Adhesive composition and laminate

Abstract

Provided is an adhesive composition that contains: a compound (A) having an Si-O bond and a cationic functional group including at least one of a primary nitrogen atom and a secondary nitrogen atom; a crosslinking agent (B) which has a weight average molecular weight of 200-600 and has three or more -C(=O)OX groups in the molecule, where X denotes a hydrogen atom or an alkyl group having 1-6 carbon atoms, and one to six of the three or more -C(=O)OX groups is a -C(=O)OH group; and an additive (D) having a structure represented by formula (a) and a structure represented by formula (b). Also provided is a laminate.

Description

Adhesive composition and laminate

[0001] The present disclosure relates to an adhesive composition and a laminate.

[0002] As electronic devices become smaller, lighter, and more powerful, there is a demand for higher integration of semiconductor chips and the like, in which electrodes are arranged on a substrate. However, it is difficult to fully meet the demand for higher integration simply by miniaturizing circuits. Therefore, in recent years, a method for achieving higher integration by stacking multiple semiconductor substrates to form a multilayer three-dimensional structure has been proposed. Proposed methods for stacking substrates (wafers), chips, etc. (hereinafter sometimes referred to as "substrates, etc.") include a method of directly bonding substrates together (fusion bonding) and a method of bonding substrates together using an adhesive. For example, Patent Document 1 (JP 2016-47895 A) describes an adhesive that does not exhibit adhesive properties during the stacking process of semiconductor chips, etc., but softens when heated to exhibit adhesive properties and then quickly hardens.

[0003] Patent Document 1: Japanese Patent Application Laid-Open No. 2016-47895

[0004] In the examples of Patent Document 1, a laminate is produced by bonding a glass plate and a silicon plate using an adhesive, but no examples of using an adhesive to bond inorganic and organic materials are described. Furthermore, in recent years, there has been a trend toward increasingly high integration of semiconductor chips. In addition to substrates made of inorganic materials, the use of substrates made of organic materials such as thermosetting resins (hereinafter also referred to as organic substrates) has been considered. When using inorganic substrates, the substrate may be surface-treated with an organic solvent or a so-called leveling agent may be added to the adhesive composition to improve the adhesive's wettability. On the other hand, surface treatment of organic substrates with an organic solvent or the like is undesirable due to the risk of damaging the surface of the resin substrate. Furthermore, known leveling agents added to adhesive layers do not provide sufficient wettability to organic substrates, and, particularly when forming thin resin layers, may result in an insufficient coating film and the generation of foreign matter on the coating film surface. One embodiment of the present disclosure aims to provide an adhesive composition capable of forming a uniform coating film even when used with an organic substrate, and a laminate using this adhesive composition.

[0005] Specific means for solving the above problems include the following aspects: <1> An adhesive composition comprising: (A) a compound having a cationic functional group containing at least one selected from a primary nitrogen atom and a secondary nitrogen atom and an Si—O bond; (B) a crosslinking agent having three or more —C(═O)OX groups in the molecule, where X represents a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms, and one to six of the three or more —C(═O)OX groups are —C(═O)OH groups, and having a weight average molecular weight of 200 to 600; and (D) an additive having a structure represented by the following formula (a) and a structure represented by the following formula (b):

[0006]

[0007]

[0008] <2> The adhesive composition according to <1>, wherein the content of the additive (D) is 0.1 parts by mass or more and 7 parts by mass or less, relative to 100 parts by mass of the total content of the compound (A) and the crosslinking agent (B). <3> The adhesive composition according to <1> or <2>, further comprising a polar solvent (C). <4> The adhesive composition according to <3>, wherein the polar solvent (C) contains at least water. <5> The adhesive composition according to <3> or <4>, wherein the content of the additive (D) is 0.01 parts by mass or more and 0.8 parts by mass or less, relative to 100 parts by mass of the total content of the compound (A), the crosslinking agent (B), and the polar solvent (C).

[0009] <6> A laminate comprising an inorganic material layer, an organic material layer, and an adhesive layer disposed between the inorganic material layer and the organic material layer and bonding the inorganic material layer to the organic material layer, wherein the adhesive layer comprises the adhesive composition according to claim 1 or 2. <7> A laminate comprising: an inorganic material layer; an organic material layer; and an adhesive layer disposed between the inorganic material layer and the organic material layer and bonding the inorganic material layer to the organic material layer, wherein the adhesive layer comprises: a reaction product of a compound (A) having a cationic functional group containing at least one selected from a primary nitrogen atom and a secondary nitrogen atom and a Si—O bond; and a crosslinking agent (B) having three or more —C(═O)OX groups (X is a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms) in the molecule, wherein one to six of the three or more —C(═O)OX groups are —C(═O)OH groups, and having a weight-average molecular weight of 200 to 600; and an additive (D) having a structure represented by the following formula (a) and a structure represented by the following formula (b):

[0010]

[0011]

[0012] <8> The adhesive composition according to any one of <1> to <5>, wherein the additive (D) has a structure represented by the following formula (c):

[0013]

[0014] In formula (c), R １ and R ２ each independently represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, n represents an integer of 1 to 40, m represents an integer of 1 to 30, x represents an integer of 1 to 300, and y represents an integer of 1 to 100.

[0015] According to one embodiment of the present disclosure, there are provided an adhesive composition that can form a uniform coating film even when an organic substrate is used, and a laminate using this adhesive composition.

[0016] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the upper and lower limits. In numerical ranges described in stages in the present disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in numerical ranges described in the present disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples. In the present disclosure, a "laminate" refers to a structure in which an inorganic material layer, an adhesive layer, and an organic material layer are arranged in this order, and the inorganic material layer and the organic material layer are bonded via the adhesive layer.

[0017] <Adhesive Composition> The adhesive composition of the present disclosure includes: a compound (A) having a cationic functional group containing at least one selected from 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 in the molecule, where X represents a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms, and of the three or more —C(═O)OX groups, one to six of which are —C(═O)OH groups, and having a weight average molecular weight of 200 or more and 600 or less; and an additive (D) having a structure represented by the following formula (a) and a structure represented by the following formula (b).

[0018]

[0019]

[0020] The adhesive composition contains the compound (A) and the crosslinking agent (B), improving its adhesion to inorganic substrates and its adhesive strength after heating. Furthermore, the adhesive composition contains the additive (D), improving its affinity for resin substrates. The mechanism by which the affinity for resin substrates is improved is unclear, but is presumed to be as follows: Additive (D) containing a siloxane bond represented by formula (a) as a partial structure improves adhesion to inorganic and organic materials. Furthermore, the presence of an ether bond represented by formula (b) causes the ether bond to be unevenly distributed toward the organic substrate in the adhesive composition, improving its affinity for organic substrates. For example, even when the adhesive composition contains a polar solvent, repelling of the adhesive composition when applied to an organic substrate is suppressed, enabling the formation of a uniform coating film. In a preferred embodiment of the present disclosure, the presence of a partial structure represented by formula (b) in the side chain of additive (D) improves the mobility of the ether bond, improving its affinity for resin substrates and resulting in superior coatability.

