Adhesive paste, its application method, and the manufacturing method of semiconductor devices

Abstract

This invention relates to an adhesive paste containing a thermosetting organic polysiloxane compound and a liquid component satisfying requirements 1 and 2 below, wherein the content of the liquid component is 15% by mass or more relative to the total mass of the adhesive paste, and the adhesive paste has a detack time of 20 minutes or more. According to this invention, an adhesive paste can be provided that allows for good mounting of semiconductor devices (excellent wafer mounting performance) even after prolonged placement on a coated object, and exhibits excellent adhesion of the cured product obtained by heating at high temperatures. Furthermore, an adhesive paste is provided that achieves an excellent balance between wafer mounting performance and the adhesion of the cured product obtained under either high-temperature or low-temperature heating conditions. [Requirement 1] Viscosity at 25°C is 20,000 mPa·s or less. [Requirement 2] It is a silane-based compound.

Description

[Technical Field]

[0001] The present invention relates to an adhesive paste that can properly mount semiconductor devices even after being applied to a coated object for a long time, and that the cured product obtained under either high temperature heating or low temperature heating conditions has excellent adhesion; a method of using the adhesive paste as an adhesive for fixing semiconductor devices; and a method of manufacturing a semiconductor device using the adhesive paste as an adhesive for fixing semiconductor devices. [Previous Technology]

[0002] In the past, adhesive pastes have been modified in various ways according to their uses and have been widely used in industry as raw materials, adhesives, coating agents, etc. for optical components, molded bodies, etc. Furthermore, adhesive pastes for semiconductor device fixing materials, such as adhesives for semiconductor device fixing materials, continue to receive attention.

[0003] Semiconductor elements include light-emitting elements such as lasers and light-emitting diodes (LEDs), light-receiving semiconductor elements such as solar cells, transistors, sensors such as temperature sensors and pressure sensors, and integrated circuits.

[0004] Adhesive for semiconductor devices used to fix semiconductor devices is typically applied to a substrate such as a lead frame using a coating apparatus with a discharge tube (needle) as described in Patent Document 1. In such a coating apparatus, for example, the discharge tube descends vertically to approach the substrate, discharges a predetermined amount of adhesive from its front end, and then rises to leave the substrate while the substrate moves laterally. This operation is then repeated to continuously apply the adhesive for semiconductor devices onto the substrate. Subsequently, the semiconductor device is mounted (embedded) on the applied adhesive and bonded to the substrate.

[0005] Normally, after the adhesive paste is applied to the substrate, the semiconductor device is quickly mounted onto the applied adhesive paste and bonded to the substrate. However, in production lines and the like, for various reasons, sometimes the applied adhesive paste is left unattached for an extended period of time without the semiconductor device being installed. In such cases, if the applied adhesive paste is left unattached for a long time, the viscosity of the adhesive paste may change, making it impossible to mount the semiconductor device in a satisfactory condition.

[0006] Furthermore, in recent years, optical semiconductor devices with shorter peak wavelengths, such as blue and white light, have been developed and widely used. The brightness of these short-peak-wavelength optical semiconductor devices has advanced dramatically, but along with this, the heat generated by these devices tends to increase further. However, with the increasing brightness of optical semiconductor devices in recent years, the adhesive used to fix these devices is exposed to higher-energy light and higher-temperature heat generated by the semiconductor devices for extended periods, which may lead to problems such as reduced adhesion, deterioration, and peeling.

[0007] Therefore, there is a need for an adhesive that can properly mount semiconductor devices on the adhesive even after being applied to the coated object for a long time, and that produces a cured product with excellent adhesion when heated at high temperatures.

[0008] On the other hand, optical components and sensor chips used in semiconductor devices are easily affected by heat. Therefore, when using a heat curing method as a method for curing adhesives, from the viewpoint of avoiding the impact of heat on optical components and sensor chips, it is preferable to cure the adhesive at the lowest possible temperature.

[0009] Therefore, in order to precisely adjust the temperature range for obtaining a cured product by heating the adhesive, it is required not only that the cured product obtained by heating at high temperatures has excellent adhesion, but also that the cured product obtained by heating at low temperatures has excellent adhesion. [Prior Art Documents] [Patent Documents]

[0010] [Patent Document 1] Japanese Patent Application Publication No. 2002-009232 [Summary of the Invention]

[0011] [The problem the invention aims to solve]

