silane coupling agent

Abstract

Provided is a silane coupling agent having low viscosity and excellent coatability, and having an excellent effect of improving the adhesiveness between inorganic materials and organic materials. This silane coupling agent contains a silicon compound described below and water, the silicon compound concentration being 0.01-10 wt%. Silicon compound: contains a compound (I) represented by formula (1) and a polycondensate thereof, the ratio (compound (I) / compound (II); ratio by weight) of the amount of compound (I) and the amount of a compound (II), which is the portion of the polycondensate of compound (I) having a weight-average molecular weight expressed in terms of standard polystyrene of 200-10000, being 1 / 99-95 / 5

Description

[Technical Field]

[0001] The present disclosure relates to a silane coupling agent that is effective in improving adhesion between inorganic and organic substances and has excellent storage stability. This application claims priority from Japanese Patent Application No. 2020-139427, filed on August 20, 2020, the contents of which are incorporated herein by reference. [Background technology]

[0002] Conventionally, compounds having a reactive group with organic matter and a silanol group that forms a chemical bond with the surface of inorganic matter (silanol compounds), or oligomers thereof, have been known as compounds that act to firmly bind inorganic and organic matter with different chemical properties.

[0003] The silanol compounds and their oligomers are used as surface modifiers or primers for inorganic substrates. For example, in the WOW (Wafer On Wafer) method in which multiple wafers with circuits formed thereon are stacked, the COW (Chip On Wafer) method in which multiple chips are stacked on a wafer with circuits formed thereon, and the COC (Chip On Chip) method in which multiple chips are stacked, the surfaces of both the stacking side and the stacking side are modified with a silanol compound or its oligomer, and then bonded with a permanent adhesive.

[0004] However, silanol compounds and their oligomers have the problem of low storage stability due to the presence of highly reactive silanol groups, and are prone to gelation due to the progress of dehydration condensation reactions.

[0005] Patent Document 1 describes that a composition containing a silane oligomer obtained by hydrolytic condensation of a silane compound having a reactive functional group and three hydrolyzable groups, such as 3-glycidoxypropyltrimethoxysilane, a hydrolytic polycondensate of tetramethoxysilane, and an alcohol having 1 to 6 carbon atoms, has excellent storage stability. However, the viscosity of the composition is too high for use in applying it to a substrate (especially a thinned substrate such as a wafer or chip) to modify its surface, and therefore it has been necessary to dilute it each time by adding water and / or alcohol. Another problem is that the concentration of silanol groups, which contribute to the development of adhesive properties, is low, and when the composition is diluted to a level that ensures good application properties, sufficient adhesiveness cannot be obtained. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 10-251516 Summary of the Invention [Problem to be solved by the invention]

[0007] Therefore, an object of the present disclosure is to provide a silane coupling agent that has low viscosity, excellent coating properties, and the effect of firmly bonding inorganic and organic substances. Another object of the present disclosure is to provide a silane coupling agent that has excellent application properties and storage stability and is effective in firmly bonding inorganic and organic substances. Another object of the present disclosure is to provide an adhesive that contains the silane coupling agent and a curable compound and has excellent adhesion and storage stability. Another object of the present disclosure is to provide a three-dimensional laminate formed by stacking wafers and / or chips using the adhesive. Another object of the present disclosure is to provide a semiconductor device including the three-dimensional stack. [Means for solving the problem]

[0008] The present inventors conducted extensive research to solve the above problems and found that hydrolysis of an alkoxysilane under acidic conditions, in the absence of an organic solvent or, even in the presence of an organic solvent, at a concentration of 0.7 parts by weight or less of the organic solvent per 1 part by weight of the compound represented by the following formula (2), can promote hydrolysis and dehydration condensation while suppressing gelation, resulting in a silane coupling agent containing a specific proportion of polycondensates with a high silanol group concentration, that the silane coupling agent has the effect of firmly bonding inorganic and organic substances, and that diluting the silane coupling agent with a specific solvent can improve storage stability and coatability while maintaining high adhesive strength between inorganic and organic substances. The present disclosure has been completed based on these findings.

[0009] That is, the present disclosure provides a silane coupling agent containing the following silicon compound and water, wherein the concentration of the silicon compound is 0.01 to 10% by weight. Silicon compound: A silicon compound containing a compound (I) represented by the following formula (1) and a polycondensate thereof, wherein the content ratio of the compound (I) to a polycondensate of the compound (II) having a weight average molecular weight of 200 to 10,000 in terms of standard polystyrene [compound (I) / compound (II); weight ratio] is 1 / 99 to 95 / 5. [ka] (wherein Y represents a hydrocarbon group having 1 to 10 carbon atoms and containing a group reactive with an organic substance)

[0010] The present disclosure also provides the silane coupling agent, which has a pH of 4 or less.

[0011] The present disclosure also provides the silane coupling agent containing a solvent having the following properties: Solvent: The evaporation rate is 10-400, assuming that the evaporation rate of butyl acetate is 100.

[0012] The present disclosure also provides the silane coupling agent, further comprising a solvent having the following properties: Solvent: The evaporation rate is 10 to 400, assuming that the evaporation rate of butyl acetate is 100, and the SP value at 25°C is 6 to 15.

[0013] The present disclosure also provides the silane coupling agent as a surface modifier.

[0014] The present disclosure also provides a method for producing a compound represented by the following formula (2) under conditions of pH 4 or less, in the absence of an organic solvent or, even if an organic solvent is present, under conditions in which the content of the organic solvent is 0.7 parts by weight or less per part by weight of a compound represented by the following formula (2): [ka] (wherein Y represents a hydrocarbon group having 1 to 10 carbon atoms and containing a group reactive with an organic substance, and OR 1 ~OR 3 are the same or different and represent hydrolyzable groups. The compound represented by the following formula (1) is hydrolyzed to [ka] (wherein Y is the same as above) and a step of subjecting the obtained compound represented by formula (1) to a polycondensation reaction to obtain the silane coupling agent.

[0015] The present disclosure also provides an adhesive comprising the silicon compound and a curable compound described below. Silicon compound: A silicon compound containing a compound (I) represented by the following formula (1) and a polycondensate thereof, wherein the content ratio of the compound (I) to a polycondensate of the compound (II) having a weight average molecular weight of 200 to 10,000 in terms of standard polystyrene [compound (I) / compound (II); weight ratio] is 1 / 99 to 95 / 5. [ka] (wherein Y represents a hydrocarbon group having 1 to 10 carbon atoms and containing a group reactive with an organic substance)

[0016] The present disclosure also provides the adhesive, wherein the content of the silicon compound is 0.01 to 40 parts by weight per 100 parts by weight of the curable compound.

[0017] The present disclosure also provides a three-dimensional laminate having a configuration in which wafers are laminated together, chips are laminated together, or wafers are laminated together via the adhesive.