[0021] An example of the structure represented by formula (a) is a structure represented by the following formula (a-1).

[0022]

[0023] In formula (a-1), R ０１ and R ０２ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a group represented by the following formula (a-2):

[0024]

[0025] In formula (a-2), R １ and R ２ each independently represents a hydrogen atom or an organic group having 1 to 10 carbon atoms. １ and R ２When represents an organic group having 1 to 10 carbon atoms, examples of the organic group include an aliphatic hydrocarbon group having 1 to 10 carbon atoms and an aromatic hydrocarbon group having 1 to 10 carbon atoms. Examples of the aliphatic hydrocarbon group include an alkyl group having 1 to 5 carbon atoms, such as a methyl group or an ethyl group, and examples of the aliphatic hydrocarbon group include a phenyl group. In formula (a-2), x represents an integer of 1 to 300, preferably 1 to 280, more preferably 1 to 100, and even more preferably 1 to 50. y represents an integer of 1 to 100, preferably 1 to 90, more preferably 1 to 50, and even more preferably 1 to 20.

[0026] In formula (a-1), R ０１ and R ０２ When represents an organic group having 1 to 10 carbon atoms, examples of the organic group include an aliphatic hydrocarbon group having 1 to 10 carbon atoms and an aromatic hydrocarbon group having 1 to 10 carbon atoms. Examples of the aliphatic hydrocarbon group include an alkyl group having 1 to 5 carbon atoms, such as a methyl group and an ethyl group, and examples of the aliphatic hydrocarbon group include a phenyl group.

[0027] Among these, additive (D) may be a compound having a structure represented by the following formula (c): According to formula (c), by having a siloxane bond represented by the above formula (a) in the main chain and an ether bond represented by formula (b) in the side chain, the adhesive composition can be more easily formed into a uniform coating film on an organic substrate.

[0028]

[0029] In formula (c), R １ and R ２ R each independently represents a hydrogen atom or an organic group having 1 to 10 carbon atoms. １ and R ２ When represents an organic group having 1 to 10 carbon atoms, examples of the organic group include an aliphatic hydrocarbon group having 1 to 10 carbon atoms and an aromatic hydrocarbon group having 1 to 10 carbon atoms. More specific examples of the hydrocarbon group include alkyl groups such as a methyl group, an ethyl group, and a propyl group, and a phenyl group. Among these, from the viewpoint of improving affinity with the organic substrate, in formula (c), R １ is a hydrogen atom or a methyl group, and R ２is preferably a methyl group or an ethyl group. From the same viewpoint, in formula (c), n represents an integer of 1 to 40, preferably 1 to 38, and more preferably 1 to 10. m represents an integer of 1 to 30, preferably 1 to 29, and more preferably 1 to 10. x represents an integer of 1 to 300, preferably 1 to 280, more preferably 1 to 100, and even more preferably 1 to 50. y represents an integer of 1 to 100, preferably 1 to 90, more preferably 1 to 50, and even more preferably 1 to 20.

[0030] The weight average molecular weight of additive (D) can be in the range of 500 to 5000, preferably 700 to 3000, more preferably 800 to 2000, and even more preferably 800 to 1000. When the weight average molecular weight of additive (D) is 500 or more, the affinity for resin substrates is improved, and when it is 5000 or less, the solubility during preparation of the adhesive composition and the uniformity in the solution are improved.

[0031] In the present disclosure, the weight-average molecular weight refers to the weight-average molecular weight in terms of polyethylene glycol, measured by gel permeation chromatography (GPC) for components other than the monomer. Specifically, the weight-average molecular weight is measured using tetrahydrofuran as a developing solvent, a Shodex DET RI-101 analyzer, and an analytical column (2x PLgel 5μ MIXED-D, 7.5 x 300 mm / 40°C, manufactured by Agilent Technologies) at a flow rate of 1.0 mL / min to detect the refractive index, and polyethylene glycol / polyethylene oxide as a standard.

[0032] Below, exemplary compounds of the additive (D) and their weight average molecular weights are listed by defining each partial structure in formula (c), but the additive (D) of the present disclosure is not limited thereto. １ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ２ represents an organic group having 1 to 10 carbon atoms.

[0033]

[0034] Commercially available products of additive (D) may be used. Examples of commercially available products of additive (D) that can be used in the adhesive composition of the present disclosure include silicone surface conditioners from BYK Japan Corporation: BYK-333, BYK-307, BYK-302, BYK-325, BYK-331, BYK-342, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349, BYK-378, BYK-3455, and BYK-3456.

[0035] The adhesive composition of the present disclosure contains at least a compound (A), a crosslinking agent (B), and an additive (D). Details of the compound (A) and the crosslinking agent (B) will be described later. In the adhesive composition of the present disclosure, the content of the additive (D) is preferably 0.1 parts by mass or more and 7 parts by mass or less, relative to 100 parts by mass of the total content of the compound (A) and the crosslinking agent (B). When the content of the additive (D) is within the above range, the adhesive composition exhibits better ability to form a uniform coating film on an organic substrate. In particular, the content of the additive (D) is preferably 0.1 parts by mass or more and 7 parts by mass or less, more preferably 0.1 parts by mass or more and 5 parts by mass or less, and even more preferably 1 part by mass or more and 3 parts by mass or less, relative to 100 parts by mass of the total content of the compound (A) and the crosslinking agent (B) (hereinafter also referred to as (A+B)).

[0036] The adhesive composition of the present disclosure may further contain a polar solvent (C). By including the polar solvent (C) in the adhesive composition of the present disclosure, the environmental impact is reduced and the composition can be more easily prepared. The polar solvent (C) preferably contains at least water. Generally, when an adhesive composition contains a polar solvent (C) such as water, its affinity to organic substrates decreases, making it more likely to crater when applied to a resin substrate. However, by including the additive (D) in the adhesive composition, the occurrence of crater is suppressed, resulting in better uniform application to resin substrates. Therefore, it is believed that the adhesive composition of the present disclosure is particularly effective in an embodiment containing the polar solvent (C) as a solvent. The polar solvent (C) will be described in detail below.