[0012] The present invention has been made in view of this situation, and its object is to: (i) provide an adhesive paste that can properly mount semiconductor devices even after being placed on a coated object for a long time (excellent wafer mounting performance), and that has excellent adhesion to the cured product obtained by heating at high temperature; (ii) provide an adhesive paste that has an excellent balance between wafer mounting performance and adhesion to the cured product obtained under either high-temperature heating or low-temperature heating; and (iii) provide a method of using such adhesive pastes as adhesives for semiconductor device fixing materials, and a method of manufacturing a semiconductor device using such adhesive pastes as adhesives for semiconductor device fixing materials. Furthermore, in the present invention, "high-temperature heating (hereinafter sometimes referred to as "heating at high temperature")" means "heating at 150°C to 190°C," and "low-temperature heating (hereinafter sometimes referred to as "heating at low temperature")" means "heating at 80°C to 120°C." Moreover, "excellent adhesion" means "high adhesion strength." [Means for solving the problem]

[0013] In order to solve the above problems, the inventors of this invention conducted in-depth research. As a result, it was found that an adhesive paste containing a liquid component of a thermosetting organopolysiloxane compound and a silane compound of a specific viscosity in a specific amount can still properly mount semiconductor devices even after more than 20 minutes when it is applied to the substrate. Furthermore, the adhesion of the cured product obtained under either high-temperature heating or low-temperature heating conditions is excellent, thus completing the present invention.

[0014] Therefore, according to the present invention, the following adhesive pastes [1] to

[12] , the method of using the adhesive paste

[13] , and the method of manufacturing a semiconductor device using the adhesive paste

[14] are provided.

[0015] [1] An adhesive paste containing a thermosetting organic polysiloxane compound (A) and a liquid component (L) satisfying the following requirements 1 and 2, wherein the content of the liquid component (L) is 15% by mass or more relative to the total mass of the adhesive paste, and the tack-free time of the adhesive paste is 20 minutes or more: [Requirement 1] The viscosity at 25°C is 20,000 mPa·s or less; [Requirement 2] It is a silane compound.

[0016] [2] The adhesive as described in [1], wherein the thermosetting organic polysiloxane compound (A) is a polysilsesquioxane compound. [3] The adhesive as described in [1] or [2], wherein the liquid component (L) is at least one selected from the group consisting of difunctional silane compounds, trifunctional silane compounds, and silicone oils. [4] The adhesive as described in [1] or [2] further contains a solvent (S), wherein the solvent (S) contains an organic solvent (SL) with a boiling point of 100°C or higher and less than 254°C. [5] The adhesive as described in [4], wherein the organic solvent (SL) has a boiling point of 100°C or higher and less than 200°C. [6] The adhesive as described in [4], wherein the content of the organic solvent (SL) is 10% by mass or higher and 50% by mass or less relative to the total mass of the adhesive.

[0017] [7] The adhesive paste as described in [1] or [2] further contains the following component (B): (B) component: microparticles. [8] The adhesive paste as described in [1] or [2] wherein the concentration of the solid component is 50% by mass or more and 90% by mass or less. [9] The adhesive paste as described in [1] or [2] wherein, after heating the adhesive paste at 170°C for 2 hours, the mass reduction rate of the adhesive paste before and after heating at 170°C for 2 hours is less than 55%.

[10] The adhesive paste described in [1] or [2] is wherein, when the adhesive paste is heated at 170°C for 2 hours, the mass reduction rate of the adhesive paste before and after heating is set to a mass reduction rate of 170°C for 2 hours, and when the adhesive paste is heated at 100°C for 2 hours, the mass reduction rate of the adhesive paste before and after heating is set to a mass reduction rate of 100°C for 2 hours, and the mass reduction rate of 170°C for 2 hours - the mass reduction rate of 100°C for 2 hours is less than 14%.

[11] The adhesive paste described in [1] or [2] is substantially free of noble metal catalysts.

[12] The adhesive paste described in [1] or [2] is an adhesive for semiconductor device fixing materials.

[0018]

[13] A method of use, wherein the adhesive paste described in any one of [1] to

[12] is used as an adhesive for fixing semiconductor elements.

[14] A method of manufacturing a semiconductor device, wherein the method of manufacturing a semiconductor device using the adhesive paste described in any one of [1] to

[12] as an adhesive for fixing semiconductor elements comprises the following steps (BI) and (BII): Step (BI): applying the adhesive paste to the bonding surface of one or both of the semiconductor element and the support substrate and performing pressure bonding; Step (BII): heating and curing the adhesive paste of the pressure bonding body obtained in step (BI) to fix the semiconductor element to the support substrate. [Effects of the Invention]

[0019] According to the present invention, an adhesive paste can be provided that balances wafer mounting performance, which allows for good mounting of semiconductor devices even after prolonged placement on a coated object, with the adhesion of a cured product obtained by heating at high temperatures. Furthermore, according to the present invention, an adhesive paste with an excellent balance between wafer mounting performance and the adhesion of a cured product obtained under either high-temperature or low-temperature heating conditions can be provided. In addition, according to the present invention, a method of using such adhesive pastes as adhesives for semiconductor device fixing materials can be provided; and a method of manufacturing a semiconductor device using such adhesive pastes as adhesives for semiconductor device fixing materials can be provided.

