Composition, laminate, and method for producing laminate

Abstract

To provide a composition having excellent removability of edges with an organic solvent.SOLUTION: Provide is a composition comprising: a compound (A) having a cationic functional group including at least one of a primary nitrogen atom and a secondary nitrogen atom and an Si-O bond; a crosslinking agent (B) having three or more -C(=O)OX groups (where X is a hydrogen atom or a C1-C6 alkyl group) in a molecule, wherein one or more and six or less of the three or more -C(=O)OX groups are -C(=O)OH groups; and a polar solvent (D), wherein the proportion of water in the polar solvent (D) is 30 mass% or less. Also provided are a laminate using the composition and a method for producing the laminate.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a composition, a laminate, and a method for manufacturing the laminate.

Background Art

[0002] Conventionally, in various technical fields such as the field of electronic devices, a composition containing a polymer has been applied to a member. For example, Patent Document 1 describes a compound (A) having a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom and having a weight average molecular weight of 130 or more and 400,000 or less, and a -C(=O)OX group (X is a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms) in the molecule. A crosslinking agent (B) having 3 or more and having 1 or more and 6 or less of the 3 or more -C(=O)OX groups being -C(=O)OH groups and having a weight average molecular weight of 200 or more and 600 or less, and water (D). A film composition for a semiconductor is described.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Disclosure of the Invention

Problems to be Solved by the Invention

[0004] In the composition described in Patent Document 1, the solubility in an organic solvent is not sufficient. For example, after coating on a silicon substrate, the edge portion cannot be removed by an edge rinse solution (organic solvent) used for general semiconductor applications. There was a problem.

[0005] The present disclosure has been made in view of the above problems, and an object thereof is to provide a composition excellent in edge removability by an organic solvent, a laminate using the composition, and a method for manufacturing the same.

Means for Solving the Problems

[0006] The specific means for solving the above problems are as follows. <1> A compound (A) having a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom and an Si—O bond, and having three or more —C(═O)OX groups (X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the molecule, and among the three or more —C(═O)OX groups, one or more and six or less are —C(═O)OH groups, a crosslinking agent (B), and a polar solvent (D), wherein the proportion of water in the polar solvent (D) is 30% by mass or less based on the total mass of the polar solvent (D). <2> The composition according to <1>, wherein the polar solvent (D) contains alcohols. <3> The composition according to <2>, wherein the proportion of alcohols in the polar solvent (D) is 70% by mass or more based on the total mass of the polar solvent (D). <4> The composition according to any one of <1> to <3>, wherein the weight average molecular weight of the crosslinking agent (B) is 200 or more and 600 or less. <5> The composition according to any one of <1> to <4>, wherein the crosslinking agent (B) has a ring structure in the molecule. <6> The composition according to <5>, wherein the ring structure is at least one of a benzene ring and a naphthalene ring. <7> The composition according to any one of <1> to <6>, which is used for manufacturing a semiconductor member. <8> A laminate having an adhesive layer formed from the composition according to any one of <1> to <7> and a substrate. <9> The laminate according to <8>, wherein the substrate is a semiconductor substrate or a resin substrate. <10> The laminate according to <8> or <9>, wherein the substrate includes a first substrate and a second substrate, and the first substrate, the adhesive layer, and the second substrate are laminated in this order. <11> The laminate according to any one of <8> to <10>, wherein one of the first substrate and the second substrate is a semiconductor substrate and the other is a resin substrate. <12> Step A of applying the composition according to any one of <1> to <7> to a first substrate, and step B of heating the composition applied to the first substrate to form an adhesive layer. A method for manufacturing a laminate having these steps. <13> The method for manufacturing a laminate according to <12>, wherein the first substrate is a semiconductor substrate or a resin substrate. <14> The method for manufacturing a laminate according to <12> or <13>, further comprising a step of laminating a second substrate on the adhesive layer formed in step B.

Advantages of the Invention

[0007] The present disclosure can provide a composition excellent in edge removability by an organic solvent, a laminate using the composition, and a method for manufacturing the same.

Embodiments for Carrying Out the Invention

[0008] In this specification, a numerical range represented by "~" or "-" means a range including the numerical values described before and after "~" or "-" as a lower limit value and an upper limit value.

[0009] 〔Composition〕 The composition according to the present disclosure includes a compound (A) having a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom and a Si-O bond, and three or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the molecule, and among the three or more -C(=O)OX groups, one or more to six are -C(=O)OH groups, a crosslinking agent (B), and a polar solvent (D), and the proportion of water in the polar solvent (D) is 30% by mass or less based on the total mass of the polar solvent (D).

[0010] As described above, in the conventional composition, the solubility in an organic solvent is not sufficient. For example, after coating on a silicon substrate, there is a problem that the edge portion cannot be removed by an edge rinse solution (organic solvent) used for general semiconductor applications. In the composition according to the present disclosure, the proportion of water in the polar solvent (D) is 30% by mass or less based on the total mass of the polar solvent (D). Although the detailed mechanism is unknown, the solubility of the edge portion of the film after coating and drying in the edge rinse liquid (organic solvent) is improved, and a composition excellent in edge removability by an organic solvent can be provided. Further, in the composition according to the present disclosure, the proportion of water in the polar solvent (D) is 30% by mass or less based on the total mass of the polar solvent (D). Although the detailed mechanism is unknown, excellent coatability with respect to a resin substrate can also be exhibited.

[0011] (Polar solvent (D)) The composition according to the present disclosure contains a polar solvent (D), and the proportion of water in the polar solvent (D) is 30% by mass or less based on the total mass of the polar solvent (D). Here, the polar solvent (D) refers to a solvent having a relative permittivity of 5 or more at room temperature (25°C). Specific examples of the polar solvent (D) include protic inorganic compounds such as water and heavy water; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, benzyl alcohol, diethylene glycol, triethylene glycol, and glycerin; ethers such as tetrahydrofuran and dimethoxyethane; aldehydes or ketones such as furfural, acetone, ethyl methyl ketone, and cyclohexane; acid derivatives such as acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, formaldehyde, N-methylformamide, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and hexamethylphosphoric triamide; nitriles such as acetonitrile and propionitrile; nitro compounds such as nitromethane and nitrobenzene; and sulfur compounds such as dimethyl sulfoxide.

[0012] In the composition according to the present disclosure, the proportion of water in the polar solvent (D) is 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, further more preferably 1% by mass or less, and particularly preferably 0% by mass, from the viewpoints of edge removal property and coatability on a resin substrate. For example, in the composition according to the present disclosure, the proportion of water in the polar solvent (D) may be 0% by mass or more and 30% by mass or less, may be 0% by mass or more and 20% by mass or less, may be 0% by mass or more and 10% by mass or less, may be 0% by mass or more and 5% by mass or less, or may be 0% by mass or more and 1% by mass or less, based on the total mass of the polar solvent (D).

[0013] From the viewpoint of edge removal property, the polar solvent (D) preferably contains an alcohol, more preferably contains a monoalcohol, still more preferably contains a monoalcohol having an alkoxy group, and particularly preferably contains 1-methoxy-2-propanol. Also, from the viewpoint of edge removal property, the proportion of alcohol in the polar solvent (D) is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, even more preferably 95% by mass or more, still even more preferably 99% by mass or more, and particularly preferably 100% by mass. For example, in the composition according to the present disclosure, the proportion of alcohol in the polar solvent (D) may be 70% by mass or more and 100% by mass or less, may be 80% by mass or more and 100% by mass or less, may be 90% by mass or more and 100% by mass or less, may be 95% by mass or more and 100% by mass or less, or may be 99% by mass or more and 100% by mass or less.