[0018] The present disclosure also provides a semiconductor device including the three-dimensional stack. [Effects of the Invention]

[0019] The silane coupling agent of the present disclosure has a high silanol group concentration, and therefore can firmly bond inorganic and organic substances even at a low concentration. In addition, it has excellent storage stability and can suppress gelation over a long period of time. Furthermore, by using an adhesive obtained by blending a curable compound with the silane coupling agent of the present disclosure, it is possible to firmly bond and fix the adherends by applying the adhesive to one of the surfaces and then laminating them together, which previously required applying the adhesive to both surfaces of the adherends, and this provides excellent workability. If the silane coupling agent or adhesive is used in semiconductor chip stacking techniques such as the WOW (Wafer on Wafer) method, COW (Chip on Wafer) method, or COC (Chip on Chip) method, extremely small and thin wafers or chips can be efficiently stacked and strongly bonded, making it possible to produce three-dimensional stacked bodies with good yield. [Brief explanation of the drawings]

[0020] [Figure 1] FIG. 1 is a graph showing the effect of pH on the conversion rate in a hydrolysis reaction and a polycondensation reaction under conditions of a temperature of 50° C. and 6 eq of water. [Figure 2] FIG. 1 is a graph showing the effect of reaction temperature on the conversion rate in a hydrolysis reaction and a polycondensation reaction under conditions of pH 4 and 6 eq of water. [Figure 3]FIG. 1 is a graph showing the effect of the amount of water on the conversion rate in the hydrolysis reaction and polycondensation reaction under conditions of pH 4 and a temperature of 70° C. [Figure 4] FIG. 1 shows the Si-NMR measurement results of the silane coupling agent obtained in Example 1 (A) and the Si-NMR measurement results of the silane coupling agent obtained in Comparative Example 2 (B). [Figure 5] FIG. 1 is a graph showing the storage stability at 5° C. and 40° C. of the silane coupling agent obtained in Example 1 (+ethanol) and the silane coupling agent obtained in Example 2 (+PGMEA). DETAILED DESCRIPTION OF THE INVENTION

[0021] [Silane coupling agents] The silane coupling agent of the present disclosure contains the following silicon compound and water, and the concentration of the silicon compound is 0.01 to 10% by weight. Silicon compound: Contains compound (I) and its polycondensate, wherein the ratio of the content of compound (I) to the content of a compound (II) among the polycondensates of compound (I) having a weight average molecular weight of 200 to 10,000 in terms of standard polystyrene [compound (I) / compound (II); weight ratio] is 1 / 99 to 95 / 5. Compound (I) is a compound represented by the following formula (1): [ka]

[0022] In the above formula (1), Y represents a hydrocarbon group having 1 to 10 carbon atoms and containing a group reactive with an organic substance.

[0023] The reactive group with the organic substance includes an addition reactive group with the organic substance, a substitution reactive group, or a polymerization reactive group (a radical polymerization reactive group or a cation polymerization reactive group), for example, an amino group, an epoxy group, a (meth)acryloyloxy group, a vinyl group, a mercapto group, an isocyanurate group, etc. When the silane coupling agent of the present disclosure is used for the purpose of improving the adhesion between the inorganic substance and the adhesive, for example, when bonding an inorganic substance (e.g., a silicon wafer, glass, etc.) using an adhesive, the reactive group with the organic substance is preferably a group that has excellent reactivity with the adhesive, and when the adhesive contains an epoxy resin as a curable compound, an epoxy group is preferred, and when the adhesive uses an acrylic resin as a curable compound, a (meth)acryloyloxy group is preferred.

[0024] The epoxy group includes groups represented by the following formulae (e-1) to (e-3): R in the following formulae is a hydrogen atom or C 1-3 Indicates an alkyl group. [ka]

[0025] The hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and groups formed by combining these groups.

[0026] Examples of the aliphatic hydrocarbon group include alkyl groups having about 1 to 10 (preferably 1 to 3) carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, and decyl groups; alkenyl groups having about 2 to 10 (preferably 2 to 3) carbon atoms, such as vinyl, allyl, and 1-butenyl groups; and alkynyl groups having about 2 to 10 (preferably 2 to 3) carbon atoms, such as ethynyl and propynyl groups.

[0027] Alicyclic hydrocarbon groups include C 3-10Alicyclic hydrocarbon groups are preferred, and examples thereof include cycloalkyl groups having about 3 to 10 members (preferably 5 to 8 members) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups; cycloalkenyl groups having about 3 to 10 members (preferably 5 to 8 members) such as cyclopentenyl and cyclohexenyl groups; perhydronaphthalen-1-yl groups, norbornyl groups, adamantyl groups, and tricyclo[5.2.1.0] groups. 2,6 ] and bridged cyclic hydrocarbon groups such as decan-8-yl group.

[0028] The aromatic hydrocarbon group is C 6-10 Aromatic hydrocarbon groups are preferred, and examples thereof include phenyl and naphthyl groups.

[0029] The polycondensate of compound (I) is a resin (oligomer or polymer) having a siloxane (Si-O-Si) skeleton, and the structure of the resin may be cyclic, chain (linear or branched), cage, ladder, or the like.

[0030] Among the polycondensates, those having a chain structure (particularly, a straight chain structure) are preferred because they have excellent solvent solubility and can be applied by a spin coating method or the like when used for the purpose of modifying the surface of a substrate or the like, and compounds represented by the following formula (3) are particularly preferred. In the following formula, Y is the same as above. n is the number of repeating units shown in parentheses and represents an integer of 1 or more. The n+1 Ys may be the same or different. [ka]

[0031] The silane coupling agent contains, as silicon compounds, compound (I) and compound (II), which is a polycondensate of compound (I) (preferably a compound represented by the above formula (3)) and has a weight average molecular weight of 200 to 10,000 in terms of standard polystyrene.

[0032] The ratio of the content of the compound (I) to the compound (II) [compound (I) / compound (II); weight ratio] is 1 / 99 to 95 / 5, and the lower limit is preferably 3 / 97, more preferably 5 / 95, particularly preferably 10 / 90, and most preferably 20 / 80 from the viewpoint of suppressing the generation of gelled matter. The upper limit is preferably 93 / 7, particularly preferably 90 / 10 from the viewpoint of improving adhesiveness.

[0033] If the content of compound (I) exceeds the above range (in other words, if the content of compound (II) is below the above range), the adhesiveness tends to decrease, and if the content of compound (II) exceeds the above range (i.e., if the content of compound (I) is below the above range), gelation tends to occur more easily.

[0034] The weight-average molecular weight of the silicon compound contained in the silane coupling agent, calculated in terms of standard polystyrene, is, for example, 150 to 9500. The lower limit is preferably 200, more preferably 230, and particularly preferably 250. The upper limit is preferably 8000, more preferably 7000, more preferably 5000, even more preferably 2000, even more preferably 1000, particularly preferably 800, most preferably 600, and particularly preferably 550, in view of the high silanol group concentration and the ability to exhibit the effect of improving adhesion between inorganic and organic substances at lower concentrations. The molecular weight distribution (Mw / Mn) of the silicon compound is, for example, 1.1 to 4.0, preferably 1.1 to 2.0, and particularly preferably 1.1 to 1.5.

[0035] The silane coupling agent of the present disclosure may contain silicon compounds having structures other than compound (I) and compound (II) as silicon compounds. For example, the silane coupling agent may contain a disilanol represented by the following formula (1') or a monosilanol represented by the following formula (1") together with compound (I) (=trisilanol). Y in the following formulas is the same as defined above. [ka]

[0036] In the formula, OR 1 , OR 2 are the same or different and represent a hydrolyzable group. Examples of the hydrolyzable group include C 1-5 Alkoxy group, C 1-5 acyloxy group, etc. Therefore, R 1 , R 2 For example, C 1-5 Alkyl group or C 1-5 It is an acyl group.

[0037] In addition, together with compound (II), a polycondensate of compound (I) may be contained, in which the weight-average molecular weight, as calculated on standard polystyrene, is less than the lower limit of the weight-average molecular weight of compound (II) (e.g., 200) (= compound (II')), or the weight-average molecular weight of compound (II) exceeds the upper limit (e.g., 10,000) (= compound (II")). However, in terms of a high silanol group concentration and the ability to exhibit the effect of improving adhesion between inorganic and organic substances at lower concentrations, and excellent storage stability, the total content of compound (II') and compound (II") is, for example, preferably 30 wt% or less of the total silicon compounds contained in the silane coupling agent, more preferably 20 wt% or less, particularly preferably 10 wt% or less, most preferably 5 wt% or less, and particularly preferably 1 wt% or less.