[0037] When the adhesive composition of the present disclosure further contains a polar solvent (C) in addition to the compound (A), the crosslinking agent (B), and the additive (D), the content of the additive (D) is preferably 0.01 parts by mass or more and 0.8 parts by mass or less per 100 parts by mass of the total content of the compound (A), the crosslinking agent (B), and the polar solvent (C). When the content of the additive (D) is within the above range, the adhesive composition can better form a uniform coating film on a resin substrate even when it contains the polar solvent (C). In particular, the content of the additive (D) is more preferably 0.1 parts by mass or more and 0.6 parts by mass or less, and even more preferably 0.1 parts by mass or more and 0.5 parts by mass or less per 100 parts by mass of the total content of the compound (A), the crosslinking agent (B), and the polar solvent (C) (hereinafter also referred to as (A + B + C)).

[0038] The adhesive composition of the present disclosure may contain only one type of additive (D), or may contain two or more types. The content of the additive (D) relative to the total mass of the adhesive composition is preferably 0.1 mass % to 0.6 mass %, and more preferably 0.1 mass % to 0.5 mass %.

[0039] The inorganic material layer (inorganic substrate) and organic material layer (organic substrate) to which the adhesive composition of the present disclosure is applied will be described.

[0040] (Inorganic Material Layer) The adhesive composition of the present disclosure is disposed between an inorganic material layer and an organic material layer, and is used to bond the inorganic material layer and the organic material layer. The type of inorganic material constituting the inorganic material layer to which the adhesive composition of the present disclosure is applied is not particularly limited. Specific examples of inorganic materials include semiconductors such as Si, InP, GaN, GaAs, InGaAs, InGaAlAs, SiGe, and SiC; boron silicate glass (Pyrex (registered trademark)); quartz glass (SiO ２ ), sapphire (Al ２ O ３ ), ZrO ２ , Si ３ N ４ , SiCN, AlN, MgAl ２ O ４ Oxides, carbides or nitrides of BaTiO ３ , LiNbO ３ , SrTiO ３, LiTaO ３ , etc.; diamond; metals such as Al, Ti, Fe, Cu, Ag, Au, Pt, Pd, Ta, Nb, etc.; carbon, etc. Among the inorganic materials mentioned above, Si, SiO ２ , SiC and SiCN are preferred.

[0041] The inorganic material layer may be a self-supporting object or may be formed as a layer on the surface of another object. When the inorganic material layer is formed as a layer on the surface of another object, the type of the other object is not particularly limited and may be an inorganic material or an organic material. The inorganic material layer may have an electrode on the surface facing the organic material layer.

[0042] (Organic Material Layer) The type of organic material constituting the organic substrate (organic material layer) to which the adhesive composition of the present disclosure is applied is not particularly limited. Specific examples of organic materials include epoxy resins, phenolic resins, silicone resins, polyimides, benzocyclobutene resins, and polybenzoxazoles.

[0043] The organic material layer may be a self-supporting object or may be formed as a layer on the surface of another object. When the organic material layer is formed as a layer on the surface of another object, the type of the other object is not particularly limited and may be an inorganic material or an organic material. The organic material layer may have an electrode on the surface facing the inorganic material layer.

[0044] The adhesive composition of the present disclosure contains at least the following compound (A) and crosslinking agent (B) in addition to the additive (D), and may further contain a polar solvent (C) as desired: Compound (A): 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; Crosslinking agent (B): A compound having three or more —C(═O)OX groups (X is a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms) in the molecule, and one to six of the three or more —C(═O)OX groups are —C(═O)OH groups.

[0045] -Compound (A)- Compound (A) has 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 bear a positive charge and is a functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom. Compound (A) may contain a tertiary nitrogen atom in addition to the primary nitrogen atom and the secondary nitrogen atom. The number of Si-O bonds contained in compound (A) is preferably two or three.

[0046] In the present disclosure, a "primary nitrogen atom" refers to a nitrogen atom that is bonded to only two hydrogen atoms and one atom other than a hydrogen atom (e.g., a primary amino group (-NH ２ "Secondary nitrogen atom" refers to a nitrogen atom bonded to only one hydrogen atom and two atoms other than hydrogen atoms (i.e., a nitrogen atom contained in a functional group represented by formula (a1) below), or a nitrogen atom (cation) bonded to only two hydrogen atoms and two atoms other than hydrogen atoms. "Tertiary nitrogen atom" refers to a nitrogen atom bonded to only three atoms other than hydrogen atoms (i.e., a nitrogen atom that is a functional group represented by formula (b1) below), or a nitrogen atom (cation) bonded to only one hydrogen atom and three atoms other than hydrogen atoms.

[0047]

[0048] In formula (a1) and formula (b1), * indicates the bonding position to an atom other than a hydrogen atom. The functional group represented by formula (a1) is a secondary amino group (-NHR ａ group; where R ａ The functional group represented by formula (b1) (i.e., a 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 represents an alkyl group), or may be a trivalent linking group contained in the skeleton of the polymer.

[0049] 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 even more preferably 130 or more and 2,000 or less.

[0050] In the present disclosure, the weight-average molecular weight of a compound refers to a polyethylene glycol-equivalent weight-average molecular weight measured by gel permeation chromatography (GPC). Specifically, the weight-average molecular weight of a compound is calculated using an aqueous solution of sodium nitrate with a concentration of 0.1 mol / L as a developing solvent, a Shodex DET RI-101 analyzer, and two analytical columns (TSKgel G6000PWXL-CP and TSKgel G3000PWXL-CP, manufactured by Tosoh Corporation) to detect the refractive index at a flow rate of 1.0 mL / min, and analysis software (Empower3, manufactured by Waters Corporation) using polyethylene glycol / polyethylene oxide as standards.

[0051] Compound (A) may further have an anionic functional group, a nonionic functional group, or the like, 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, and an ether group (—O—). There are no particular limitations on the anionic functional group, as long as it is a functional group that can bear a negative charge. Examples of the anionic functional group include a carboxylic acid group, a sulfonic acid group, and a sulfate group.

[0052] Compound (A) may be a compound having an Si—O bond and an amino group. Examples of compounds having an Si—O bond and an amino group include siloxane diamine, silane coupling agents having an amino group, and siloxane polymers. Examples of silane coupling agents having an amino group include compounds represented by the following formula (A-3):

[0053]

[0054] In formula (A-3), R １represents an alkyl group having 1 to 4 carbon atoms which may be substituted. ２ and R ３ R each independently represents an alkylene group having 1 to 12 carbon atoms, an ether group, or a carbonyl group which may be substituted (the skeleton may contain a carbonyl group, an ether group, etc.). ４ and R ５ each 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 alkyl group having 1 to 5 carbon atoms which may be substituted. X ２ represents hydrogen, a cycloalkyl group, a heterocyclic group, an aryl group, or an alkyl group having 1 to 5 carbon atoms which may be substituted (which may contain a carbonyl group, an ether group, etc. in the skeleton). １ , R ２ , R ３ , R ４ , R ５ , X １ may be the same or different. １ , R ２ , R ３ , R ４ , R ５ , X １ , X ２ In X, the substituents of the alkyl group and alkylene group each independently include an amino group, a hydroxy group, an alkoxy group, a cyano group, a carboxylic acid group, a sulfonic acid group, a halogen atom, etc. The divalent or trivalent aromatic ring in Ar includes, for example, a divalent or trivalent benzene ring. ２ Examples of the aryl group in the formula (I) include a phenyl group, a methylbenzyl group, and a vinylbenzyl group.