[0014] The polar solvent (D) may be used alone or in combination of two or more. The content of the polar solvent (D) in the composition according to the present disclosure is not particularly limited, but is preferably 1.0% by mass or more and 99.99896% by mass or less, more preferably 40% by mass or more and 99.99896% by mass or less, based on the total mass of the composition.

[0015] (Compound (A)) The composition according to the present disclosure contains a compound (A) having a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom and an Si—O bond. The compound (A) may be a compound having a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom and an Si—O bond and having a weight average molecular weight of 130 or more and 10,000 or less.

[0016] Compound (A) is a compound having a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom. The cationic functional group is not particularly limited as long as it can carry a positive charge and contains at least one of a primary nitrogen atom and a secondary nitrogen atom.

[0017] Furthermore, compound (A) may contain a tertiary nitrogen atom in addition to the primary nitrogen atom and the secondary nitrogen atom.

[0018] In the present specification, the “primary nitrogen atom” refers to a nitrogen atom bonded to only two hydrogen atoms and one atom other than a hydrogen atom (for example, the nitrogen atom contained in a primary amino group (—NH 2 group)), or a nitrogen atom bonded to only three hydrogen atoms and one atom other than a hydrogen atom (cation). Also, the “secondary nitrogen atom” refers to a nitrogen atom bonded to only one hydrogen atom and two atoms other than a hydrogen atom (that is, the nitrogen atom contained in the functional group represented by the following formula (a)), or a nitrogen atom bonded to only two hydrogen atoms and two atoms other than a hydrogen atom (cation). Further, the "tertiary nitrogen atom" refers to a nitrogen atom bonded to only three atoms other than hydrogen atoms (i.e., the nitrogen atom of the functional group represented by the following formula (b)), or a nitrogen atom (cation) bonded to one hydrogen atom and only three atoms other than hydrogen atoms.

[0019]

Chemical formula

[0020] In formula (a) and formula (b), * indicates the bonding position with an atom other than a hydrogen atom. Here, the functional group represented by the formula (a) may be a functional group constituting a part of a secondary amino group (-NHR a group; where R a represents an alkyl group), or may be a divalent linking group contained in the polymer backbone. Further, the functional group represented by the formula (b) (i.e., the tertiary nitrogen atom) may be a functional group constituting a part of a tertiary amino group (-NR b R c group; where R b and R c each independently represent an alkyl group), or may be a trivalent linking group contained in the polymer backbone.

[0021] The weight average molecular weight of the compound (A) is preferably 130 or more and 10,000 or less, more preferably 130 or more and 5,000 or less, and still more preferably 130 or more and 2,000 or less.

[0022] In this specification, the weight average molecular weight refers to the weight average molecular weight in terms of polyethylene glycol, measured by the GPC (Gel Permeation Chromatography) method. Specifically, the weight-average molecular weight is calculated using an aqueous solution with a sodium nitrate concentration of 0.1 mol / L as the developing solvent, detecting the refractive index at a flow rate of 1.0 mL / min using an analytical instrument Shodex DET RI-101 and two types of analytical columns (TSKgel G6000PWXL-CP and TSKgel G3000PWXL-CP manufactured by Tosoh Corporation), and using polyethylene glycol / polyethylene oxide as a standard product with analytical software (Empower3 manufactured by Waters).

[0023] In addition, the compound (A) may further have an anionic functional group, a nonionic functional group, etc. as necessary. The nonionic functional group may be a hydrogen bond acceptor group or a hydrogen bond donor group. Examples of the nonionic functional group include a hydroxy group, a carbonyl group, an ether group (-O-), etc. The anionic functional group is not particularly limited as long as it can carry a negative charge. Examples of the anionic functional group include a carboxylic acid group, a sulfonic acid group, a sulfate group, etc.

[0024] Examples of the compound having an Si-O bond and an amino group include siloxanediamine, a silane coupling agent having an amino group, a siloxane polymer, etc. Examples of the silane coupling agent having an amino group include a compound represented by the following formula (A-3).

[0025]

Chemical formula

[0026] In formula (A-3), R 1 represents an optionally substituted alkyl group having 1 to 4 carbon atoms. R 2 and R 3 each independently represent an optionally substituted alkylene group having 1 to 12 carbon atoms (which may contain a carbonyl group, an ether group, etc. in the skeleton), an ether group or a carbonyl group. R 4 and R5 independently represents an optionally substituted alkylene group having 1 to 4 carbon atoms or a single bond. Ar represents a divalent or trivalent aromatic ring. X 1 represents hydrogen or an optionally substituted alkyl group having 1 to 5 carbon atoms. X 2 represents hydrogen, a cycloalkyl group, a heterocyclic group, an aryl group, or an optionally substituted alkyl group having 1 to 5 carbon atoms (which may contain a carbonyl group, an ether group, etc. in the skeleton). A plurality of R 1 , R 2 , R 3 , R 4 , R 5 , X 1 may be the same or different. R 1 , R 2 , R 3 , R 4 , R 5 , X 1 , X 2 Examples of the substituents of the alkyl group and the alkylene group in include, independently of each other, an amino group, a hydroxy group, an alkoxy group, a cyano group, a carboxylic acid group, a sulfonic acid group, a halogen atom, and the like. Examples of the divalent or trivalent aromatic ring in Ar include, for example, a divalent or trivalent benzene ring. X 2 Examples of the aryl group in include, for example, a phenyl group, a methylbenzyl group, a vinylbenzyl group, and the like.

[0027] Specific examples of the silane coupling agent represented by formula (A-3) include, for example, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminoisobutyldimethylmethoxysilane, N-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, N-(2-aminoethyl)-11-aminoundecyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, (aminoethylaminoethyl)phenyltriethoxysilane, methylbenzylaminoethylaminopropyltrimethoxysilane, benzylaminoethylaminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, (aminoethylaminoethyl)phenethyltrimethoxysilane, (aminoethylaminomethyl)phenethyltrimethoxysilane, N-{2-[3-(trimethoxysilyl)propylamino]ethyl}ethylenediamine, 3-aminopropyldiethoxymethylsilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldimethylmethoxysilane, trimethoxy[2-(2-aminoethyl)-3-aminopropyl]silane, diaminomethyldimethylethoxysilane, methylaminomethyldimethylethoxysilane, p-aminophenyltrimethoxysilane, N-methylaminopropyltriethoxysilane, N-methylaminopropylmethyldiethoxysilane, (phenylaminomethyl)methyldiethoxysilane, acetamidopropyltrimethoxysilane, and hydrolysis products thereof.

[0028] Examples of silane coupling agents containing amino groups other than formula (A-3) include N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, bis[(3-triethoxysilyl)propyl]amine, piperazinylpropylmethyldimethoxysilane, bis[3-(triethoxysilyl)propyl]urea, bis(methyldiethoxysilylpropyl)amine, 2,2-dimethoxy-1,6-diaza-2-silacyclooctane, 3,5-diamino-N-[4-(methoxydimethylsilyl)phenyl]benzamide, 3,5-diamino-N-[4-(triethoxysilyl)phenyl]benzamide, 5-(ethoxydimethylsilyl)benzene-1,3-diamine, and their hydrolyzates.

[0029] The above-mentioned silane coupling agents having amino groups may be used alone or in combination of two or more. Also, a silane coupling agent having an amino group and a silane coupling agent having no amino group may be used in combination. For example, a silane coupling agent having a mercapto group may be used to improve adhesion to a metal.