Implementation Method

[0021] [Form for implementing the invention]

[0022] Hereinafter, the present invention will be described in detail as 1) adhesive paste, 2) method of using adhesive paste, and method of manufacturing semiconductor device using adhesive paste.

[0023] 1) Adhesive The adhesive of the present invention is an adhesive containing a thermosetting organic polysiloxane compound (A) and a liquid component (L) that satisfies the following requirements 1 and 2, wherein the content of the liquid component (L) is 15% by mass or more relative to the total mass of the adhesive, and the tack-free time of the adhesive is 20 minutes or more: [Requirement 1] The viscosity at 25°C is 20,000 mPa·s or less; [Requirement 2] It is a silane compound.

[0024] Furthermore, in this invention, the term "adhesive paste" refers to "a substance that is a viscous liquid at room temperature (23°C) and has a fluid state." Because the adhesive paste of this invention possesses the characteristics described above, it exhibits excellent processability in the coating process. Here, "excellent processability in the coating process" means that "in the coating process, when the adhesive paste is discharged from the discharge tube and then the discharge tube is pulled up, the amount of stringing is small or immediately interrupted, without resin splashing or contamination of the surrounding area due to the diffusion of droplets after coating."

[0025] The adhesive paste of the present invention has a de-adhesion time of 20 minutes or more, preferably 30 minutes or more, more preferably 50 minutes or more, and particularly preferably 70 minutes or more. With a de-adhesion time of 20 minutes or more, the adhesive paste achieves excellent chip mounting properties. The de-adhesion time can be measured using the method described in the examples.

[0026] [Thermosetting Organopolysiloxane Compound (A)] The adhesive of the present invention contains a thermosetting organopolysiloxane compound (A) (hereinafter sometimes referred to as "(A) component"). Because the adhesive of the present invention contains (A) component, a cured product with excellent adhesion can be easily obtained even under temperature conditions of either high temperature heating or low temperature heating.

[0027] The thermosetting organopolysiloxane compound (A) of the present invention is a compound having carbon-silicon bonds and siloxane bonds (-Si-O-Si-) within its molecule. From the viewpoint of easily obtaining an adhesive paste that can readily exhibit excellent adhesion, it is preferable that component (A) is a solid at 25°C. Furthermore, since component (A) is a thermosetting compound, it is preferable to have at least one functional group selected from the group consisting of functional groups capable of undergoing condensation reactions by heating and functional groups capable of undergoing condensation reactions by hydrolysis. As such a functional group, it is preferable to have at least one selected from the group consisting of hydroxyl and alkoxy groups, more preferably hydroxyl or alkoxy groups having 1 to 10 carbon atoms. The main chain structure of the thermosetting organopolysiloxane compound (A) is not limited and can be any of linear, ladder-like, or cage-like structures. For example, a linear main chain structure can be represented by the following formula (a-1); a ladder-like main chain structure can be represented by the following formula (a-2); and a cage-like main chain structure can be represented by the following formula (a-3).

[0028] [Chemical Formula 1]

[0029] [Chemical Formula 2]

[0030] [Chemical Formula 3]

[0031] In formulas (a-1) to (a-3), Rx, Ry, and Rz each independently represent a hydrogen atom or an organic group. Preferably, the organic group is an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aromatic group, or an alkylsilyl group. The plurality of Rx in formula (a-1), the plurality of Ry in formula (a-2), and the plurality of Rz in formula (a-3) may be the same as or different from each other. However, there will not be a case where both Rx in formula (a-1) are hydrogen atoms.

[0032] The alkyl groups that are unsubstituted or have substituents as described above can be exemplified by, for example, alkyl groups with 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, etc.

[0033] Cycloalkyl groups that are unsubstituted or have substituents can be listed as, for example, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, etc., having 3 to 10 carbon atoms.

[0034] Examples of alkenyl groups that are unsubstituted or have substituents include, for example, alkenyl groups with 2 to 10 carbon atoms such as vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, and 3-butenyl.

[0035] As substituents for the above-mentioned alkyl, cycloalkyl and alkenyl groups, examples include, for example, halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.; hydroxyl groups; thiol groups; epoxy groups; glycidoxy groups; (meth)acryloyloxy groups; unsubstituted or substituted aromatic groups such as phenyl, 4-methylphenyl, 4-chlorophenyl groups, etc.

[0036] Aromatic groups that are unsubstituted or have substituents can be exemplified by, for example, aromatic groups with 6 to 10 carbon atoms such as phenyl, 1-naphthyl, and 2-naphthyl.