[0055] Specific examples of the silane coupling agent represented by formula (A-3) include 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)phenyltriethoxysilane,

[0033] Examples of suitable silanes include (2-(2-aminoethyl)-3-aminopropyl)phenylaminoethyl)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, diaminomethylmethyldiethoxysilane, methylaminomethylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, N-methylaminopropyltriethoxysilane, N-methylaminopropylmethyldiethoxysilane, (phenylaminomethyl)methyldiethoxysilane, acetamidopropyltrimethoxysilane, and hydrolysates thereof.

[0056] Examples of silane coupling agents having an amino group other than those represented by 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 hydrolysates thereof.

[0057] The silane coupling agent having the amino group may be used alone or in combination of two or more kinds.In addition, the silane coupling agent having the amino group may be used in combination with the silane coupling agent not having the amino group.For example, the silane coupling agent having the mercapto group may be used to improve adhesion with metal.

[0058] The compound (A) may be a polymer (siloxane polymer) formed from the above-mentioned silane coupling agent via a siloxane bond (Si—O—Si). For example, a hydrolyzate of 3-aminopropyltrimethoxysilane can produce a polymer having a linear siloxane structure, a polymer having a branched siloxane structure, a polymer having a cyclic siloxane structure, a polymer having a cage siloxane structure, or the like. The cage siloxane structure is represented, for example, by the following formula (A-1):

[0059]

[0060] Examples of siloxane diamines include compounds represented by the following formula (A-2): In formula (A-2), i is an integer of 0 to 4, j is an integer of 1 to 3, and Me is a methyl group.

[0061]

[0062] Examples of siloxane diamines include 1,3-bis(3-aminopropyl)tetramethyldisiloxane (in formula (A-2), i = 0, j = 1) and 1,3-bis(2-aminoethylamino)propyltetramethyldisiloxane (in formula (A-2), i = 1, j = 1).

[0063] The compound (A) has a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom, and therefore can strongly adhere to the surface of the inorganic material layer and / or the organic material layer by electrostatic interaction with functional groups such as hydroxyl groups, epoxy groups, carboxy groups, amino groups, and mercapto groups that may be present on the surface of the inorganic material layer and / or the organic material layer, or by forming a covalent bond with the functional groups.

[0064] The compound (A) has a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom, and therefore is easily soluble in the polar solvent (C). By using the compound (A) that is easily soluble in the polar solvent (C), when the surface of the inorganic material layer or the organic material layer is hydrophilic, the compound (A) has a high affinity with these surfaces. Therefore, a smooth adhesive layer can be formed.

[0065] It is preferable that the molar ratio of Si element in the molecule to non-crosslinkable groups such as methyl groups bonded to the Si element (non-crosslinkable group / Si element) is less than 2 (satisfying the relationship non-crosslinkable group / Si element < 2). By satisfying this condition, it is thought that the crosslinking density (crosslinking between Si-O-Si bonds and amide bonds, imide bonds, etc.) of the formed film is improved, and excellent bonding strength can be obtained.

[0066] When compound (A) contains a primary nitrogen atom, the proportion of the primary nitrogen atoms in the total nitrogen atoms in compound (A) is preferably 20 mol % or more, more preferably 25 mol % or more, and even more preferably 30 mol % or more. Compound (A) may also have a cationic functional group that contains a primary nitrogen atom and does not contain any nitrogen atoms other than the primary nitrogen atom (e.g., a secondary nitrogen atom or a tertiary nitrogen atom).

[0067] When compound (A) contains a secondary nitrogen atom, the proportion of the secondary nitrogen atoms in all 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.

[0068] Compound (A) may contain a tertiary nitrogen atom in addition to a primary nitrogen atom and a secondary nitrogen atom. When compound (A) contains a tertiary nitrogen atom, the proportion of tertiary nitrogen atoms in all 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.

[0069] The content of compound (A) in the composition is not particularly limited, but can be, for example, 0.001% by mass or more and 20% by mass or less, preferably 0.01% by mass or more and 20% by mass or less, and more preferably 0.04% by mass or more and 20% by mass or less, relative to the entire composition.

[0070] —Crosslinking Agent (B)—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.

[0071] In the crosslinking agent (B), X in the -C(=O)OX group may be a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms, and among these, a hydrogen atom, a methyl group, an ethyl group, or a propyl group is preferred. Note that X in the -C(=O)OX group may be the same or different.

[0072] The crosslinking agent (B) is a compound having one to six -C(=O)OH groups in which X is a hydrogen atom in the molecule, preferably one to four -C(=O)OH groups in the molecule, more preferably two to four -C(=O)OH groups in the molecule, and even more preferably two or three -C(=O)OH groups in the molecule.

[0073] The weight-average molecular weight of the compound (B) is not particularly limited. For example, the weight-average molecular weight of the compound (B) may be 200 or more and 600 or less, 200 or more and 500 or less, 200 or more and 450 or less, or 200 or more and 400 or less. When the weight-average molecular weight of the compound (B) is within the above range, the solubility in the composition is improved.

[0074] 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. The crosslinking agent (B) may have multiple ring structures in the molecule, and the multiple ring structures may be the same or different. When the compound (B) has a ring structure in the molecule, the heat resistance of the adhesive layer is improved.

[0075] Examples of the alicyclic structure include an alicyclic structure having from 3 to 8 carbon atoms, preferably from 4 to 6 carbon atoms, and the ring structure may be saturated or unsaturated. More specific examples of the alicyclic structure include saturated alicyclic structures such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring; and unsaturated alicyclic structures such as a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, and a cyclooctene ring.

[0076] The aromatic ring structure is not particularly limited as long as it is a ring structure exhibiting aromaticity, and examples thereof include benzene-based aromatic rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a perylene ring; aromatic heterocycles such as a pyridine ring and a thiophene ring; and non-benzene-based aromatic rings such as an indene ring and an azulene ring.