[0038] Furthermore, the silane coupling agent of the present disclosure may contain a compound represented by the following formula (2) (for example, it may remain without being hydrolyzed), but in order to be able to exhibit the effect of improving the adhesion between inorganic and organic substances at a low concentration, the content of the compound represented by the following formula (2) is, for example, preferably 50% by weight or less of the total silicon compounds contained in the silane coupling agent, more preferably 40% by weight or less, particularly preferably 30% by weight or less, and most preferably 25% by weight or less. 1 , R 2 is the same as above. [ka]

[0039] In the formula, OR 3 represents a hydrolyzable group. Examples of the hydrolyzable group include C 1-5 Alkoxy group, C 1-5 acyloxy group, etc. Therefore, R 3 For example, C 1-5 Alkyl group or C 1-5 It is an acyl group.

[0040] The silane coupling agent is preferably acidic in terms of excellent storage stability, and the pH of the silane coupling agent is, for example, 4 or less (i.e., a pH of 4 or more acidic than 4), more preferably 2 to 4, and particularly preferably 3 to 4. If the pH of the silane coupling agent deviates from the above range to the basic side, the dehydration condensation reaction of the silicon compound in the silane coupling agent proceeds, resulting in gelation, which is undesirable when used for the purpose of modifying the surface of a substrate or the like, as it becomes difficult to apply the agent by a spin coating method or the like. On the other hand, if the pH of the silane coupling agent deviates from the above range to the acidic side, the reactive group becomes easily decomposed, which is undesirable.

[0041] The viscosity of the silane coupling agent is preferably, for example, about 1 to 300 mPa·s in terms of providing good coating properties. The viscosity can be measured, for example, using a digital viscometer (model number "DVU-EII" manufactured by Tokimec Inc.) under the following conditions: rotor: standard 1°34' x R24, temperature: 25°C, rotation speed: 0.5 to 10 rpm.

[0042] The silane coupling agent can be used with water or a solvent as a diluent. It is preferable to use a solvent that is easily volatile as the solvent. A silane coupling agent containing a solvent that is easily volatile can be applied thickly because the fluidity decreases due to the solvent quickly evaporating after application, thereby increasing the concentration of silanol groups in the coating film and enhancing the effect of improving the adhesion between inorganic and organic substances.

[0043] As the solvent, a solvent whose evaporation rate at a specific temperature and pressure is, for example, 10 to 400, where the evaporation rate of butyl acetate at the same temperature and pressure is taken as 100, is preferred. In terms of obtaining the effect of improving storage stability, the lower limit of the evaporation rate is more preferably 20, particularly preferably 50, most preferably 100, and especially preferably 150, and the upper limit of the evaporation rate is more preferably 350, particularly preferably 300, and most preferably 250. The evaporation rate of the solvent is, for example, the evaporation rate at room temperature (preferably 25°C) and under normal pressure.

[0044] Furthermore, it is preferable to use a solvent having an SP value (measured by the Fedors method) at 25°C of 6 to 15 (more preferably 9 to 15, particularly preferably 9 to 14, and most preferably 10 to 13), since the solvent caps the silanol groups and inhibits the progress of the dehydration condensation reaction of the silicon compound, thereby further improving storage stability.

[0045] As the solvent, it is particularly preferable to use a solvent whose evaporation rate, when the evaporation rate of butyl acetate is taken as 100, is in the above range and whose SP value at 25°C is in the above range, in that this can improve both the adhesion between inorganic and organic substances and storage stability.

[0046] Examples of the solvent include aliphatic alcohols such as ethanol, 1-propanol, 1-butanol, and 1-pentanol; glycol ether esters such as propylene glycol methyl ether acetate (PGMEA); and the like. These can be used alone or in combination of two or more.

[0047] Among these, the solvent is preferably an aliphatic alcohol, particularly preferably a monohydric aliphatic alcohol, and particularly preferably a monohydric C 2-6 An aliphatic alcohol, particularly preferably ethanol, is preferred.

[0048] The silane coupling agent has excellent storage stability, and when stored at 5°C for 30 days, the increase in weight average molecular weight is, for example, 500 or less, preferably 200 or less, particularly preferably 100 or less, and most preferably 50 or less.

[0049] The silane coupling agent has excellent storage stability even in a high-temperature environment, and when stored at 40°C for 30 days, the increase in weight-average molecular weight is, for example, 2000 or less, preferably 1500 or less, particularly preferably 1000 or less, and most preferably 700 or less.

[0050] The silane coupling agent of the present disclosure has low viscosity and excellent coating properties. It also has the effect of improving the adhesion between inorganic and organic materials. Therefore, by applying the silane coupling agent to the surface of an inorganic material (e.g., silicon wafer, glass, etc.), the adhesion with an organic adhesive is improved. Therefore, the silane coupling agent can be suitably used as a surface modifier for inorganic materials.

[0051] [Method of manufacturing silane coupling agents] The silane coupling agent can be produced through the following steps [I] and [II]. Step [I]: A method for preparing a compound represented by the following formula (2) under conditions of pH 4 or less, in the absence of an organic solvent or, even if an organic solvent is present, under conditions in which the content of the organic solvent is 0.7 parts by weight or less per part by weight of a compound represented by the following formula (2): [ka] (wherein Y represents a hydrocarbon group having 1 to 10 carbon atoms and containing a group reactive with an organic substance, and OR 1 ~OR 3 are the same or different and represent hydrolyzable groups. The compound represented by the following formula (1) is hydrolyzed to [ka] (wherein Y is the same as above) A process for obtaining a compound represented by the formula: Step [II]: A step of subjecting the compound represented by formula (1) obtained through the above step to a polycondensation reaction.

[0052] The steps [I] and [II] will be explained in detail below. [ka]

[0053] In the above formula, R 1 , R 2 , R 3 , Y, and n are the same as above.

[0054] Examples of the compound represented by formula (2), in which Y is a hydrocarbon group having 1 to 10 carbon atoms and containing an epoxy group, include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane.

[0055] Examples of the compound represented by formula (2), in which Y is a hydrocarbon group having 1 to 10 carbon atoms and containing a (meth)acryloyloxy group, include 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, and 3-(meth)acryloyloxypropyltriethoxysilane.

[0056] The above-mentioned step [I] is a step of carrying out a hydrolysis reaction of the compound represented by formula (2) to obtain the compound represented by formula (1). The amount of water used is, for example, 0.6 to 12 moles per mole of the compound represented by formula (2).

[0057] The hydrolysis reaction is carried out under conditions of pH 4 or less (preferably pH 2 to 4, particularly preferably pH 3 to 4).

[0058] The hydrolysis reaction is carried out in the absence of an organic solvent, or even if an organic solvent is present, under conditions in which the content of the organic solvent is 0.7 parts by weight or less per part by weight of the compound represented by the following formula (2):

[0059] Examples of the organic solvent include polar organic solvents such as monohydric aliphatic alcohols such as ethanol, 1-propanol, 1-butanol, and 1-pentanol; and glycol ether esters such as propylene glycol methyl ether acetate.

[0060] The upper limit of the content of the organic solvent (total amount when two or more types are contained) is 0.7 parts by weight, preferably 0.5 parts by weight, particularly preferably 0.3 parts by weight, and particularly preferably 0.2 parts by weight, per part by weight of the compound represented by formula (2).

[0061] Since the hydrolysis reaction is carried out under the above conditions, the progress of the hydrolysis reaction of the compound represented by formula (2) is accelerated, the amount of silanol groups generated can be increased, and the compound represented by formula (1) can be efficiently produced.

[0062] If the organic solvent (particularly the polar organic solvent) is present in the reaction system during the hydrolysis reaction in an amount exceeding the above range, the progress of the hydrolysis reaction of the compound represented by formula (2) is inhibited, making it difficult to efficiently produce the compound represented by formula (1).

