°C for 2 minutes, and then heated at 200°C for 20 minutes in an oven replaced with nitrogen to form a film with a thickness of 0.1 μm. The peripheral and central parts of the film were observed using a 20x microscope. At this time, the case where there was no uneven coating (uneven film thickness, etc.) and cracks was judged as "good (○)", and the case where at least any one of uneven coating and cracks was observed was judged as "poor (×)". As a result, the film forming property was evaluated as "good (○)".

[0189] In addition, the same operation was performed except that the solid content concentration of the polymer solution was changed to form a film with a thickness of 1 μm, and the film forming property was evaluated in the same manner, and the result was "good (○)". In addition, the thicker the film, the more noticeable the unevenness of the film thickness is, and cracks are also more likely to occur.

[0190] (2) Developability

[0191] 100 parts by mass of polymer (P-1) and 15 parts by mass of IRGACURE OXE-02 (manufactured by BASF) as a photopolymerization initiator were dissolved in a mixed solvent of NMP and BC (NMP / BC=80 / 20 (mass ratio)) to prepare a polymer solution having a solid content concentration of 30% by mass of polymer (P-1). The obtained polymer solution was applied to a silicon wafer using a spinner, pre-baked on a 100°C hot plate for 2 minutes, and then heated at 200°C for 20 minutes in an oven replaced with nitrogen to form a film with a thickness of 1.0 μm. The obtained film was exposed to light using a high-pressure mercury lamp (exposure at 365 nm was 100 mJ / cm 2), the entire surface was exposed, and then developed using a 2.38 mass % tetramethylammonium hydroxide aqueous solution at 25°C by a liquid covering method for 60 seconds. Subsequently, ultrapure water was used for running water cleaning for 60 seconds, and then dried to form a film on the silicon wafer. The average film thickness before and after development was measured, and the residual film rate (residual film rate before and after development) was calculated by the following formula (E1).

[0192] Residual film rate (%) = {(average film thickness after development) / (average film thickness before development)}×100…(E1)

[0193] Based on the calculated residual film rate, the difference in solubility of the film in the developer before and after exposure (developability) was evaluated. At this time, the case where the residual film rate was 85% or more was judged as "good (○)", the case where the residual film rate was 70% or more and less than 85% was judged as "acceptable (△)", and the case where the residual film rate was less than 70% was judged as "poor (×)". As a result, the evaluation of the developability based on the residual film rate was "good (○)".

[0194] [Example 13 to Example 22 and Comparative Example 4 to Comparative Example 6]

[0195] The film forming property and the developing property were evaluated in the same manner as in Example 12 except that the type of the polymer was changed as described in Table 2. Table 2 shows the evaluation results.

[0196] [Table 2]

[0197]

[0198] As shown in Table 2, Examples 12 to 22 were all evaluated as "○" for film forming properties and "○" or "△" for developability, showing various properties in a well-balanced manner.

[0199] In contrast, in Comparative Example 4 using a polysilsesquioxane compound having only two specific side chains and Comparative Example 5 using only one specific side chain, uneven coating and cracks are noticeable when the film is thickened, and the developability is also evaluated as poor (×). The reasons are considered to be that polymers (Q-1) and (Q-2) have higher crystallinity than polymers (P-1) to (P-11) having three or more specific side chains, resulting in poor film forming properties, and that the developability is reduced due to the lack of an alkali-soluble group. In addition, Comparative Example 6 using a polysilsesquioxane compound having a cage structure has poor film forming properties (×).

Claims

1. A polysilsesquioxane compound having a ladder-like polysilsesquioxane skeleton and containing three or more specific side chains having one or more carbon atoms and not having a primary amino group or a salt thereof.

2. The polysilsesquioxane compound according to claim 1, wherein the specific side chain has a partial structure represented by the following formula (2): *——X 1 ——R 1 (2) In formula (2), X 1 For-NR 2 -CO-、-NR 2 -、-NR 2 -CO-NR 3 -、-CO-NR 2 -CO- or a group represented by the following formula (n), R 2 and R 3 are independently a hydrogen atom or a monovalent hydrocarbon group; R 1 It is a monovalent organic group; "*" indicates a bonding bond; In formula (n), R 7 is a monovalent organic group; m is an integer from 0 to 3; when m is 2 or 3, multiple R 7 Same or different; "* 1 " represents the same as R in the formula (2) 1 "*" indicates a bonding bond. 3 . The polysilsesquioxane compound according to claim 1 , wherein at least one of the specific side chains has one or more selected from the group consisting of a carboxyl group, a hydroxyl group, a protected carboxyl group, and a protected hydroxyl group. 4 . The polysilsesquioxane compound according to claim 1 , wherein at least one of the specific side chains has a crosslinkable carbon-carbon unsaturated bond group.

5. The polysilsesquioxane compound according to claim 1 or 2, wherein the specific side chains include a first side chain, a second side chain, and a third side chain having structures different from each other, At least any one of the first side chain, the second side chain, and the third side chain has one or more selected from the group consisting of a carboxyl group, a hydroxyl group, a protected carboxyl group, and a protected hydroxyl group, At least any one of the first side chain, the second side chain, and the third side chain has a crosslinkable carbon-carbon unsaturated bond group. 6 . The polysilsesquioxane compound according to claim 5 , wherein at least one of the specific side chains has a monovalent hydrophobic group having 1 to 50 carbon atoms, wherein the monovalent hydrophobic group having 1 to 50 carbon atoms does not include a crosslinkable carbon-carbon unsaturated bond group. The polysilsesquioxane compound according to claim 5 , wherein at least one of the specific side chains has a heterocyclic ring. 8 . The polysilsesquioxane compound according to claim 1 , wherein the weight average molecular weight is 10,000 or more.

9. A method for producing a polysilsesquioxane compound, comprising a reaction step of reacting a hydrolysis condensate salt of an alkoxysilane compound having an amino group with a reactive compound having a functional group capable of reacting with the hydrolysis condensate salt, The hydrolysis condensation product salt has a ladder structure. In the reaction step, the hydrolysis-condensation product salt is reacted with three or more reactive compounds simultaneously.

10. The method for producing a polysilsesquioxane compound according to claim 9, wherein the three or more reactive compounds have at least one selected from the group consisting of anhydride groups, cyclic ether groups, protected carboxyl groups and protected hydroxyl groups, and a cross-linkable carbon-carbon unsaturated bond group in different molecules, or have at least one selected from the group consisting of anhydride groups, cyclic ether groups, protected carboxyl groups and protected hydroxyl groups, and a cross-linkable carbon-carbon unsaturated bond group in the same molecule.

11. The method for producing a polysilsesquioxane compound according to claim 9 or 10, wherein the reactive compound has a 2 (in, X 2 is a halogen atom), at least one of the group consisting of a cyclic ether group, an isocyanate group, an anhydride group and an active ester group.

12. A composition comprising the polysilsesquioxane compound according to claim 1 or 2, and a solvent.

Images