[0030] In addition, polymers (siloxane polymers) formed through siloxane bonds (Si-O-Si) from these silane coupling agents may be used. For example, from the hydrolyzate of 3-aminopropyltrimethoxysilane, polymers having a linear siloxane structure, polymers having a branched siloxane structure, polymers having a cyclic siloxane structure, polymers having a cage-like siloxane structure, etc. can be obtained. The cage-like siloxane structure is represented by, for example, the following formula (A-1).

[0031]

Chemical formula

[0032] Examples of the siloxane diamine include compounds represented by the following formula (A-2). In the formula (A-2), i is an integer from 0 to 4, j is an integer from 1 to 3, and Me is a methyl group.

[0033]

Chemical formula

[0034] Examples of the siloxane diamine also include 1,3-bis(3-aminopropyl)tetramethyldisiloxane (in the formula (A-2), i = 0, j = 1) and 1,3-bis(2-aminoethylamino)propyltetramethyldisiloxane (in the formula (A-2), i = 1, j = 1).

[0035] Since compound (A) has an amino group, it is easily soluble in the polar solvent (D) described below. From the viewpoint of solubility, it is preferable that the ratio of the total number of primary nitrogen atoms and secondary nitrogen atoms in compound (A) to the number of silicon atoms (total number of primary nitrogen atoms and secondary nitrogen atoms / number of silicon atoms) is 0.2 or more and 5 or less.

[0036] By using compound (A) that is easily soluble in the polar solvent (D), the affinity with a hydrophilic surface such as a silicon substrate is increased, so that a smooth film can be formed.

[0037] As a more preferable compound (A), from the viewpoint of plasma resistance, it is preferable that a non-crosslinking group such as a methyl group bonded to Si satisfies the relationship of (non-crosslinking group) / Si < 2 in terms of molar ratio. By satisfying this relationship, it is presumed that the crosslinking (crosslinking between Si-O-Si bonds and amide bonds, imide bonds, etc.) density of the formed film is improved, and a film stronger against plasma is formed.

[0038] As described above, compound (A) has a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom. Here, when compound (A) contains a primary nitrogen atom, the proportion of the primary nitrogen atom in all the nitrogen atoms in compound (A) is preferably 20 mol% or more, more preferably 25 mol% or more, and still more preferably 30 mol% or more. Further, compound (A) may have a cationic functional group that contains a primary nitrogen atom and does not contain nitrogen atoms other than the primary nitrogen atom (for example, a secondary nitrogen atom, a tertiary nitrogen atom).

[0039] Also, when compound (A) contains a secondary nitrogen atom, the proportion of the secondary nitrogen atom in all the nitrogen atoms in compound (A) is preferably 5 mol% or more and 50 mol% or less, and more preferably 10 mol% or more and 45 mol% or less.

[0040] Further, compound (A) may contain a tertiary nitrogen atom in addition to the primary nitrogen atom and the secondary nitrogen atom. When compound (A) contains a tertiary nitrogen atom, the proportion of the tertiary nitrogen atom in all the nitrogen atoms in compound (A) is preferably 20 mol% or more and 50 mol% or less, and more preferably 25 mol% or more and 45 mol% or less.

[0041] The content of compound (A) in the composition according to the present disclosure is not particularly limited. For example, it can be 0.001 mass% or more and 20 mass% or less with respect to the whole composition, preferably 0.01 mass% or more and 20 mass% or less, and more preferably 0.04 mass% or more and 20 mass% or less.

[0042] (Crosslinking agent (B)) The composition according to the present disclosure contains a crosslinking agent (B) having three or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the molecule, and among three or more -C(=O)OX groups (hereinafter, also referred to as "COOX"), one or more and six or less are -C(=O)OH groups (hereinafter, also referred to as "COOH").

[0043] The crosslinking agent (B) is a compound having three or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the molecule, preferably a compound having three to six -C(=O)OX groups in the molecule, and more preferably a compound having three or four -C(=O)OX groups in the molecule.

[0044] In the crosslinking agent (B), examples of X in the -C(=O)OX group include a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among them, a hydrogen atom, a methyl group, an ethyl group, and a propyl group are preferred. Note that the Xs in the -C(=O)OX groups may be the same or different from each other.

[0045] The crosslinking agent (B) is a compound having one to six -C(=O)OH groups in the molecule where X is a hydrogen atom, preferably a compound having one to four -C(=O)OH groups in the molecule, more preferably a compound having two to four -C(=O)OH groups in the molecule, and even more preferably a compound having two or three -C(=O)OH groups in the molecule.

[0046] The crosslinking agent (B) is preferably a compound having a weight average molecular weight of 200 or more and 600 or less, and more preferably a compound having a weight average molecular weight of 200 or more and 400 or less.

[0047] The crosslinking agent (B) preferably has a ring structure in the molecule. Examples of the ring structure include an alicyclic structure and an aromatic ring structure. Further, the crosslinking agent (B) may have a plurality of ring structures in the molecule, and the plurality of ring structures may be the same or different.

[0048] Examples of the alicyclic structure include alicyclic structures having 3 to 8 carbon atoms, preferably alicyclic structures having 4 to 6 carbon atoms, and the inside of the ring structure may be saturated or unsaturated. More specifically, examples of the alicyclic structure include saturated alicyclic structures such as cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring; and unsaturated alicyclic structures such as cyclopropene ring, cyclobutene ring, cyclopentene ring, cyclohexene ring, cycloheptene ring, cyclooctene ring.

[0049] The aromatic ring structure is not particularly limited as long as it is a ring structure showing aromaticity. For example, benzene-based aromatic rings such as benzene ring, naphthalene ring, anthracene ring, perylene ring; aromatic heterocycles such as pyridine ring, thiophene ring; non-benzene-based aromatic rings such as indene ring, azulene ring, etc. can be mentioned.

[0050] Examples of the ring structure contained in the crosslinking agent (B) in the molecule include at least one selected from the group consisting of cyclobutane ring, cyclopentane ring, cyclohexane ring, benzene ring and naphthalene ring. From the viewpoint of further enhancing the heat resistance of the film obtained from the composition, at least one of the benzene ring and naphthalene ring is more preferable.

[0051] As described above, the crosslinking agent (B) may have a plurality of ring structures in the molecule. When the ring structure is benzene, it may have a biphenyl structure, a benzophenone structure, a diphenyl ether structure, etc.

[0052] The crosslinking agent (B) preferably has a fluorine atom in the molecule, more preferably has 1 to 6 fluorine atoms in the molecule, and even more preferably has 3 to 6 fluorine atoms in the molecule. For example, the crosslinking agent (B) may have a fluoroalkyl group in the molecule, and specifically, it may have a trifluoroalkyl group or a hexafluoroisopropyl group.

[0053] Furthermore, examples of the crosslinking agent (B) include carboxylic acid compounds such as alicyclic carboxylic acids, benzenecarboxylic acids, naphthalenecarboxylic acids, phthalic acids, and fluorinated aromatic ring carboxylic acids; and carboxylic acid ester compounds such as alicyclic carboxylic acid esters, benzenecarboxylic acid esters, naphthalenecarboxylic acid esters, phthalic acid esters, and fluorinated aromatic ring carboxylic acid esters. The carboxylic acid ester compound has a carboxy group (—C(═O)OH group) in the molecule, and in three or more —C(═O)OX groups, at least one X is an alkyl group having 1 to 6 carbon atoms (that is, having an ester bond). In the composition according to the present disclosure, since the crosslinking agent (B) is a carboxylic acid ester compound, aggregation due to the association of the compound (A) and the crosslinking agent (B) in the composition is suppressed, the number of aggregates and pits is reduced, and a film having higher smoothness or a film having a larger film thickness can be obtained, and the adjustment of the film thickness becomes easy.