[0063] Furthermore, if the pH in the reaction system during the hydrolysis reaction exceeds 4 and becomes alkaline, the progress of the hydrolysis reaction of the compound represented by formula (2) is inhibited, resulting in a decrease in the yield of compound (II) and an increase in the rate of by-production of compound (II') and compound (II") As a result, the formation of a three-dimensional crosslinked structure progresses, and gelation tends to become more likely. On the other hand, if the pH is lowered excessively, reactive groups tend to be more likely to decompose.

[0064] The step [II] is a step of dehydrating and condensing the compound represented by formula (1) obtained through the step [I] to obtain a compound represented by formula (3) in which (n+1) compounds represented by formula (1) are dehydrating and condensed.

[0065] When the compound represented by formula (1) is subjected to a dehydration condensation reaction under conditions of pH 4 or less (preferably pH 2 to 4, particularly preferably pH 3 to 4), a reaction to form a two-dimensional network proceeds preferentially over a reaction to form a three-dimensional crosslinked structure. This makes it possible to increase the production rate of compound (II) while suppressing gelation, and to obtain a silane coupling agent that is easy to apply by a spin coating method or the like and has excellent adhesive properties between inorganic and organic substances.

[0066] The dehydration condensation reaction may be carried out in the presence of an organic solvent. For example, the reactions of step [I] and step [II] may be carried out in one pot, and step [II] may be carried out under the same conditions as step [I], i.e., in the absence of an organic solvent, or even if an organic solvent is present, under conditions in which the content of the organic solvent is 0.7 parts by weight or less per part by weight of the compound represented by the following formula (2):

[0067] The reaction atmosphere in the above steps [I] and [II] is not particularly limited as long as it does not inhibit the reaction, and may be, for example, any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, etc.

[0068] The reaction temperature in the above steps [I] and [II] is, for example, about 40 to 85°C. The reaction time is, for example, about 20 hours or less. The reaction can be carried out by any method, such as a batch method, a semi-batch method, or a continuous method. The progress of the dehydration condensation reaction can be stopped by lowering the temperature in the reaction system to 30°C or less. Alternatively, the dehydration condensation reaction may be stopped by adding one or more solvents to lower the concentration in the reaction system.

[0069] Examples of the solvent include the same solvents that can be used as diluents for silane coupling agents.

[0070] After completion of the reaction in the above step [II], the obtained reaction product can be separated and purified by a separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, or a combination of these separation means.

[0071] [glue] The adhesive of the present disclosure contains the following silicon compound and curable compound. Silicon compound: A silicon compound containing a compound (I) represented by formula (1) and a polycondensate thereof, wherein the ratio of the content of the compound (I) to the content of a polycondensate of the compound (I) having a weight average molecular weight of 200 to 10,000 in terms of standard polystyrene [compound (I) / compound (II); weight ratio] is 1 / 99 to 95 / 5.

[0072] The silicon compound is the same as the silicon compound contained in the above-mentioned silane coupling agent.

[0073] The curable compound includes a thermoplastic resin and a heat-curable (or photo-curable) resin. The curable compound can be appropriately selected and used depending on the application. For example, it is preferable to use a heat-curable (or photo-curable) resin for the application of producing a three-dimensional stacked body in which wafers, chips, or wafers are stacked.

[0074] The thermosetting (or photosetting) resin is a compound that irreversibly hardens when heated (or irradiated with light), and includes, for example, epoxy resin, acrylic resin, etc. These can be used alone or in combination of two or more.

[0075] Examples of epoxy resins include compounds containing an alicyclic epoxy group (a group represented by the above formula (e-1)), such as 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate, (3,4,3',4'-diepoxy)bicyclohexyl, bis(3,4-epoxycyclohexylmethyl)ether, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, 2,2-bis(3,4-epoxycyclohexane-1-yl)propane, and 1,2-bis(3,4-epoxycyclohexane-1-yl)ethane; hydrogenated bisphenol A diglycidyl ether; alicyclic glycidyl ethers such as bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated biphenol diglycidyl ether, hydrogenated phenol novolac diglycidyl ether, and hydrogenated cresol novolac diglycidyl ether; and aromatic glycidyl ethers such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, biphenol diglycidyl ether, phenol novolac diglycidyl ether, and cresol novolac diglycidyl ether, and compounds containing a glycidyl ether group (the group represented by the above formula (e-3)).

[0076] In addition to the above compounds, the epoxy resins also include epoxy group-containing polyorganosilsesquioxanes, etc. The epoxy groups include groups represented by the above formulas (e-1) to (e-3).

[0077] The epoxy group-containing polyorganosilsesquioxane is a compound having a main chain skeleton formed of siloxane bonds and a group containing an epoxy group bonded to the main chain skeleton.

[0078] Epoxy group-containing polyorganosilsesquioxanes include those having various structures such as a ladder structure, a complete cage structure, an incomplete cage structure, and a random structure. Among these, silsesquioxanes having an incomplete cage structure are preferred because they can form cured products with high hardness.

[0079] The epoxy group-containing polyorganosilsesquioxane having an incomplete cage structure is represented by the following formula (S1): [R a SiO 3 / 2 ] (S1) [In formula (S1), R a represents a group containing an epoxy group, an aryl group, an aralkyl group, a cycloalkyl group, an alkyl group, an alkenyl group, or a hydrogen atom. and a structural unit represented by the following formula (S2): [R a SiO 2 / 2 (OR b )] (S2) [In formula (S2), R a is the same as above. R b represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Contains a constitutional unit represented by In the total amount of the structural units represented by the formula (S1) and the structural units represented by the formula (S2), at least one is R a is a structural unit that is a group containing an epoxy group.

[0080] The structural unit represented by the above formula (S1) is referred to as a T3 structure. The structural unit represented by the above formula (S2) is referred to as a T2 structure. Both of these structural units are T units.

[0081] Examples of the aryl group include aryl groups having 6 to 10 carbon atoms, such as a phenyl group and a naphthyl group.

[0082] Examples of the aralkyl group include aralkyl groups having 7 to 12 carbon atoms, such as a benzyl group and a phenethyl group.

[0083] Examples of the cycloalkyl group include cycloalkyl groups having 3 to 6 carbon atoms, such as a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0084] Examples of the alkyl group include linear or branched alkyl groups having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, an isopropyl group, an isobutyl group, an s-butyl group, a t-butyl group, and an isopentyl group.

[0085] Examples of the alkenyl group include linear or branched alkenyl groups having 2 to 6 carbon atoms, such as a vinyl group, an allyl group, and an isopropenyl group.

[0086] Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, and an isobutyloxy group.

[0087] The epoxy group-containing polyorganosilsesquioxane is a structural unit represented by the formula (S1) or (S2), wherein R a is a structural unit containing an epoxy group, and a structural unit represented by the formula (S1) or (S2), a may contain a structural unit in which is a substituted or unsubstituted aryl group (for example, a phenyl group).

[0088] The T3 isomer / T2 isomer (molar ratio), i.e., the ratio of the content of the structural unit represented by formula (S1) to the content of the structural unit represented by formula (S2) (former / latter; molar ratio), is, for example, 5 to 500. The lower limit of the molar ratio is preferably 7, particularly preferably 8, most preferably 9, and especially 10, in order to obtain the effect of improving the hardness and scratch resistance of the resulting cured product. The upper limit of the molar ratio is preferably 50, particularly preferably 30, most preferably 20, and especially 15. The molar ratio can be, for example, 29 It can be determined by Si-NMR spectroscopy. 29 In the Si-NMR spectrum, the silicon atom in the T3 isomer and the silicon atom in the T2 isomer have peaks at different positions, so the molar ratio can be determined by calculating the ratio of the integral values ​​of the respective peaks.