[0077] The ring structure contained in the molecule of the crosslinking agent (B) is preferably at least one selected from the group consisting of a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a benzene ring, and a naphthalene ring, and from the viewpoint of further increasing the heat resistance of the adhesive layer, at least one of a benzene ring and a naphthalene ring is more preferred.

[0078] As described above, the crosslinking agent (B) may have a plurality of ring structures in the molecule, and when the ring structure is benzene, it may have a biphenyl structure, a benzophenone structure, a diphenyl ether structure, or the like.

[0079] The crosslinking agent (B) may have a fluorine atom in the molecule. For example, it may have 1 to 6 fluorine atoms in the molecule, or may have 3 to 6 fluorine atoms in the molecule. For example, the compound (B) may have a fluoroalkyl group in the molecule, specifically, a trifluoroalkyl group or a hexafluoroisopropyl group. If the crosslinking agent (B) has a fluorine atom in the molecule, the water absorption of the adhesive layer will decrease.

[0080] Examples of the crosslinking agent (B) include carboxylic acid compounds such as alicyclic carboxylic acids, benzenecarboxylic acids, naphthalenecarboxylic acids, diphthalic acids, and fluorinated aromatic ring carboxylic acids, and carboxylic acid ester compounds such as alicyclic carboxylic acid esters, benzenecarboxylic acid esters, naphthalenecarboxylic acid esters, diphthalic acid esters, and fluorinated aromatic ring carboxylic acid esters.

[0081] A carboxylic acid ester compound is a compound that has a carboxy group (-C(=O)OH group) in the molecule and has three or more -C(=O)OX groups, where at least one X is an alkyl group having 1 to 6 carbon atoms (i.e., has an ester bond). When the crosslinking agent (B) contained in the adhesive is a carboxylic acid ester compound, aggregation due to association between the compound (A) and the crosslinking agent (B) in the composition is suppressed, and aggregates and pits in the cured product are reduced. As a result, an adhesive layer with higher smoothness is obtained, and the thickness of the adhesive layer can be easily adjusted.

[0082] The carboxylic acid compound is preferably a tetravalent or less 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.

[0083] The carboxylic acid ester compound is preferably a compound containing three or less carboxy groups (—C(═O)OH groups) and three or less ester bonds in the molecule, and more preferably a compound containing two or less carboxy groups and two or less ester bonds in the molecule.

[0084] In the carboxylic acid ester compound, when X in three or more —C(═O)OX groups is an alkyl group having from 1 to 6 carbon atoms, X is preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and from the viewpoint of further suppressing aggregation due to association between the compound (A) and the crosslinking agent (B) in the composition, X is preferably an ethyl group or a propyl group.

[0085] 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, and 1,2,3,4,5,6-cyclohexanehexacarboxylic acid; benzenecarboxylic acids such as 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid, benzenepentacarboxylic acid, and mellitic acid; and 1,4,5,8-naphthalenetetracarboxylic acid. naphthalenecarboxylic acids such as 2,3,6,7-naphthalenetetracarboxylic acid; 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'-(ethyn-1,2-dinyl)diphthalic acid (4,4'-(Ethyne-1,2-diyl)diphthalic acid acid), 4,4'-(1,4-phenylenebis(oxy))diphthalic acid, 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))diphthalic acid, 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))diphthalic acid, 4,4'-((oxybis(4,1-phenylene))bis(oxy))diphthalic acid diphthalic acids such as perylene-3,4,9,10-tetracarboxylic 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 fluorinated aromatic carboxylic acids include 4,4'-(hexafluoroisopropylidene)diphthalic acid, 9,9-bis(trifluoromethyl)-9H-xanthene-2,3,6,7-tetracarboxylic acid, and 1,4-ditrifluoromethylpyromellitic acid;

[0086] Specific examples of the carboxylic acid ester compound include compounds in which at least one carboxy group in the specific examples of the carboxylic acid compound described above is substituted with an ester group, such as half-esterified compounds represented by the following formulas (B-1) to (B-6).

[0087]

[0088] In formulas (B-1) to (B-6), R is an alkyl group having 1 to 6 carbon atoms, and among these, 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. In formula (B-2), Y is O, C═O, or C(CF ３ ) ２ is.

[0089] The half-esterified compound can be produced, for example, by mixing a carboxylic acid anhydride, which is an anhydride of the above-mentioned carboxylic acid compound, with an alcohol solvent and ring-opening the carboxylic acid anhydride.

[0090] The content of the crosslinking agent (B) in the composition is, for example, preferably an amount such that the ratio (COOH / N) of the number of carboxy groups in the crosslinking agent (B) to the total number of nitrogen atoms in the compound (A) is 0.1 to 3.0, more preferably 0.3 to 2.5, and even more preferably 0.4 to 2.2. By using a composition having a COOH / N ratio of 0.1 to 3.0, crosslinked structures such as amide bonds and imide bonds are sufficiently formed between the compound (A) and the crosslinking agent (B) after heat treatment, and an adhesive layer with superior heat resistance and insulating properties is formed.

[0091] When the composition contains an amine compound as a component other than the compound (A) and the crosslinking agent (B), 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 the total number of nitrogen atoms contained in the compound (A) is preferably 0.1 or more and 3.0 or less.

[0092] The content ratio (charge ratio) of the compound (A) to the crosslinking agent (B) in the composition is preferably a molar ratio of 2:0.9 to 2:1.1, more preferably 2:1, of the compound (A):crosslinking agent (B), from the viewpoint of minimizing the amount of unreacted crosslinking agent (B) remaining. It is believed that the compound (A) and the crosslinking agent (B) in the composition exist as a mixture in the polar solvent (C) in which the amino group of the compound (A) and the carboxy group of the crosslinking agent (B) form a salt. It is believed that the cured product obtained by heating a composition containing the compound (A) and the crosslinking agent (B) contains, as a structural unit, a reaction product of the compound (A) and the crosslinking agent (B), as exemplified below.

[0093]

[0094] - Polar Solvent (C) - The adhesive composition of the present disclosure may further contain a polar solvent (C). In the present disclosure, "polar solvent" refers to a solvent having a relative dielectric constant of 5 or more at room temperature (25°C). When the composition contains the polar solvent (C), the solubility of each component in the composition is improved. The polar solvent (C) may be used alone or in combination of two or more.

[0095] Specific examples of the polar solvent (C) include protic solvents 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, benzyl alcohol, diethylene glycol, triethylene glycol, and glycerin; ethers such as tetrahydrofuran and dimethoxyethane; aldehydes and ketones such as furfural, acetone, ethyl methyl ketone, and cyclohexanone; acid derivatives such as 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 acid amide; nitriles such as acetonitrile and propionitrile; and nitro compounds such as nitromethane and nitrobenzene; and sulfur compounds such as dimethyl sulfoxide. The polar solvent (C) preferably contains a protic solvent, more preferably contains water, and further preferably contains ultrapure water as the water.