[0054] The carboxylic acid compound is preferably a tetravalent or lower carboxylic acid compound containing four or less —C(═O)OH groups, and more preferably a trivalent or tetravalent carboxylic acid compound containing three or four —C(═O)OH groups.

[0055] The carboxylic acid ester compound preferably contains three or less carboxy groups (—C(═O)OH groups) in the molecule and three or less ester bonds, and more preferably contains two or less carboxy groups in the molecule and two or less ester bonds.

[0056] In the carboxylic acid ester compound, when X is an alkyl group having 1 to 6 carbon atoms in three or more —C(═O)OX groups, X is preferably a methyl group, an ethyl group, a propyl group, a butyl group, etc., but from the viewpoint of further suppressing aggregation due to the association of the compound (A) and the crosslinking agent (B) in the composition, an ethyl group or a propyl group is preferable.

[0057] Specific examples of the carboxylic acid compound include, but are not limited to, alicyclic carboxylic acids such as 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4,5,6-cyclohexanehexacarboxylic acid; benzene carboxylic acids such as 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid, benzene pentacarboxylic acid, mellitic acid; naphthalene carboxylic acids such as 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid; diphthalic acids such as 3,3’,5,5’-tetracarboxydiphenylmethane, biphenyl-3,3’,5,5’-tetracarboxylic acid, biphenyl-3,4’,5-tricarboxylic acid, biphenyl-3,3’,4,4’-tetracarboxylic acid, benzophenone-3,3’,4,4’-tetracarboxylic acid, 4,4’-oxydiphthalic acid, 3,4’-oxydiphthalic acid, 1,3-bis(phthalic acid)tetramethyldisiloxane, 4,4’-(ethyne-1,2-diyl)diphthalic acid, 4,4'-(1,4-phenylenebis(oxy))diphthalic acid, 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))diphthalic acid, 4,4'-((oxybis(4,1-phenylene))bis(oxy))diphthalic acid; perylene carboxylic acids such as perylene-3,4,9,10-tetracarboxylic acid; anthracene carboxylic acids such as anthracene-2,3,6,7-tetracarboxylic acid;Examples of the fluorinated aromatic ring carboxylic acids include 4,4'-(hexafluoroisopropylidene)diphthalic acid, 9,9-bis(trifluoromethyl)-9H-xanthene-2,3,6,7-tetracarboxylic acid, 1,4-ditrifluoromethylpyromellitic acid, etc.;

[0058] Specific examples of the carboxylic acid ester compound include compounds in which at least one carboxy group in the specific examples of the aforementioned carboxylic acid compound is substituted with an ester group. Examples of the carboxylic acid ester compound include half-esterified compounds represented by the following general formulas (B-1) to (B-6).

[0059] [Chemical formula]

[0060] R in the general formulas (B-1) to (B-6) is an alkyl group having 1 to 6 carbon atoms. Among them, a methyl group, an ethyl group, a propyl group, or a butyl group is preferable, and an ethyl group or a propyl group is more preferable.

[0061] The half-esterified compound can be produced, for example, by mixing a carboxylic anhydride, which is an anhydride of the aforementioned carboxylic acid compound, with an alcohol solvent and ring-opening the carboxylic anhydride.

[0062] The content of the crosslinking agent (B) in the composition according to the present disclosure is not particularly limited. For example, the ratio (COOH / N) of the number of carboxy groups in the crosslinking agent (B) to the number of all nitrogen atoms in the compound (A) is preferably 0.1 or more and 3.0 or less, more preferably 0.3 or more and 2.5 or less, and even more preferably 0.4 or more and 2.2 or less. When COOH / N is 0.1 or more and 3.0 or less, by using the composition, a film having a crosslinked structure such as amide or imide between the compound (A) and the crosslinking agent (B) after heat treatment can be produced, and the film has excellent heat resistance and insulation properties.

[0063] As a component other than the compound (A) and the crosslinking agent (B), when further containing at least one selected from the group consisting of an aliphatic amine having a weight average molecular weight of 10,000 or more and 400,000 or less and an amine compound having a ring structure in the molecule and a weight average molecular weight of 90 or more and 600 or less, the ratio (COOH / N) of the number of carboxy groups in the crosslinking agent (B) to the total number of all nitrogen atoms contained therein and all nitrogen atoms contained in the compound (A) is preferably 0.1 or more and 3.0 or less.

[0064] (Additive (C)) The composition according to the present disclosure may contain an additive (C) in addition to the aforementioned compound (A), crosslinking agent (B), and polar solvent (D). Examples of the additive (C) include an acid (C-1) having a carboxy group and a weight average molecular weight of 46 or more and 195 or less, and a base (C-2) having a nitrogen atom and a weight average molecular weight of 17 or more and 120 or less.

[0065] The acid (C-1) is an acid having a carboxy group and a weight average molecular weight of 46 or more and 195 or less. When the composition according to the present disclosure contains the acid (C-1) as the additive (C), it is presumed that the aggregation due to the association of the compound (A) and the crosslinking agent (B) is suppressed by the formation of an ionic bond between the amino group in the compound (A) and the carboxy group in the acid (C-1). More specifically, it is presumed that the interaction (for example, electrostatic interaction) between the ammonium ion derived from the amino group in the compound (A) and the carboxylate ion derived from the carboxy group in the acid (C-1) is stronger than the interaction between the ammonium ion derived from the amino group in the compound (A) and the carboxylate ion derived from the carboxy group in the crosslinking agent (B), so that the aggregation is suppressed. It should be noted that the present disclosure is not limited by the above presumption.

[0066] The acid (C-1) is not particularly limited as long as it has a carboxy group and a weight average molecular weight of 46 or more and 195 or less, and examples thereof include monocarboxylic acid compounds, dicarboxylic acid compounds, oxydicarboxylic acid compounds, and the like. More specifically, examples of the acid (C-1) include formic acid, acetic acid, malonic acid, oxalic acid, citric acid, benzoic acid, lactic acid, glycolic acid, glyceric acid, butyric acid, methoxyacetic acid, ethoxyacetic acid, phthalic acid, terephthalic acid, picolinic acid, salicylic acid, 3,4,5-trihydroxybenzoic acid, and the like.

[0067] The content of the acid (C-1) in the composition according to the present disclosure is not particularly limited. For example, the ratio (COOH / N) of the number of carboxy groups in the acid (C-1) to the total number of nitrogen atoms in the compound (A) is preferably 0.01 or more and 10 or less, more preferably 0.02 or more and 6 or less, and still more preferably 0.5 or more and 3 or less. When further containing at least one selected from the group consisting of an aliphatic amine having a weight average molecular weight of 10,000 or more and 400,000 or less and an amine compound having a ring structure in the molecule and a weight average molecular weight of 90 or more and 600 or less as components other than the compound (A) and the crosslinking agent (B), the ratio (COOH / N) of the number of carboxy groups in the acid (C-1) to the total number of nitrogen atoms contained in these and the total number of nitrogen atoms contained in the compound (A) is preferably 0.01 or more and 10 or less.

[0068] Base (C-2) is a base having a nitrogen atom and a weight average molecular weight of 17 or more and 120 or less. By including base (C-2) as additive (C) in the composition according to the present disclosure, it is presumed that aggregation due to the association of compound (A) and crosslinking agent (B) is suppressed by the formation of an ionic bond between the carboxy group in crosslinking agent (B) and the amino group in base (C-2). More specifically, it is presumed that the interaction between the carboxylate ion derived from the carboxy group in crosslinking agent (B) and the ammonium ion derived from the amino group in base (C-2) is stronger than the interaction between the ammonium ion derived from the amino group in compound (A) and the carboxylate ion derived from the carboxy group in crosslinking agent (B), and thus aggregation is suppressed. It should be noted that the present disclosure is not limited by the above presumption at all.