[0089] still,29 The Si-NMR spectrum can be measured using the following apparatus and conditions. Measuring device: Product name "JNM-ECA500NMR", manufactured by JEOL Ltd. Solvent: deuterated chloroform Accumulation count: 1800 times Measurement temperature: 25℃

[0090] The monomer components constituting the acrylic resin include a (meth)acrylic acid alkyl ester and a functional group-containing monomer, and the monomer components may further include one or more monomers copolymerizable with the (meth)acrylic acid alkyl ester and the functional group-containing monomer.

[0091] Examples of the (meth)acrylic acid alkyl ester include (meth)acrylic acid alkyl esters having an alkyl group having 1 to 20 carbon atoms, such as ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and isononyl (meth)acrylate.

[0092] Examples of the functional group-containing monomer include carboxyl group-containing monomers such as (meth)acrylic acid, maleic acid, and fumaric acid, or anhydrides thereof; hydroxyl group-containing monomers such as hydroxyethyl (meth)acrylate; epoxy group-containing monomers such as glycidyl (meth)acrylate and methylglycidyl (meth)acrylate; cyano group-containing monomers such as (meth)acrylonitrile; and amide group-containing monomers such as N-hydroxyethylacrylamide.

[0093] In addition to the silicon compound and curable compound, the adhesive of the present disclosure may contain one or more other components to the extent that the properties of the present disclosure are not impaired. Examples of other components include cationic polymerization initiators, crosslinking agents, crosslinking accelerators, tackifiers (e.g., rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenolic resins, etc.), antioxidants, fillers, UV absorbers, antioxidants, chain transfer agents, plasticizers, softeners, surfactants, antistatic agents, water, solvents, and fillers. Examples of the solvents include the same solvents that may be contained in the silane coupling agent described above.

[0094] When the adhesive contains an epoxy resin as a curable compound, it preferably further contains a cationic polymerization initiator.

[0095] The cationic polymerization initiator includes a photo or thermal cationic polymerization initiator.

[0096] The cationic polymerization initiator may be, for example, a sulfonium ion or an iodonium ion as the cation moiety, and PF6 - , S b F6 - Examples of the onium salt include those having the following as the anion moiety:

[0097] The amount of the cationic polymerization initiator used is, for example, 0.1 to 20 parts by weight based on 100 parts by weight of the epoxy compound.

[0098] When the adhesive contains an acrylic resin as the curable compound, it preferably further contains a crosslinking agent.

[0099] Suitable examples of the crosslinking agent include isocyanate-based crosslinking agents such as 1,6-hexamethylene diisocyanate and isophorone diisocyanate, and epoxy-based crosslinking agents such as 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane. The content of the crosslinking agent is, for example, about 0.05 to 2 parts by weight per 100 parts by weight of the total amount of the monomer components forming the acrylic polymer.

[0100] The adhesive preferably contains an epoxy resin as a curable compound when used in applications requiring heat resistance, curability in the presence of oxygen, and dimensional stability, and preferably contains an acrylic resin as a curable compound when used in applications requiring fast curing.

[0101] The adhesive contains the silicon compound and a curable compound, and since the silicon compound has a high silanol group concentration, it can exhibit excellent adhesive strength even at a low concentration. The content of the silicon compound in the adhesive is, for example, 0.01 to 40 parts by weight, preferably 0.03 to 20 parts by weight, particularly preferably 0.05 to 10 parts by weight, and most preferably 0.1 to 5 parts by weight, per 100 parts by weight of the curable compound (preferably an epoxy resin or an acrylic resin).

[0102] The adhesive may contain other components in addition to the silicon compound and curable compound. Examples of the other components include water, solvents, fillers, etc. Examples of the solvent include the same solvents as those that may be contained in the silane coupling agent.

[0103] In the past, when two inorganic substances were bonded together, the bonding surfaces of the two inorganic substances were first modified using a silane coupling agent or the like, and then the two inorganic substances were bonded together using an adhesive. However, when the adhesive of the present disclosure is used, the adhesive of the present disclosure is directly applied to the bonding surface of one of the two inorganic substances, and then the two inorganic substances are bonded together. This causes the silanol groups of the silicon compound contained in the adhesive to form Si-O-Si bonds with the hydroxyl groups on the surfaces of the inorganic substances, and at the same time, the reactive groups in the silicon compound that react with organic substances react with the adhesive, making it possible to firmly bond the two inorganic substances together using an extremely simple method.

[0104] Furthermore, the adhesive may contain the silicon compound and the curable compound, and may be a one-component adhesive in which they are mixed in advance, or a two-component adhesive in which they are stored separately and mixed at the time of use. In the present disclosure, it is preferable to use it as a one-component adhesive, as it has excellent workability. Since the adhesive contains a silicon compound with excellent storage stability, even when used as a one-component adhesive, it can suppress gelation over a long period of time and can be stored stably.

[0105] [3D laminate] The three-dimensional laminate of the present disclosure has a configuration in which wafers are laminated together, chips are laminated together, or wafers are laminated together via the adhesive (more specifically, the cured product of the adhesive).

[0106] Of the three-dimensional stacks, a structure in which wafers are stacked on top of each other can be produced, for example, by the following method (1) or (2). 1: When using a one-component adhesive or a mixture of two-component adhesives as the adhesive, the adhesive is applied to the bonding surface of one of the wafers, the wafers are bonded together, and then the adhesive is cured. 2: When a two-component adhesive is used as the adhesive, a first liquid containing a silicon compound is applied to the bonding surfaces of both wafers, and then the wafers are bonded together with a second liquid containing a permanent adhesive, after which the permanent adhesive is cured.

[0107] The adhesive can be cured by a method appropriate for the type of adhesive. For example, when an ultraviolet-curable adhesive is used, it can be cured by irradiating it with ultraviolet light, and when a thermosetting adhesive is used, it can be cured by applying a heat treatment.

[0108] Among the three-dimensional stacks, structures in which chips or wafers are stacked can also be produced by a method similar to the above method.

[0109] The three-dimensional stack is subjected to processes such as forming through electrodes (for example, TSVs), then dicing to separate the stack, mounting the stack on a wiring board, bonding the electrodes, and sealing with resin or the like.

[0110] [Semiconductor Devices] The semiconductor device of the present disclosure is characterized by including the above-described three-dimensional laminate, and examples of the semiconductor device of the present disclosure include mobile devices such as smartphones and tablets, servers, workstations, in-vehicle computers, personal computers, communication devices, imaging devices, and image display devices.

[0111] The semiconductor device of the present disclosure includes the above-described three-dimensional stack, and therefore can accommodate higher density, higher speed, and lower power consumption.

[0112] The above-described configurations and combinations thereof of the present disclosure are merely examples, and additions, omissions, substitutions, and modifications of the configurations are possible as appropriate within the scope of the present disclosure. Furthermore, the present disclosure is not limited to the embodiments, but is limited only by the claims. [Example]

[0113] The present disclosure will be explained in more detail below using examples, but the present disclosure is not limited to these examples. It should be noted that Examples 8 and 9 should be read as Reference Examples 1 and 2.

[0114] Example 1 (Preparation of Silane Coupling Agent) 3-glycidoxypropyltriethoxysilane and a 0.003 wt% aqueous solution of acetic acid were charged into a reaction vessel and heated at 70°C for 3 hours under conditions of pH 4 and 6 eq of water. As a result, the hydrolysis reaction and polycondensation reaction proceeded with a conversion rate of 100%. Thereafter, the heating treatment was stopped, and 39.9 g of ethanol was added to 5 g of the obtained crude product to obtain a silane coupling agent (1) (viscosity at 25°C and 0.5 rpm: <5 mPa·s). Furthermore, the evaporation rate of ethanol is 203 when the evaporation rate of butyl acetate is set at 100, and the SP value at 25°C is 12.7.