[0096] The content of the polar solvent (C) in the composition is not particularly limited, and may be, for example, 1.0 mass% or more and 99.99896 mass% or less, or 40 mass% or more and 99.99896 mass% or less, relative to the entire composition.

[0097] From the viewpoint of volatilizing the polar solvent (C) by heating the composition and reducing the amount of residual solvent in the composition, the boiling point of the polar solvent (C) is preferably 150°C or lower, more preferably 120°C or lower.

[0098] Other Components The composition may contain known additives (also referred to as other additives) other than the additive (D) described above. Examples of other additives include an acid having a carboxy group and a weight average molecular weight of 46 to 195, a base having a nitrogen atom and no ring structure and a weight average molecular weight of 17 to 120, and a solvent other than the polar solvent (C).

[0099] The composition may contain a solvent other than the polar solvent (C). Examples of the solvent other than the polar solvent include normal hexane.

[0100] The composition may also contain benzotriazole or a derivative thereof, for example to inhibit copper corrosion.

[0101] The pH of the composition is not particularly limited, but is preferably 2.0 or more and 12.0 or less. When the pH of the composition is 2.0 or more and 12.0 or less, damage to the substrate by the composition is suppressed. The composition preferably has a sodium and potassium content of 10 mass ppb or less on an elemental basis. When the sodium or potassium content is 10 mass ppb or less on an elemental basis, it is possible to suppress the occurrence of problems in the electrical characteristics of the semiconductor device, such as transistor malfunction.

[0102] When the composition contains components other than the compound (A), the crosslinking agent (B), and the additive (D), the total content of the compound (A) and the crosslinking agent (B) is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more of the total mass of nonvolatile components in the composition. In the present disclosure, "nonvolatile components" refers to components other than components (such as solvents) that are removed when the composition becomes a cured product.

[0103] -Method for Producing Composition- The method for producing the composition is not particularly limited and can be carried out by a known method. For example, the composition can be produced by a method including the following steps (a), (b), and (c). Step (a): mixing compound (A) and water to obtain solution A containing a hydrolysate of compound (A); Step (b): adding alcohol to a precursor of crosslinking agent (B), heating, and refluxing to prepare solution B containing a half ester compound of crosslinking agent (B); Step (c): blending solution A, solution B, additive (D), and, if desired, polar solvent (C).

[0104] The composition can be cured by heating to form an adhesive layer. The heating temperature for curing the composition is preferably 150°C to 450°C, more preferably 150°C to 400°C, and even more preferably 180°C to 400°C. The above temperature refers to the temperature of the surface of the composition.

[0105] The heating time of the composition 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, 5 minutes or more. In order to shorten the heating time, the composition may be irradiated with ultraviolet (UV) rays.

[0106] Whether or not the composition has cured after heating can be confirmed, for example, by measuring the peak intensity of specific bonds and structures using FT-IR (Fourier transform infrared spectroscopy). Examples of specific bonds and structures include bonds and structures generated by crosslinking reactions. For example, when amide bonds, imide bonds, etc. are formed in the composition, it can be determined that the composition has cured. The presence or absence of amide bonds can be confirmed by measuring the peak intensity of specific bonds and structures using FT-IR (Fourier transform infrared spectroscopy). Examples of specific bonds and structures include bonds and structures generated by crosslinking reactions. For example, when amide bonds, imide bonds, etc. are formed in the composition, it can be determined that the composition has cured. －１ and approximately 1520 cm －１ The presence or absence of an imide bond can be confirmed by the presence or absence of a vibration peak at approximately 1770 cm －１ and approximately 1720 cm －１ This can be confirmed by the presence or absence of a vibration peak.

[0107] <Laminate> A first embodiment of the laminate of the present disclosure has an inorganic material layer, an organic material layer, and an adhesive layer disposed between the inorganic material layer and the organic material layer and bonding the inorganic material layer to the organic material layer, and the adhesive layer contains the adhesive composition of the present disclosure described above.

[0108] The laminate of the present disclosure is in a state in which an inorganic material layer and an organic material layer are bonded via an adhesive layer formed from the adhesive composition of the present disclosure, and due to the function of the adhesive composition, the adhesive layer exhibits excellent adhesion to both the inorganic material layer and the organic material layer.

[0109] A second embodiment of the laminate of the present disclosure includes an inorganic material layer, an organic material layer, and an adhesive layer disposed between the inorganic material layer and the organic material layer and bonding the inorganic material layer and the organic material layer, wherein the adhesive layer includes a reaction product of a compound (A) having a cationic functional group containing at least one selected from a primary nitrogen atom and a secondary nitrogen atom and a Si—O bond, and 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, wherein one to six of the three or more —C(═O)OX groups are —C(═O)OH groups and having a weight average molecular weight of 200 to 600, and an additive (D) having a structure represented by the following formula (a) and a structure represented by the following formula (b):

[0110]

[0111]

[0112] From the viewpoint of ensuring sufficient bonding strength between the inorganic material layer and the organic material layer, the ratio (X / Y) of the die shear strength X (MPa) between the inorganic material layer and the organic material layer to the thickness Y (μm) of the adhesive layer is preferably 1.2 or more, more preferably 1.5 or more, and even more preferably 2.0 or more. The upper limit of the ratio (X / Y) of the die shear strength X (MPa) between the inorganic material layer and the organic material layer to the thickness Y (μm) of the adhesive layer is not particularly limited, but may be, for example, 10 or less, 8 or less, or 6 or less.

[0113] In the present disclosure, the die shear strength between the inorganic material layer and the organic material layer is measured by the method described in the examples.

[0114] From the viewpoint of ensuring sufficient bonding strength to the inorganic material layer and the organic material layer, the thickness Y of the adhesive layer is preferably 0.2 μm or more, preferably 0.5 μm or more, and more preferably 1.0 μm or more. From the viewpoint of ensuring sufficient heat dissipation, the thickness Y of the adhesive layer is preferably 10 μm or less, preferably 7.5 μm or less, more preferably 5.0 μm or less, and even more preferably 3.0 μm or less.

[0115] In the present disclosure, the thickness of the adhesive layer is measured by the method described in the Examples.

[0116] From the viewpoint of ensuring sufficient bonding strength to the inorganic material layer and the organic material layer, the die shear strength X between the inorganic material layer and the organic material layer is preferably 3 MPa or more, more preferably 4 MPa or more, and even more preferably 5 MPa or more.

[0117] The upper limit of the die shear strength X between the inorganic material layer and the organic material layer is not particularly limited, but may be, for example, 10 MPa or less, 8 MPa or less, or 6 MPa or less.