[0069] Base (C-2) is not particularly limited as long as it is a compound having a nitrogen atom and a weight average molecular weight of 17 or more and 120 or less, and examples thereof include monoamine compounds and diamine compounds. More specifically, examples of base (C-2) include ammonia, ethylamine, ethanolamine, diethylamine, triethylamine, ethylenediamine, N-acetylethylenediamine, N-(2-aminoethyl)ethanolamine, N-(2-aminoethyl)glycine, and the like.

[0070] The content of base (C-2) in the composition according to the present disclosure is not particularly limited. For example, the ratio (N / COOH) of the number of nitrogen atoms in base (C-2) to the number of carboxy groups in crosslinking agent (B) is preferably 0.5 or more and 5 or less, and more preferably 0.9 or more and 3 or less.

[0071] (Other components) The composition according to the present disclosure preferably has a sodium content and a potassium content of 10 mass ppb or less on an elemental basis, respectively. If the sodium or potassium content is 10 mass ppb or less on an elemental basis, it is possible to suppress the occurrence of disadvantages in the electrical characteristics of semiconductor devices such as malfunction of transistors.

[0072] The composition according to the present disclosure may further contain at least one selected from the group consisting of an aliphatic amine having a weight average molecular weight of 10,000 or more and 400,000 or less, and an amine compound having a weight average molecular weight of 90 or more and 600 or less and having a ring structure in the molecule. The aliphatic amine having a weight average molecular weight of 10,000 or more and 400,000 or less preferably has a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom. Specific examples of the aliphatic amine having a weight average molecular weight of 10,000 or more and 400,000 or less include polyalkyleneimines which are polymers of alkyleneimines such as ethyleneimine, propyleneimine, butyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, octyleneimine, trimethyleneimine, tetramethyleneimine, pentamethyleneimine, hexamethyleneimine, octamethyleneimine; polyallylamine; polyacrylamide.

[0073] Polyethyleneimine (PEI) can be produced by known methods described in, for example, Japanese Patent Publication No. 43-8828, Japanese Patent Publication No. 49-33120, Japanese Unexamined Patent Application Publication No. 2001-2123958, International Publication No. 2010 / 137711, etc. Other polyalkyleneimines can also be produced in the same manner as polyethyleneimine.

[0074] The aliphatic amine having a weight average molecular weight of 10,000 or more and 400,000 or less is also preferably a derivative of the above-mentioned polyalkyleneimine (a polyalkyleneimine derivative; particularly preferably a polyethyleneimine derivative). The polyalkyleneimine derivative is not particularly limited as long as it is a compound that can be produced using the above polyalkyleneimine. Specifically, examples include polyalkyleneimine derivatives obtained by introducing an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) or an aryl group into polyalkyleneimine, and polyalkyleneimine derivatives obtained by introducing a crosslinkable group such as a hydroxyl group into polyalkyleneimine. These polyalkyleneimine derivatives can be produced by the methods usually carried out using the above polyalkyleneimine. Specifically, for example, they can be produced in accordance with the methods described in JP-A-6-016809 and the like.

[0075] Also, as the polyalkyleneimine derivative, a highly branched polyalkyleneimine obtained by improving the degree of branching of polyalkyleneimine by reacting a cationic functional group-containing monomer with polyalkyleneimine is also preferable. Examples of the method for obtaining a highly branched polyalkyleneimine include a method of reacting a cationic functional group-containing monomer with a polyalkyleneimine having a plurality of secondary nitrogen atoms in the skeleton and substituting at least a part of the plurality of secondary nitrogen atoms with the cationic functional group-containing monomer, and a method of reacting a cationic functional group-containing monomer with a polyalkyleneimine having a plurality of primary nitrogen atoms at the terminal and substituting at least a part of the plurality of primary nitrogen atoms with the cationic functional group-containing monomer. Examples of the cationic functional group introduced to improve the degree of branching include an aminoethyl group, an aminopropyl group, a diaminopropyl group, an aminobutyl group, a diaminobutyl group, a triaminobutyl group, etc. From the viewpoint of reducing the cationic functional group equivalent and increasing the cationic functional group density, an aminoethyl group is preferable.

[0076] The aliphatic amine having a weight average molecular weight of 10,000 or more and 400,000 or less preferably has a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom. Here, when the aliphatic amine contains a primary nitrogen atom, the ratio of the primary nitrogen atom in all the nitrogen atoms in the aliphatic amine is preferably 20 mol% or more, more preferably 25 mol% or more, and still more preferably 30 mol% or more. Further, the aliphatic amine may have a cationic functional group containing a primary nitrogen atom and not containing a nitrogen atom other than the primary nitrogen atom (for example, a secondary nitrogen atom, a tertiary nitrogen atom).

[0077] Further, when the aliphatic amine contains a secondary nitrogen atom, the proportion of the secondary nitrogen atom in all the nitrogen atoms in the aliphatic amine is preferably 5 mol% or more and 50 mol% or less, and more preferably 10 mol% or more and 45 mol% or less.

[0078] In addition to the primary nitrogen atom and the secondary nitrogen atom, the aliphatic amine may contain a tertiary nitrogen atom. When the aliphatic amine contains a tertiary nitrogen atom, the proportion of the tertiary nitrogen atom in all the nitrogen atoms in the aliphatic amine is preferably 20 mol% or more and 50 mol% or less, and more preferably 25 mol% or more and 45 mol% or less.

[0079] Also, the polyethyleneimine and its derivatives may be commercially available ones. For example, they can be appropriately selected and used from the polyethyleneimine and its derivatives commercially available from Nippon Shokubai Co., Ltd., BASF, MP-Biomedicals, etc.

[0080] Examples of the amine compound having a ring structure in the molecule and a weight average molecular weight of 90 or more and 600 or less include alicyclic amines, aromatic ring amines, heterocyclic amines, etc. It may have a plurality of ring structures in the molecule, and the plurality of ring structures may be the same or different. As the amine compound having a ring structure, a compound having an aromatic ring is more preferable because a more stable compound can be easily obtained thermally.

[0081] In addition, as the amine compound having a ring structure in the molecule and a weight average molecular weight of 90 or more and 600 or less, a compound having a primary amino group is preferable because it easily forms a thermal crosslinked structure such as imide, imide amide, or amide together with the crosslinking agent (B) and can enhance heat resistance. Further, as the aforementioned amine compound, a diamine compound having two primary amino groups, a triamine compound having three primary amino groups, etc. are preferable because they can easily increase the number of thermal crosslinked structures such as imide, imide amide, or amide together with the crosslinking agent (B) and can further enhance heat resistance.