[0115] The weight ratio of compound (I) / compound (II) in the silane coupling agent (1) was determined by GPC measurement.

[0116] Furthermore, the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the silicon compound in the silane coupling agent (1) in terms of standard polystyrene were determined by GPC measurement.

[0117] The GPC measurement was carried out using the following equipment under the following conditions. Measuring device: Product name "LC-20AD", manufactured by Shimadzu Corporation Column: Shodex KF-801 x 2 + KF-802 x 1 + KF-803 x 1 (Showa Denko K.K.) Measurement temperature: 40℃ Eluent:THF Sample concentration: 0.1 to 0.2% by weight Flow rate: 1mL / min Detector: UV-VIS detector (product name "SPD-20A", manufactured by Shimadzu Corporation)

[0118] Example 2 (Preparation of Silane Coupling Agent) A silane coupling agent (2) was obtained in the same manner as in Example 1, except that PGMEA was used instead of ethanol. The evaporation rate of PGMEA is 19 when the evaporation rate of butyl acetate is taken as 100, and the SP value at 25°C is 8.7.

[0119] Example 3 (Preparation of Silane Coupling Agent) Silane coupling agent (3) was obtained in the same manner as in Example 1, except that the heating temperature was changed to 50°C and the pH of the acetic acid aqueous solution was changed to 2.67. Silane coupling agent (3) was subjected to Si-NMR measurement. The results are shown in Figure 4(A).

[0120] Example 4 (Preparation of Silane Coupling Agent) A silane coupling agent (4) was obtained in the same manner as in Example 1, except that the heating temperature was changed to 50°C, the heating time was changed to 4 hours, and the pH of the acetic acid aqueous solution was changed to 3.

[0121] Example 5 (Preparation of Silane Coupling Agent) The procedure was the same as in Example 1, except that the heating temperature was changed to 50°C and the heating time was changed to 6 hours. As a result, the hydrolysis reaction and polycondensation reaction proceeded with a conversion rate of 90%, and a silane coupling agent (5) was obtained.

[0122] Example 6 (Preparation of silane coupling agent) Except for changing the amount of water to 3 eq and the heating time to 11 hours, the procedure was the same as in Example 1. As a result, the hydrolysis reaction and polycondensation reaction proceeded with a conversion rate of 78%, and a silane coupling agent (6) was obtained.

[0123] Example 7 (Preparation of silane coupling agent) Except for changing the amount of water to 9 eq, the procedure was the same as in Example 1. As a result, the hydrolysis reaction and polycondensation reaction proceeded with a conversion rate of 100%, and a silane coupling agent (7) was obtained.

[0124] Example 8 (Preparation of silane coupling agent) 100 parts by weight of 3-glycidoxypropyltriethoxysilane and 20 parts by weight of a 10% by weight aqueous acetic acid solution were placed in a reaction vessel and stirred for 6 hours at 50° C. Thereafter, the reaction solution was concentrated for 2 hours at 40° C., and PGMEA was added to obtain a silane coupling agent (8).

[0125] Example 9 100 parts by weight of 3-glycidoxypropyltriethoxysilane and 20 parts by weight of a 10% by weight aqueous solution of acetic acid were placed in a reaction vessel and stirred for 6 hours at 50° C. Then, PGMEA was added to the reaction solution to obtain a silane coupling agent (9).

[0126] Comparative Example 1 (Preparation of Silane Coupling Agent) A silane coupling agent (10) was obtained in the same manner as in Example 1, except that ethanol was added from the beginning of the reaction instead of after the reaction was completed. That is, 3-glycidoxypropyltriethoxysilane, an aqueous solution of acetic acid, and ethanol were charged into a reaction vessel, and the reaction vessel was heated at 70° C. for 3 hours under conditions of pH 4, water 6 eq, and ethanol 6 eq. Thereafter, the heat treatment was stopped, and 36.9 g of ethanol was added to 5 g of the resulting crude product to obtain a silane coupling agent (10).

[0127] Comparative Example 2 A reaction vessel was charged with 50 parts by weight of 3-glycidoxypropyltriethoxysilane, 50 parts by weight of PGMEA, and 2 parts by weight of water. The pH inside the reaction vessel was 5. The reaction vessel was heated at 45°C for 30 days. Thereafter, the heat treatment was stopped to obtain a silane coupling agent (11). Silane coupling agent (11) was subjected to Si-NMR measurement, and the results are shown in Figure 4(B).

[0128] The storage stability of the silane coupling agents obtained in Examples 1 to 9 and Comparative Examples 1 and 2 was evaluated by the following method. That is, an experiment was carried out in which the silane coupling agent was allowed to stand at room temperature, and the increase in weight average molecular weight was measured from immediately after the start of the experiment until 40 days later, and the storage stability was evaluated according to the following criteria. Evaluation criteria ◎ (Very good): After 40 days from the start of the experiment, no white precipitate was formed and the increase in weight-average molecular weight was 100 or less. ○ (Good): After 40 days from the start of the experiment, no white precipitate was formed, and the increase in the weight-average molecular weight was more than 100 and less than 500. △ (slightly poor): After 40 days from the start of the experiment, no white precipitate was formed, but the weight-average molecular weight increased by more than 500. × (bad): White precipitate formed

[0129] The results are summarized in Table 1 below. [Table 1]

[0130] Furthermore, the storage stability of the silane coupling agents obtained in Examples 1 and 2 at 5°C or 40°C was evaluated by the following method. An experiment was conducted in which the silane coupling agent was left to stand at 5°C or 40°C, and the increase in weight-average molecular weight was measured from immediately after the start of the experiment until 40 days later. The results are shown in Figure 5.

[0131] Examples 10 to 18, Comparative Examples 3 and 4 A two-component adhesive was obtained containing the silane coupling agents obtained in Examples 1 to 9 and Comparative Examples 1 and 2 (the silicon compound concentrations in the silane coupling agents were changed as shown in Table 2 below by adding the solvents shown in Table 2 below) and the curable composition (1) obtained in Preparation Example 1 below.

[0132] Preparation Example 1 A 300 mL flask (reaction vessel) equipped with a thermometer, stirrer, reflux condenser, and nitrogen inlet tube was charged with 161.5 mmol (39.79 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 9 mmol (1.69 g) of phenyltrimethoxysilane, and 165.9 g of acetone under a nitrogen stream and heated to 50°C. To the resulting mixture, 4.70 g of 5% aqueous potassium carbonate solution (1.7 mmol of potassium carbonate) was added dropwise over 5 minutes, followed by 1700 mmol (30.60 g) of water over 20 minutes. No significant temperature increase occurred during the addition. The polycondensation reaction was then carried out under a nitrogen stream at 50°C for 4 hours. Analysis of the product in the reaction solution after the polycondensation reaction revealed that the number average molecular weight was 1900 and the molecular weight dispersity was 1.5. 29 The ratio of T2 to T3 isomers [T3 / T2] calculated from the Si-NMR spectrum was 10.3. The reaction solution was then cooled and washed with water until the lower layer became neutral. The upper layer was separated and the solvent was then distilled off from the upper layer at 1 mmHg and 40°C until the solvent content was 25% by weight, yielding a colorless, transparent liquid product (epoxy group-containing polyorganosilsesquioxane).