[0118] The adhesive layer preferably contains a cured product of the adhesive. When the adhesive layer contains a cured product of the adhesive, the adhesive layer is sufficiently hard, and misalignment can be effectively suppressed when bonding the inorganic material layer and the organic material layer. The adhesive layer when bonding the inorganic material layer and the organic material layer may be in a completely cured state or in a completely incurable state.

[0119] From the viewpoint of suppressing the generation of voids due to outgassing, the cure rate of the adhesive layer is more preferably 80% or more, even more preferably 85% or more, particularly preferably 90% or more, and even more preferably 93% or more. The cure rate of the adhesive layer may be 100%, 99% or less, 95% or less, or 90% or less.

[0120] The curing rate of the adhesive layer may be determined by, for example, measuring the peak intensity of a specific bond and structure (the sum of the peak intensities when there are multiple peaks, such as imide, amide, etc.) using FT-IR (Fourier transform infrared spectroscopy) in the adhesive layer to be measured and in the fully cured adhesive layer obtained by fully curing the adhesive layer, and determining the rate of increase or decrease in the peak intensity. Note that when there are band-like peaks that are difficult to separate, such as siloxane bonds, the maximum peak intensity may be used.

[0121] Specifically, when specific bonds and structures are generated by the curing reaction, the rate of increase in peak intensity can be calculated using the following formula, and the calculated value can be used as the curing rate of the adhesive layer. Peak intensity increase rate (curing rate of adhesive layer) = [(peak intensity of specific bonds and structures in the adhesive layer to be measured) / (peak intensity of specific bonds and structures in the fully cured adhesive layer obtained by heating the adhesive layer to be measured at 300°C for 1 hour)] × 100. Note that background signals can be removed using a conventional method. Furthermore, FT-IR measurement can be performed using a transmission method or a reflection method, as necessary.

[0122] In the above-mentioned rate of increase in peak intensity, when there are multiple bonds and structures resulting from the increase in peak intensity, the peak intensity may be interpreted as the total intensity of the multiple peak intensities.

[0123] <Method for Producing Laminate> There are no particular limitations on the method for producing the laminate of the present disclosure. For example, the laminate can be produced by a method including the steps of: applying the adhesive composition of the present disclosure to a surface of at least one of an organic material layer and an inorganic material layer to form an adhesive composition layer; and bonding the inorganic material layer and the organic material layer via the adhesive composition layer.

[0124] In the above method, the method for applying the adhesive composition to the surface of at least one of the organic material layer and the inorganic material layer is not particularly limited and can be performed by a known method, such as a spin coating method, an inkjet method, or a screen printing method.

[0125] When the adhesive composition layer is formed by applying the adhesive composition to the surface of the organic material layer, the surface of the organic material layer on which the adhesive composition layer is to be formed may be in a state where it has been subjected to a plasma treatment. By applying the plasma treatment, for example, the wettability of the adhesive to the organic material layer is further improved.

[0126] In the above method, the method for bonding the inorganic material layer and the organic material layer via the adhesive layer is not particularly limited. For example, a method can be used in which the adhesive layer disposed between the organic material layer and the inorganic material layer is pressurized while being heated. The temperature at which the adhesive layer is heated is not particularly limited and can be selected depending on the type of adhesive. The temperature at which the adhesive is heated may be, for example, 150°C or higher, 200°C or higher, or 400°C or lower, or 300°C or lower. The pressure at which the adhesive layer is pressurized is not particularly limited and can be selected depending on the type of adhesive.

[0127] In the above method, the step of forming the adhesive layer may include a step of curing the adhesive. That is, the adhesive layer may be in a state containing a cured product of the adhesive when the inorganic material layer and the organic material layer are bonded. In the step of curing the adhesive, the adhesive may or may not be completely cured. If the adhesive layer is in a state containing a cured product of the adhesive when the inorganic material layer and the organic material layer are bonded, misalignment when the inorganic material layer and the organic material layer are bonded can be effectively suppressed. Furthermore, the adhesive layer has low adhesion when the inorganic material layer and the organic material layer are bonded, allowing the bonding operation to be performed efficiently.

[0128] The method for curing the adhesive is not particularly limited and can be selected depending on the composition of the adhesive composition. For example, the heating temperature when the adhesive composition is cured by heating to form an adhesive layer is not particularly limited, but can be, for example, 150°C or higher and 350°C or lower. The laminate of the present disclosure has good uniform applicability to an organic substrate, which is an organic material layer, and therefore can reliably bond an organic substrate and an inorganic substrate, which is an inorganic material layer, and can be used in a variety of applications.

[0129] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0130] Example 1 (1) Preparation of adhesive composition 50% by mass of 3-aminopropyldiethoxymethylsilane (3APDES: structure below: compound (A)) and 50% by mass of water (polar solvent (c)) were blended to obtain a solution A containing a hydrolysate of 3APDES.

[0131]

[0132] Solution B was obtained, containing 70% by mass of ethyl oxydiphthalate half ester (eheODPA: crosslinker (B)) and 30% by mass of ethanol. eheODPA was produced by adding oxydiphthalic anhydride (ODPA: structure shown below) to ethanol, refluxing in an oil bath heated to 90°C for 5 hours, and completely dissolving the raw material powder. Proton NMR confirmed that ester groups were formed in the produced eheODPA.

[0133]

[0134] The obtained solution A (24 g), solution B (15.6 g), 1-propanol (20 g), water (40.4 g), and additive (D-1) (additive (D)) were blended to prepare an adhesive composition. The above-mentioned exemplified compound (D-1) was used as additive (D-1).

[0135] Examples 2 to 5, Comparative Examples 1 and 2 Adhesive compositions were prepared in the same manner as in Example 1, except that the components of the adhesive composition were changed to those shown in Table 1 below.

[0136] (2) Formation of Adhesive Layer on Organic Substrate An epoxy resin composition (R4121-2C) manufactured by Nagase ChemteX Corporation was molded under the following conditions to obtain an epoxy resin substrate: Molding: 125°C x 400 seconds Post-mold cure: 150°C x 30 minutes

[0137] The adhesive composition prepared in (1) above was applied to an epoxy resin substrate by spin coating and dried at 150°C for 1 minute. An adhesive layer was then formed by heating at 200°C for 1 hour in a nitrogen atmosphere. The adhesive composition was wetted and spread over the entire surface of the epoxy resin substrate without any gaps, and there were no uncoated defects, so it was determined that a uniform coating film (adhesive layer) had been formed on the organic substrate (epoxy resin substrate).