[0082] Examples of the alicyclic amine include cyclohexylamine, dimethylaminocyclohexane, and the like. Examples of the aromatic ring amine include diaminodiphenyl ether, xylenediamine (preferably para-xylenediamine), diaminobenzene, diaminotoluene, methylenedianiline, dimethyldiaminobiphenyl, bis(trifluoromethyl)diaminobiphenyl, diaminobenzophenone, diaminobenzanilide, bis(aminophenyl)fluorene, bis(aminophenoxy)benzene, bis(aminophenoxy)biphenyl, dicarboxydiaminodiphenylmethane, diaminoresorcin, dihydroxybenzidine, diaminobenzidine, 1,3,5-triaminophenoxybenzene, 2,2'-dimethyldiaminobenzidine, tris(4-aminophenyl)amine, and the like. Examples of the heterocyclic ring of the heterocyclic amine include a heterocyclic ring containing a sulfur atom as a hetero atom (e.g., thiophene ring), or a heterocyclic ring containing a nitrogen atom as a hetero atom (e.g., 5-membered rings such as pyrrole ring, pyrrolidine ring, pyrazole ring, imidazole ring, triazole ring; 6-membered rings such as isocyanuric ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, triazine ring; condensed rings such as indole ring, indoline ring, quinoline ring, acridine ring, naphthyridine ring, quinazoline ring, purine ring, quinoxaline ring, etc.). For example, examples of the heterocyclic amine having a nitrogen-containing heterocyclic ring include melamine, ammeline, melam, melem, tris(4-aminophenyl)amine, and the like. Furthermore, examples of the amine compound having both a heterocyclic ring and an aromatic ring include N2,N4,N6-tris(4-aminophenyl)-1,3,5-triazine-2,4,6-triamine, and the like.

[0083] Regarding the composition according to the present disclosure, when selectivity of plasma etching resistance is required (e.g., for gap filling materials, embedded insulating film applications), a metal alkoxide represented by the general formula (I) may be contained. R1 n M(OR2) m-n···(I) (In the formula, R1 is a non-hydrolyzable group, R2 is an alkyl group having 1 to 6 carbon atoms, M represents at least one metal atom selected from the group of metal atoms of Ti, Al, Zr, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La, Nd, and In, m is the valence of the metal atom M and is 3 or 4, n is an integer of 0 to 2 when m is 4, and is 0 or 1 when m is 3. When there are a plurality of R1, each R1 may be the same as or different from each other. When there are a plurality of OR2, each OR2 may be the same as or different from each other.)

[0084] When insulation is required for the film produced from the composition according to the present disclosure (for example, for the use of an insulating film for a silicon through via, for the use of a buried insulating film), in order to improve insulation or mechanical strength, tetraethoxysilane, tetramethoxysilane, bistriethoxysilylethane, bistriethoxysilylmethane, bis(methyldiethoxysilyl)ethane, 1,1,3,3,5,5 - hexaethoxy - 1,3,5 - trisilacyclohexane, 1,3,5,7 - tetramethyl - 1,3,5,7 - tetrahydroxylcyclosiloxane, 1,1,4,4 - tetramethyl - 1,4 - diethoxydisilylethylene, 1,3,5 - trimethyl - 1,3,5 - trimethyl - 1,3,5 - triethoxy - 1,3,5 - trisilacyclohexane may be mixed. Further, in order to improve the hydrophobicity of the insulating film, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, etc. may be mixed. These compounds may be mixed for the control of etching selectivity.

[0085] The composition according to the present disclosure may contain a solvent other than the polar solvent (D), and examples thereof include normal hexane.

[0086] Also, the composition according to the present disclosure may contain phthalic acid, benzoic acid, etc., or derivatives thereof, for example, for improving electrical properties. Also, the composition according to the present disclosure may contain benzotriazole or a derivative thereof, for example, for suppressing the corrosion of copper.

[0087] Although the pH of the composition according to the present disclosure is not particularly limited, it is preferably 2.0 or more and 12.0 or less.

[0088] (Use of the composition) The use of the composition according to the present disclosure is not particularly limited, and it can be used for various applications including the manufacture of semiconductor devices. For example, it may be used to form a layer on or between substrates, or it may be used in the manufacture of the laminate described later. Among them, the composition according to the present disclosure is suitable as a composition used in the manufacture of semiconductor members. In addition, the composition according to the present disclosure can be suitably used as an adhesive or a composition for forming an adhesive layer.

[0089] 〔Laminate〕 The laminate according to the present disclosure has an adhesive layer formed from the composition according to the present disclosure and a substrate. The adhesive layer is disposed, for example, in contact with the surface of the substrate and joined to the substrate. As described above, since the adhesive layer obtained from the composition according to the present disclosure has a low coefficient of thermal expansion, strain caused by the difference in the coefficient of thermal expansion from the substrate is less likely to occur at the joint surface, and the reliability of the laminate is excellent.

[0090] The number of substrates included in the laminate is not particularly limited, and may be one or a plurality. When there are two or more substrates, their materials may be the same or different. As the substrate, a substrate having a coefficient of thermal expansion equal to or smaller than that of the adhesive layer is preferable.

[0091] Examples of the material of the substrate include inorganic materials, organic materials, and composites thereof. Specific examples of the inorganic material include semiconductors such as Si, InP, GaN, GaAs, InGaAs, InGaAlAs, SiGe, and SiC; borosilicate glass (Pyrex (registered trademark)), quartz glass (SiO 2 ), sapphire (Al 2 O 3 ), ZrO 2 , Si 3 N4 , AlN, MgAl 2 O 4 , and other oxides, carbides or nitrides; BaTiO 3 , LiNbO 3 , SrTiO 3 , LiTaO 3 , and other piezoelectric or dielectric materials; diamond; metals such as Al, Ti, Fe, Cu, Ag, Au, Pt, Pd, Ta, Nb, etc.; carbon, etc. Specific examples of the organic material (i.e., resin material) include polydimethylsiloxane (PDMS), epoxy resin, phenolic resin, polyimide, benzocyclobutene resin, polybenzoxazole, etc. For example, when the laminate includes a first substrate and a second substrate, the first substrate, the adhesive layer, and the second substrate may be laminated in this order. And, among the first substrate and the second substrate, one may be a substrate made of semiconductor (i.e., semiconductor substrate), and the other may be a substrate made of resin material (i.e., resin substrate).

[0092] Each material is mainly used for the following applications. Si is used for semiconductor memory, LSI lamination, CMOS image sensor, MEMS encapsulation, optical device, LED, etc.; SiO 2 is used for semiconductor memory, LSI lamination, MEMS encapsulation, microchannel, CMOS image sensor, optical device, LED, etc.; BaTiO 3 , LiNbO 3 , SrTiO 3 , LiTaO 3 are used for surface acoustic wave devices; PDMS is used for microchannel; InGaAlAs, InGaAs, InP are used for optical devices; InGaAlAs, GaAs, GaN are used for LED, etc.

[0093] The surface of the substrate (at least the surface in contact with the adhesive layer) preferably has at least one selected from the group consisting of a hydroxy group, an epoxy group, a carboxy group, an amino group, and a mercapto group. Thereby, the bonding strength with the layer of the cured product of the composition can be made stronger.

[0094] A surface having a hydroxy group can be obtained by performing surface treatment such as plasma treatment, chemical treatment, or ozone treatment on the surface of the substrate.

[0095] A surface having an epoxy group, a carboxy group, an amino group, or a mercapto group can be obtained by performing surface treatment using a silane coupling having an epoxy group, a carboxy group, an amino group, or a mercapto group on the surface of the substrate.

[0096] At least one selected from the group consisting of a hydroxy group, an epoxy group, a carboxy group, an amino group, and a mercapto group is preferably in a state of being bonded to an element contained in the substrate, more preferably in a state of being bonded to at least one element selected from the group consisting of Si, Al, Ti, Zr, Hf, Fe, Ni, Cu, Ag, Au, Ga, Ge, Sn, Pd, As, Pt, Mg, In, Ta, and Nb, and still more preferably in a state of a silanol group (Si-OH group) containing a hydroxy group.

[0097] The substrate may have electrodes on at least one side (preferably the side facing the adhesive layer).

[0098] The thickness of the substrate is preferably 1 μm to 1 mm, and more preferably 2 μm to 900 μm. When there are a plurality of substrates, the above thickness is the thickness of each substrate, which may be the same or different.