[0133] 100 parts by weight of the obtained epoxy group-containing polyorganosilsesquioxane, 50 parts by weight of propylene glycol monomethyl ether acetate, 0.1 parts by weight of "Sanaid SI-150L" (manufactured by Sanshin Chemical Industry Co., Ltd., antimony-based sulfonium salt), and 0.005 parts by weight of "Sanaid SI Auxiliary Agent" (manufactured by Sanshin Chemical Industry Co., Ltd., (4-hydroxyphenyl)dimethylsulfonium methylsulfite) were mixed to obtain a curable composition (1).

[0134] <Adhesion evaluation> The adhesive properties of the two-component adhesives obtained in the Examples and Comparative Examples were evaluated by the following method. A silane coupling agent whose concentration had been adjusted with a dilution solvent was applied by spin coating to one side of a glass plate (4 inches, manufactured by SCHOTT Japan Co., Ltd.), and heated at 100°C for 15 minutes to obtain a silane coupling agent layer (thickness: 0.01 μm). Then, the curable composition (1) was applied by spin coating to the surface of the obtained silane coupling agent layer to prepare a curable composition layer (thickness: 2.5 μm), thereby obtaining a laminate having a structure of glass plate / silane coupling agent layer / curable composition layer.

[0135] The laminate obtained above was heated at 150°C for 30 minutes, and then heated at 170°C for 30 minutes to be used as a sample. The obtained samples (five for each sample) were evaluated by a cross-cut tape test in accordance with JIS K5400-8.5. ○ (very good adhesion): No peeling in any of the five samples △ (good adhesion): Peeling occurred in 1-2 samples × (poor adhesion): Peeling observed on 3 or more samples

[0136] The results are summarized in Table 2 below. [Table 2]

[0137] Example 19 The silane coupling agent (1) obtained in Example 1 and the curable composition (1) obtained in Preparation Example 1 were mixed and dissolved while changing the amount of silane coupling agent added so that the silicon compound concentration in the silane coupling agent relative to the curable composition (1) would be as shown in Table 3 below, to obtain 10 g of a one-component adhesive.

[0138] Comparative Example 5 A one-component adhesive was obtained in the same manner as in Example 19, except that silane coupling agent (11) was used instead of silane coupling agent (1).

[0139] <Adhesion evaluation> The adhesive properties of the one-component adhesives obtained in Example 19 and Comparative Example 5 were evaluated by the following method. The resulting one-component adhesive was spin-coated onto one side of a glass plate (4 inches, manufactured by SCHOTT Japan Co., Ltd.), heated at 80°C for 4 minutes, then heated at 100°C for 2 minutes to remove residual solvent, and then heated at 150°C for 30 minutes, then heated at 170°C for 30 minutes to obtain a laminate having a glass plate / adhesive layer configuration. The laminates obtained above (number of samples: 5) were evaluated by a cross-cut tape test in accordance with JIS K5400-8.5, using the same evaluation criteria as those for evaluating the adhesion of two-component adhesives.

[0140] The results are summarized in Table 3 below. [Table 3]

[0141] In summary, the configuration of the present disclosure and its variations are noted below. [1] A silane coupling agent containing the following silicon compound and water, wherein the concentration of the silicon compound is 0.01 to 10% by weight: Silicon compound: A compound (I) represented by formula (1) and a polycondensate thereof, wherein the content ratio of the compound (I) to the content of a polycondensate of the compound (I), the polycondensate of the compound (II), having a weight average molecular weight of 200 to 10,000 in terms of standard polystyrene [compound (I) / compound (II); weight ratio] is 1 / 99 to 95 / 5. [2] A silane coupling agent containing the following silicon compound and water, wherein the concentration of the silicon compound is 0.01 to 10% by weight: Silicon compound: A compound (I) represented by formula (1) and a compound represented by formula (3), wherein the ratio of the content of the compound (I) to the content of the compound (II) represented by formula (3) having a weight average molecular weight of 200 to 10,000 in terms of standard polystyrene [compound (I) / compound (II); weight ratio] is 1 / 99 to 95 / 5. [3] The silane coupling agent according to [1] or [2], wherein the content of a polycondensate of compound (I) (or a compound represented by formula (3)) having a weight-average molecular weight of less than 200 in terms of standard polystyrene is 30% by weight or less of the total amount of silicon compounds contained in the silane coupling agent. [4] The silane coupling agent according to [1] or [2], wherein the content of a polycondensate of compound (I) (or a compound represented by formula (3)) having a weight-average molecular weight of more than 10,000 in terms of standard polystyrene is 30% by weight or less of the total amount of silicon compounds contained in the silane coupling agent. [5] The silane coupling agent according to [1] or [2], wherein the total content of the polycondensate of compound (I) (or the compound represented by formula (3)), which is a compound having a weight-average molecular weight of less than 200 in terms of standard polystyrene, and the compound having a weight-average molecular weight of more than 10,000 in terms of standard polystyrene, is 30% by weight or less of the total amount of silicon compounds contained in the silane coupling agent. [6] The silane coupling agent according to any one of [1] to [5], wherein the content of the compound represented by formula (2) is 50% by weight or less of the total amount of silicon compounds contained in the silane coupling agent. [7] The silane coupling agent according to any one of [1] to [6], which has a pH of 4 or less. [8] The silane coupling agent according to any one of [1] to [7], further comprising a solvent having the following properties: Solvent: The evaporation rate is 10-400, assuming that the evaporation rate of butyl acetate is 100. [9] The silane coupling agent according to any one of [1] to [7], further comprising a solvent having the following properties: Solvent: The evaporation rate is 10 to 400, assuming that the evaporation rate of butyl acetate is 100, and the SP value at 25°C is 6 to 15.

[10] The silane coupling agent according to any one of [1] to [7], further comprising an aliphatic alcohol.

[11] The silane coupling agent according to any one of [1] to [7], further containing a monohydric aliphatic alcohol.

[12] Furthermore, monovalent C 2-6 The silane coupling agent according to any one of [1] to [7], which contains an aliphatic alcohol.

[13] The silane coupling agent according to any one of [1] to [7], further containing ethanol.

[14] The silane coupling agent according to any one of [1] to

[13] , which has a viscosity of 1 to 300 mPa·s at 25°C and a rotation speed of 0.5 rpm.

[15] The silane coupling agent according to any one of [1] to

[14] , wherein the increase in weight-average molecular weight, calculated as standard polystyrene, when stored at 25°C for 30 days is 500 or less.

[16] The silane coupling agent according to any one of [1] to

[15] , wherein the increase in weight-average molecular weight, calculated as standard polystyrene, when stored at 40°C for 30 days is 2000 or less.

[17] The silane coupling agent according to any one of [1] to

[16] , which is a surface modifier.

[18] A method for producing a silane coupling agent, comprising: a step of hydrolyzing a compound represented by formula (2) under conditions of pH 4 or less, in the absence of an organic solvent, or in the presence of an organic solvent, in which the content of the organic solvent is 0.7 parts by weight or less per 1 part by weight of the compound represented by formula (2); and a step of subjecting the obtained compound represented by formula (1) to a polycondensation reaction, thereby obtaining the silane coupling agent according to any one of [1] to

[17] .

[19] An adhesive comprising the following silicon compound and a curable compound: Silicon compound: A silicon compound containing a compound (I) represented by formula (1) and a polycondensate thereof, wherein the ratio of the content of the compound (I) to the content of a polycondensate of the compound (I) having a weight average molecular weight of 200 to 10,000 in terms of standard polystyrene [compound (I) / compound (II); weight ratio] is 1 / 99 to 95 / 5.

[20] The adhesive according to

[19] , wherein the content of the silicon compound is 0.01 to 40 parts by weight per 100 parts by weight of the curable compound.

[21] An adhesive comprising the following silicon compound and an epoxy group-containing polyorganosilsesquioxane: Silicon compound: A silicon compound containing a compound (I) represented by formula (1) and a polycondensate thereof, wherein the ratio of the content of the compound (I) to the content of a polycondensate of the compound (I) having a weight average molecular weight of 200 to 10,000 in terms of standard polystyrene [compound (I) / compound (II); weight ratio] is 1 / 99 to 95 / 5.