[0138] <Evaluation criteria for coatability on organic substrates> By visual observation, a substrate in which the adhesive composition had wetted and spread over the entire surface of the epoxy resin substrate (organic substrate) without any gaps, had no uncoated defects, and formed a uniform coating film was rated as A, and a substrate in which the adhesive composition had not wetted and spread over some parts of the epoxy resin substrate (organic substrate) (i.e., cissing) and a uniform coating film had not been formed was rated as B. The results are shown in Table 2.

[0139] (2) Formation of Adhesive Layer on Inorganic Substrate The adhesive composition prepared in (1) above was applied to a 4-inch diameter silicon substrate (inorganic substrate) by spin coating and dried at 150°C for 1 minute. An adhesive layer was then formed by heating at 200°C for 1 hour in a nitrogen atmosphere. The adhesive composition was wetted and spread over the entire surface of the 4-inch diameter silicon substrate without any gaps, and there were no uncoated defects, so it was determined that a uniform coating film (adhesive layer) had been formed on the inorganic substrate (4-inch substrate).

[0140] <Evaluation criteria for coatability on inorganic substrates> When visually observed, a substrate in which the adhesive composition had spread over the entire surface of a 4-inch diameter silicon substrate (inorganic substrate) without any gaps, had no uncoated defects, and formed a uniform coating film was rated as A, and a substrate in which the adhesive composition had not spread over part of the 4-inch diameter silicon substrate (inorganic substrate) (i.e., repelling) occurred, and a uniform coating film was not formed was rated as B. The results are shown in Table 2.

[0141] (3) Preparation of substrate laminate for bond strength evaluation A 4-inch diameter silicon substrate was prepared as the first substrate. After treating the silicon substrate with UV ozone for 5 minutes, the composition prepared in (1) above was spin-coated. After drying at 150°C for 1 minute, the substrate was heated at 200°C for 1 hour in a nitrogen atmosphere to form a film (adhesive layer) containing imide-crosslinked siloxane. A silicon substrate, which was the second substrate, was bonded to the adhesive layer side obtained above at room temperature and temporarily fixed. Temporary fixing refers to temporary bonding in a room temperature (25°C) atmosphere.

[0142] <Evaluation criteria for bonding strength in room temperature temporary bonding> When the bonded silicon substrates were fixed to each other during the room temperature temporary bonding described above, the bonded silicon substrates were evaluated as A, and when the bonded silicon substrates were not fixed to each other, the bonded silicon substrates were evaluated as B. The results are shown in Table 2.

[0143] After the room temperature temporary bonding, the substrates were heated in an inert oven at 200°C for 1 hour to produce a substrate laminate consisting of a first substrate, adhesive layer, and second substrate. The surface energy (bonding strength) of the bonding interface of the substrate laminate was measured by a blade insertion test according to the method described in a non-patent document (M.P. Maszara, G. Goetz, A. Cavigila, and J.B. Mckitterick, Journal of Applied Physics, 64 (1988) 4943-4950). A blade with a thickness of 0.1 mm to 0.3 mm was inserted into the bonding interface of the substrate laminate, and the distance from the blade edge to the substrate laminate peeled was measured using an infrared light source and an infrared camera. The surface energy was then measured based on the following formula: γ = 3 × 10 ９ ×t ｂ ２ ×E ２ ×t ６ / (32 x L ４ ×E×t ３ ) where γ is the surface energy (J / m ２ ), t ｂ represents the blade thickness (m), E represents the Young's modulus (GPa) of the substrate such as a silicon substrate included in the first substrate stack and the second substrate, etc., t represents the thickness (m) of the substrate in the first substrate stack and the substrate in the second substrate, etc., and L represents the stack peeling distance (m) from the blade cutting edge.

[0144] <Evaluation criteria for bonding strength after heating (baking)> The surface energy measured above is 2.5 J / m ２ A if the surface energy is 2.5 J / m or more ２ If the value was less than 100%, the evaluation was B. The results are shown in Table 2.

[0145]

[0146]

[0147] As shown in Table 2, in Examples 1 to 5, which used the adhesive composition of the present disclosure, the coatability to organic substrates was good in addition to the coatability to inorganic substrates, and it was possible to form uniform coating films on both inorganic and organic substrates. On the other hand, in Comparative Examples 1 and 2, which did not contain additive (D), repelling occurred when applied to an organic substrate, and it was not possible to form a uniform coating film.

[0148] The disclosure of Japanese Patent Application No. 2023-203350, filed on November 30, 2023, is incorporated herein by reference. All documents, patent applications, and technical standards mentioned in this disclosure are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. An adhesive composition comprising: (A) a compound having a cationic functional group containing at least one selected from a primary nitrogen atom and a secondary nitrogen atom and a Si-O bond; (B) a crosslinking agent having three or more -C(=O)OX groups in the molecule, X representing a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms, and of the three or more -C(=O)OX groups, from 1 to 6 are -C(=O)OH groups, and having a weight average molecular weight of 200 to 600; and (D) an additive having a structure represented by the following formula (a) and a structure represented by the following formula (b).

2. The adhesive composition according to claim 1, wherein the content of the additive (D) is 0.1 parts by mass or more and 7 parts by mass or less per 100 parts by mass of the total content of the compound (A) and the crosslinking agent (B).

3. The adhesive composition according to claim 1, further comprising a polar solvent (C).

4. The adhesive composition according to claim 3, wherein the polar solvent (C) contains at least water.

5. The adhesive composition according to claim 3, wherein the content of the additive (D) is 0.01 parts by mass or more and 0.8 parts by mass or less per 100 parts by mass of the total content of the compound (A), the crosslinking agent (B), and the polar solvent (C).

6. A laminate comprising an inorganic material layer, an organic material layer, and an adhesive layer disposed between the inorganic material layer and the organic material layer to bond the inorganic material layer and the organic material layer, the adhesive layer comprising the adhesive composition according to claim 1 or claim 2.

7. A laminate comprising an inorganic material layer, an organic material layer, and an adhesive layer disposed between the inorganic material layer and the organic material layer for bonding the inorganic material layer and the organic material layer, wherein the adhesive layer comprises: a reaction product of a compound (A) having a cationic functional group containing at least one selected from a primary nitrogen atom and a secondary nitrogen atom and a Si-O bond, and 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, wherein one to six of the three or more -C(=O)OX groups are -C(=O)OH groups, and having a weight average molecular weight of 200 to 600; and an additive (D) having a structure represented by the following formula (a) and a structure represented by the following formula (b).

8. The adhesive composition according to claim 1 or 2, wherein the additive (D) has a structure represented by the following formula (c): In formula (c), R １ and R ２ each independently represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, n represents an integer of 1 to 40, m represents an integer of 1 to 30, x represents an integer of 1 to 300, and y represents an integer of 1 to 100.