[0099] The shape of the substrate is not particularly limited. For example, when the substrate is a silicon substrate, it may be a silicon substrate on which an interlayer insulating layer (Low-k film) is formed. The substrate may have fine grooves (recesses), fine through-holes, etc.

[0100] The laminate according to the present disclosure may further include a substrate that is not in contact with the adhesive layer. Preferred materials and other aspects of the substrate that is not in contact with the adhesive layer are the same as those of the substrate described above.

[0101] The thickness of the adhesive layer is not particularly limited and can be set according to the application. For example, it may be 0.1 nm to 20,000 nm, may be 0.5 nm to 10,000 nm, may be 5 nm to 5,000 nm, or may be 5 nm to 3,000 nm.

[0102] (Examples of the laminated structure of the laminate) The laminate can be used in various applications including components of semiconductor devices. Examples of the laminated structure of the substrate laminate in each application are shown below. For MEMS packaging; Si / adhesive layer / Si, SiO 2 / adhesive layer / Si, SiO 2 / adhesive layer / SiO 2 , Cu / adhesive layer / Cu, For microchannels; PDMS / adhesive layer / PDMS, PDMS / adhesive layer / SiO 2 , For CMOS image sensors; SiO 2 / adhesive layer / SiO 2 , Si / adhesive layer / Si, SiO 2 / adhesive layer / Si, For silicon through vias (TSV); SiO 2 (with Cu electrodes) / adhesive layer / SiO 2 (with Cu electrodes), For memories, LSIs; SiO 2 / adhesive layer / SiO 2 , For optical devices; (InGaAlAs, InGaAs, InP, GaAs) / adhesive layer / Si, For LEDs; (InGaAlAs, GaAs, GaN) / adhesive layer / Si, (InGaAlAs, GaAs, GaN) / adhesive layer / SiO 2 , (InGaAlAs, GaAs, GaN) / adhesive layer / (Au, Ag, Al), (InGaAlAs, GaAs, GaN) / adhesive layer / sapphire, For surface acoustic wave devices; (BaTiO 3 , LiNbO 3 , SrTiO 3 , LiTaO 3 ) / adhesive layer / (MgAl 2 O 4 , SiO 2 , Si, Al 2 O 3 ).

[0103] In addition to the above-described configuration, the laminate may include a cured product formed as an insulating film on the surface of the substrate, in the recess formed on the surface, in the through-hole, etc. The adhesive layer may be formed temporarily. For example, it can also be used for applications that are temporarily formed on a substrate in the manufacturing process of a semiconductor device such as a sacrificial film and removed in a subsequent process.

[0104] [Method for manufacturing a laminate] The method for manufacturing a laminate according to the present disclosure includes a step A of applying the composition according to the present disclosure to a first substrate, and a step B of heating the composition applied to the first substrate to form an adhesive layer.

[0105] The details and preferred embodiments of the first substrate used in the above method are the same as the details and preferred embodiments of the substrate described with respect to the above-described laminate.

[0106] (Step A) The method for carrying out step A is not particularly limited. For example, the method for forming the composition according to the present disclosure is not particularly limited and may be carried out by a commonly used method. For example, dipping method, spraying method, spin coating method, bar coating method, etc. may be mentioned. Among these, when forming a layer having a micron-sized thickness, it is preferable to use the bar coating method, and when forming a layer having a nano-sized (several nm to several hundred nm) thickness, it is preferable to use the spin coating method.

[0107] The method for forming a layer by the spin coating method is not particularly limited. For example, a method can be used in which a solution is dropped onto the surface of a substrate while rotating the substrate with a spin coater, and then the rotation speed of the substrate is increased to dry it. Various conditions such as the rotation speed of the substrate, the dropping amount and dropping time of the solution, and the rotation speed of the substrate during drying are not particularly limited, and can be appropriately adjusted while considering the thickness of the layer to be formed and the like.

[0108] Further, the method for manufacturing a laminate according to the present disclosure preferably includes a step of removing the composition applied to the edge portion of the substrate with an organic solvent after step A and before step B. There is no particular limitation on the organic solvent, and a known edge rinse solution can be used. Among them, from the viewpoint of edge removability, it is preferably included in alcohol, more preferably included in monoalcohol, still more preferably included in 1-methoxy-2-propanol, and particularly preferably included in 1-methoxy-2-propanol and propylene glycol monomethyl ether acetate.

[0109] (Step B) In step B, the composition applied to the first substrate is heated and cured. Specifically, at least the compound (A) and the crosslinking agent (B) contained in the composition are reacted to form a layer (adhesive layer) containing the reaction products thereof. Examples of the method for reacting the compound (A) and the crosslinking agent (B) include heating at a temperature at which these components react (for example, 70°C to 450°C). The temperature is preferably 100°C to 450°C, more preferably 100°C to 400°C, still more preferably 150°C to 350°C. Further, the temperature may be 70°C to 280°C, may be 80°C to 250°C, or may be 90°C to 200°C.

[0110] The pressure during heating is not particularly limited. For example, it may be carried out at an absolute pressure exceeding (17 Pa) and below atmospheric pressure. The pressure is preferably 1,000 Pa or more and below atmospheric pressure, more preferably 5,000 Pa or more and below atmospheric pressure, and still more preferably 10,000 Pa or more and below atmospheric pressure.

[0111] The heating method is not particularly limited and can be carried out by a normal method using a furnace or a hot plate. As the furnace, for example, SPX-1120 manufactured by APEX, VF-1000LP manufactured by Koyo Thermo System Co., Ltd., etc. can be used. Also, the heating in the heating step may be carried out in an air atmosphere or in an inert gas (nitrogen gas, argon gas, helium gas, etc.) atmosphere.

[0112] The heating time is not particularly limited and may be, for example, 3 hours or less, or 1 hour or less. The lower limit of the heating time is not particularly limited and may be, for example, 30 seconds or more, 3 minutes or more, or 5 minutes or more.

[0113] When heating at 70°C to 250°C, the heating time may be 300 seconds or less, 200 seconds or less, 120 seconds or less, or 80 seconds or less. In this case, the heating time may be 10 seconds, 20 seconds or more, or 30 seconds or more.

[0114] The heating temperature may be constant or variable. For example, it may include a step of heating in a low-temperature heating step (70°C to 250°C) and a step of heating at a higher temperature (100°C to 450°C).

[0115] For the purpose of shortening the time of the heating step, ultraviolet irradiation may be performed on the composition applied on the substrate. As the ultraviolet light, ultraviolet light with a wavelength of 170 nm to 230 nm, excimer light with a wavelength of 222 nm, excimer light with a wavelength of 172 nm, etc. are preferable. Also, it is preferable to perform ultraviolet irradiation in an inert gas atmosphere.

[0116] (Lamination step) The method for manufacturing a laminate according to the present disclosure preferably further includes a step of laminating a second substrate on the adhesive layer formed in step B.

[0117] (Pressing step) In the method for manufacturing a laminate according to the present disclosure, it is preferable to include a pressing step of pressing the laminate simultaneously with or after step B. By pressing the laminate, the area of contact between the substrate and the adhesive layer increases, and the bonding strength tends to be further improved.

[0118] When pressing the laminate while heating it, the pressing pressure is preferably 0.1 MPa to 50 MPa, more preferably 0.1 MPa to 10 MPa, and still more preferably 0.1 MPa to 5 MPa. As the pressing device, for example, TEST MINI PRESS manufactured by Toyo Seiki Seisakusho Co., Ltd. may be used. When pressing the laminate while heating it, the heating temperature is preferably 100°C to 450°C, more preferably 100°C to 400°C, and still more preferably 150°C to 350°C. Thereby, when a semiconductor circuit is formed on the substrate, damage to the semiconductor circuit tends to be suppressed.