[22] The adhesive according to

[21] , wherein the content of the silicon compound is 0.01 to 40 parts by weight per 100 parts by weight of the epoxy group-containing polyorganosilsesquioxane.

[23] A three-dimensional laminate having a configuration in which wafers and wafers, chips and chips, or wafers and chips are laminated via the adhesive according to any one of

[19] to

[22] .

[24] A semiconductor device comprising the three-dimensional stack described in

[23] .

[25] A method for producing a three-dimensional laminate, comprising the steps of bonding wafers together, chips together, or wafers together using an adhesive containing the following silicon compound and curable compound: Silicon compound: A silicon compound containing a compound (I) represented by formula (1) and a polycondensate thereof, wherein the ratio of the content of the compound (I) to the content of a polycondensate of the compound (I) having a weight average molecular weight of 200 to 10,000 in terms of standard polystyrene [compound (I) / compound (II); weight ratio] is 1 / 99 to 95 / 5.

[26] Use of the silane coupling agent according to any one of [1] to

[17] as a surface modifier.

[27] Use of a composition containing the following silicon compound and curable compound in an adhesive. Silicon compound: A silicon compound containing a compound (I) represented by formula (1) and a polycondensate thereof, wherein the ratio of the content of the compound (I) to the content of a polycondensate of the compound (I) having a weight average molecular weight of 200 to 10,000 in terms of standard polystyrene [compound (I) / compound (II); weight ratio] is 1 / 99 to 95 / 5.

[28] Use of a composition for an adhesive, which comprises the following silicon compound and a curable compound, wherein the content of the silicon compound is 0.01 to 40 parts by weight per 100 parts by weight of the curable compound: Silicon compound: A silicon compound containing a compound (I) represented by formula (1) and a polycondensate thereof, wherein the ratio of the content of the compound (I) to the content of a polycondensate of the compound (I) having a weight average molecular weight of 200 to 10,000 in terms of standard polystyrene [compound (I) / compound (II); weight ratio] is 1 / 99 to 95 / 5.

[29] Use of a composition containing the following silicon compound and an epoxy group-containing polyorganosilsesquioxane in an adhesive: Silicon compound: A silicon compound containing a compound (I) represented by formula (1) and a polycondensate thereof, wherein the ratio of the content of the compound (I) to the content of a polycondensate of the compound (I) having a weight average molecular weight of 200 to 10,000 in terms of standard polystyrene [compound (I) / compound (II); weight ratio] is 1 / 99 to 95 / 5.

[30] Use of a composition for an adhesive, comprising the following silicon compound and an epoxy group-containing polyorganosilsesquioxane, wherein the content of the silicon compound is 0.01 to 40 parts by weight per 100 parts by weight of the epoxy group-containing polyorganosilsesquioxane: Silicon compound: A silicon compound containing a compound (I) represented by formula (1) and a polycondensate thereof, wherein the ratio of the content of the compound (I) to the content of a polycondensate of the compound (I) having a weight average molecular weight of 200 to 10,000 in terms of standard polystyrene [compound (I) / compound (II); weight ratio] is 1 / 99 to 95 / 5. [Industrial Applicability]

[0142] The silane coupling agent of the present disclosure can firmly bond inorganic and organic substances even at a low concentration, and also has excellent storage stability. When an adhesive containing the silane coupling agent of the present disclosure is used in semiconductor chip stacking techniques such as the WOW method, COW method, or COC method, extremely small and thin wafers or chips can be strongly bonded and fixed, making it possible to produce three-dimensional stacks with high yield.

Claims

1. A silane coupling agent comprising the following silicon compound and water, wherein the concentration of the silicon compound is 0.01 to 10% by weight: Silicon compound: A silicon compound containing a compound (I) represented by the following formula (1) obtained by hydrolyzing a compound represented by the following formula (2) under the following conditions: pH 4 or less, in the absence of an organic solvent or, even if an organic solvent is present, the content of the organic solvent is 0.2 parts by weight or less relative to 1 part by weight of the compound represented by the following formula (2), and the amount of water used is 3 to 12 moles relative to 1 mole of the compound represented by the following formula (2), and a polycondensate thereof, wherein the content ratio of the compound (I) to the content of a compound (II) of the polycondensate of compound (I) having a weight average molecular weight of 200 to 10,000 in terms of standard polystyrene [compound (I) / compound (II; weight ratio]] is 1 / 99 to 95 / 5. 【Chemical 1】 (wherein Y represents a hydrocarbon group having 1 to 10 carbon atoms and containing a group reactive with an organic substance, OR １ ~OR ３ are the same or different and represent hydrolyzable groups) 【Chemistry 2】 (wherein Y represents a hydrocarbon group having 1 to 10 carbon atoms and containing a group reactive with an organic substance)

2. The silane coupling agent according to claim 1, which has a pH of 4 or less.

3. The silane coupling agent according to claim 1 or 2, further comprising a solvent having the following properties: Solvent: The evaporation rate is 10 to 400, assuming that the evaporation rate of butyl acetate is 100.

4. The silane coupling agent according to claim 1 or 2, further comprising a solvent having the following properties: Solvent: The evaporation rate is 10 to 400, where the evaporation rate of butyl acetate is 100, and the SP value at 25°C is 6 to 15.

5. The silane coupling agent according to any one of claims 1 to 4, which is a surface modifier.

6. The compound represented by the following formula (2) can be obtained under the conditions of pH 4 or less, in the absence of an organic solvent or, even if an organic solvent is present, in an amount of 0.2 parts by weight or less per 1 part by weight of the compound represented by the following formula (2). 【Chemistry 3】 (wherein Y represents a hydrocarbon group having 1 to 10 carbon atoms and containing a group reactive with an organic substance, OR 1 ~OR 3 are the same or different and represent hydrolyzable groups) to hydrolyze a compound represented by the following formula (1): 【Chemistry 4】 (wherein Y is the same as above) and subjecting the compound represented by formula (1) to a polycondensation reaction to obtain the silane coupling agent according to any one of claims 1 to 5.

7. An adhesive comprising the following silicon compound and a curable compound: Silicon compound: A silicon compound containing a compound (I) represented by the following formula (1) obtained by hydrolyzing a compound represented by the following formula (2) under the following conditions: pH 4 or less, in the absence of an organic solvent or, even if an organic solvent is present, the content of the organic solvent is 0.2 parts by weight or less relative to 1 part by weight of the compound represented by the following formula (2), and the amount of water used is 3 to 12 moles relative to 1 mole of the compound represented by the following formula (2), and a polycondensate thereof, wherein the content ratio of the compound (I) to the content of a compound (II) of the polycondensate of compound (I) having a weight average molecular weight of 200 to 10,000 in terms of standard polystyrene [compound (I) / compound (II; weight ratio]] is 1 / 99 to 95 / 5. 【Chemistry 5】 (wherein Y represents a hydrocarbon group having 1 to 10 carbon atoms and containing a group reactive with an organic substance, OR １ ~OR ３ are the same or different and represent hydrolyzable groups) 【Chemistry 6】 (wherein Y represents a hydrocarbon group having 1 to 10 carbon atoms and containing a group reactive with an organic substance)

8. 8. The adhesive according to claim 7, wherein the content of the silicon compound is 0.01 to 40 parts by weight per 100 parts by weight of the curable compound.

9. A three-dimensional laminate having a configuration in which wafers are laminated together, chips are laminated together, or wafers are laminated together via the adhesive according to claim 7 or 8.

10. A semiconductor device comprising the three-dimensional stack according to claim 9.

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