[0119] When pressing the laminate after heating it, the pressing pressure is preferably 0.1 MPa to 50 MPa, and more preferably 0.1 MPa to 10 MPa. As the pressing device, for example, TEST MINI PRESS manufactured by 5 Seiki Seisakusho Co., Ltd. may be used. Also, the pressurization time is not particularly limited, but can be, for example, 0.5 seconds to 1 hour.

[0120] When pressing the laminate after heating it, the temperature is preferably 10°C or more and less than 100°C, more preferably 10°C to 70°C, still more preferably 15°C to 50°C, and particularly preferably 20°C to 30°C. The temperature refers to the temperature of the surface of the substrate to which compound (A), compound (B), and compound (C) are applied.

[0121] (Post-heating step) The method for manufacturing a laminate according to the present disclosure may include a post-heating step of further heating the laminate after step B. By including the post-heating step, the bonding strength tends to be more excellent.

[0122] The heating temperature in the post-heating step is preferably 100°C to 450°C, more preferably 150°C to 420°C, and even more preferably 150°C to 400°C. The pressure during the post-heating step may be more than 17 Pa absolute pressure and below atmospheric pressure, preferably 1,000 Pa or more and below atmospheric pressure, more preferably 5,000 Pa or more and below atmospheric pressure, and even more preferably 10,000 Pa or more and below atmospheric pressure. In the post-heating step, it is preferable not to press the laminate.

Examples

[0123] Hereinafter, the present disclosure will be specifically described by way of examples, but the present disclosure is not limited to these examples. Hereinafter, as the "water", ultrapure water (Milli-Q water manufactured by Millipore, resistance 18 MΩ·cm or less at 25°C) was used.

[0124] <Preparation of Composition (Adhesive)> (Comparative Example 1) As a material for forming an organic substance-containing layer, 50% by mass of 3-aminopropyldiethoxymethylsilane (3APDES, the following structure) and 50% by mass of water were blended to obtain Solution A containing a hydrolyzate of 3APDES. Solution B containing 70% by mass of oxydiphthalic acid half ester (Y is O and R is an ethyl group in the above formula (B-2)) and 30% by mass of ethanol was obtained. 24 g of Solution A, 18 g of Solution B, 20 g of 1-propanol, and 38 g of water were blended to prepare a solution containing a material for forming an organic substance-containing layer.

[0125]

Chemical Formula

[0126] (Example 1) A solution B containing 70% by mass of oxy-diphthalic acid half-ester (eheODPA) and 30% by mass of ethanol was obtained. EheODPA is a compound in which Y is O and R is an ethyl group in the above formula (B-2), which was produced by adding oxy-diphthalic anhydride (ODPA: the following structure) to ethanol and refluxing for 5 hours in an oil bath heated to 90 °C to completely dissolve the raw material powder. By proton nuclear magnetic resonance spectroscopy (NMR), it was confirmed that an ester group was formed in the produced eheODPA. 2 g of 3-aminopropyldiethoxymethylsilane (3APDES), 1.56 g of solution B, and 16 g of propylene glycol monomethyl ether (1-methoxy-2-propanol, PGME) were blended to prepare a solution containing a material for forming an organic substance-containing layer.

[0127] [Chemical formula]

[0128] [Preparation of substrate] For the evaluation of the edge cutting property of a silicon wafer, a 4-inch silicon wafer manufactured by Tonic Corporation was prepared. For the evaluation of the coating property on a resin substrate, an epoxy resin composition (R4121-2C) manufactured by Nagase ChemteX Corporation was molded under the following conditions to obtain an epoxy resin substrate. Mold: 125 °C × 400 seconds Post-mold cure: 150 °C × 30 minutes

[0129] [Coating and evaluation] (1) Evaluation of edge cutting property for silicon wafer Each of the above-prepared compositions (adhesives) was spin-coated on a silicon wafer. After drying the solvent, an edge rinse solution of 50% by mass of PGME and 50% by mass of propylene glycol monomethyl ether acetate (PGMEA) was ejected from the nozzle attached to the apparatus and washed and dried on the outer peripheral portion 5 mm of the spinning wafer. Then, an adhesive layer was formed by heating at 200 °C for 1 hour under a nitrogen atmosphere. Regarding the adhesive layer formed above, in order to measure the step difference between the edge-cut portion and other portions, measurements were taken using a stylus profilometer (DektakXT manufactured by Bruker) under the following conditions. Centering on the step portion of the edge cut, the film thickness of 2,500 μm at the edge cut portion and the film thickness at a location of 2,500 μm in the non-edge cut portion were measured. The removal rate was calculated from the film thickness difference between the edge cut portion and the non-edge cut portion. The results are shown in Table 1. Measured height range: 6.5 μm Type of needle: Radius 2.0 μm Touch pressure: 3 mg Measurement distance: 5,000 μm Measurement time: 100 sec

[0130] (2) Evaluation of coatability on resin substrate On the epoxy resin substrate (4 cm square) prepared above, each composition (adhesive) prepared above was applied by spin coating and dried at 150 °C for 1 minute. Thereafter, an adhesive layer was formed by heating at 200 °C for 1 hour under a nitrogen atmosphere. The wetting spread of the liquid on the 4 cm square substrate was visually observed to judge the coatability. The evaluation criteria are shown below. The results are also shown in Table 2. A: Uniformly wets and spreads to the edge B: There are areas such as repellency, and it does not uniformly wet and spread to the edge

[0131]

Table 1

[0132]

Table 2

[0133] As shown in Table 1, the composition of Example 1 was excellent in edge removability by an organic solvent. Also, as shown in Table 2, the composition of Example 1 was excellent in coatability.

Claims

1. A compound (A) having a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom and an Si—O bond, A crosslinking agent (B) having three or more —C(═O)OX groups (X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the molecule, and among the three or more —C(═O)OX groups, one or more and six or less are —C(═O)OH groups, A polar solvent (D), Comprising, wherein the proportion of water in the polar solvent (D) is 30% by mass or less based on the total mass of the polar solvent (D), Composition.

2. The composition according to claim 1, wherein the polar solvent (D) contains alcohol.

3. The composition according to claim 2, wherein the proportion of alcohol in the polar solvent (D) is 70% by mass or more based on the total mass of the polar solvent (D).

4. The composition according to claim 1, wherein the weight average molecular weight of the crosslinking agent (B) is 200 or more and 600 or less.

5. The composition according to claim 1, wherein the crosslinking agent (B) has a ring structure in the molecule.

6. The composition according to claim 5, wherein the ring structure is at least one of a benzene ring and a naphthalene ring.

7. The composition according to claim 1, which is used for the production of semiconductor members.

8. A laminate having an adhesive layer formed from the composition according to any one of claims 1 to 7 and a substrate.

9. The laminate according to claim 8, wherein the substrate is a semiconductor substrate or a resin substrate.

10. The substrate includes a first substrate and a second substrate, The laminate according to claim 8, wherein the first substrate, the adhesive layer, and the second substrate are laminated in this order.

11. The laminate according to claim 8, wherein one of the first substrate and the second substrate is a semiconductor substrate and the other is a resin substrate.

12. A method for producing a laminate, comprising: step A of applying the composition according to any one of claims 1 to 7 to a first substrate; and step B of heating the composition applied to the first substrate to form an adhesive layer.

13. The method for producing a laminate according to claim 12, wherein the first substrate is a semiconductor substrate or a resin substrate.

14. The method for producing a laminate according to claim 12, further comprising a step of laminating a second substrate on the adhesive layer formed in step B.

15.

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