[0037] As substituents for the above-mentioned aromatic groups, examples include halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; alkyl groups such as methyl and ethyl with 1 to 6 carbon atoms; alkoxy groups such as methoxy and ethoxy with 1 to 6 carbon atoms; nitro groups; cyano groups; hydroxyl groups; thiols; epoxy groups; epoxypropoxy groups; (meth)acryloxy groups; and unsubstituted or substituent aromatic groups such as phenyl, 4-methylphenyl, and 4-chlorophenyl groups.

[0038] As alkylsilyl groups, examples include trimethylsilyl, triethylsilyl, triisopropylsilyl, tritertylbutylsilyl, methyldiethylsilyl, dimethylsilyl, diethylsilyl, methylsilyl, ethylsilyl, etc.

[0039] Wherein, Rx, Ry, and Rz are preferably hydrogen atoms, unsubstituted or substituted alkyl groups having 1 to 6 carbon atoms, or phenyl groups, and particularly preferably unsubstituted or substituted alkyl groups having 1 to 6 carbon atoms.

[0040] The thermosetting organopolysiloxane compound (A) can be obtained by, for example, conventional manufacturing methods of condensation polymerization of a silane compound having hydrolyzable functional groups (alkoxy groups, halogen atoms, etc.).

[0041] The silane compound used can be appropriately selected according to the structure of the target thermosetting organopolysiloxane compound (A). Preferred examples include difunctional silane compounds such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, and diethyldiethoxysilane; and trifunctional silane compounds such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and phenyldiethoxymethoxysilane. Tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetratert-butoxysilane, tetradi-butoxysilane, methoxytriethoxysilane, dimethoxydiethoxysilane, trimethoxyethoxysilane, and other tetrafunctional silane compounds.

[0042] The mass average molecular weight (Mw) of the thermosetting organopolysiloxane compound (A) is typically 800 or more and 30,000 or less; preferably 1,000 or more and 20,000 or less; more preferably 1,200 or more and 15,000 or less; and particularly preferably 3,000 or more and 10,000 or less. By using a thermosetting organopolysiloxane compound (A) with a mass average molecular weight (Mw) within the above range, it is easy to obtain an adhesive paste that provides better heat resistance and adhesion.

[0043] The molecular weight distribution (Mw / Mn) of the thermosetting organopolysiloxane compound (A) is not particularly limited, and is generally 1.0 or higher and 10.0 or lower; preferably 1.1 or higher and 6.0 or lower. By using a thermosetting organopolysiloxane compound (A) with a molecular weight distribution (Mw / Mn) within the above range, it is easy to obtain an adhesive that provides a cured product with superior heat resistance and adhesion. The mass average molecular weight (Mw) and number average molecular weight (Mn) of the thermosetting organopolysiloxane compound (A) can be obtained by, for example, by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, converting them to standard polystyrene equivalents.

[0044] The thermosetting organopolysiloxane compound (A) of the present invention is preferably a polysilsesquioxane compound formed by the condensation polymerization of a trifunctional organosiloxane compound. Since the adhesive of the present invention contains a polysilsesquioxane compound as component (A), a cured product with superior adhesion can be easily obtained even under either high-temperature heating or low-temperature heating conditions.

[0045] The polysilsesquioxane compound of the present invention is a compound having repeating units represented by the following formula (a-4). Since the adhesive of the present invention contains a polysilsesquioxane compound having repeating units represented by the following formula (a-4) as component (A), a cured product with better adhesion can be easily obtained even under temperature conditions of either high temperature heating or low temperature heating.

[0046] [Chemical Formula 4]

[0047] In formula (a-4), R1 represents an organic group. Preferably, the organic group is selected from the group consisting of unsubstituted alkyl, substituted alkyl, unsubstituted cycloalkyl, substituted cycloalkyl, unsubstituted alkenyl, substituted alkenyl, unsubstituted aromatic, substituted aromatic and alkylsilyl groups; more preferably, it is selected from the group consisting of unsubstituted alkyl with 1 to 10 carbon atoms, substituted alkyl with 1 to 10 carbon atoms, unsubstituted aromatic with 6 to 12 carbon atoms, and substituted aromatic with 6 to 12 carbon atoms.

[0048] Examples of "unsubstituted alkyl groups having 1 to 10 carbon atoms" include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, and n-decyl. The number of carbon atoms in the "unsubstituted alkyl group having 1 to 10 carbon atoms" represented by R1 is preferably 1 to 6, and more preferably 1 to 3.

[0049] The number of carbon atoms in the "alkyl group having 1 to 10 carbon atoms" represented by R1 is preferably 1 to 6, and more preferably 1 to 3. Furthermore, this number of carbon atoms refers to the number of carbon atoms excluding the substituent portion (the alkyl portion). Therefore, when R1 is "an alkyl group having 1 to 10 carbon atoms," the number of carbon atoms in R1 may exceed 10. Examples of alkyl groups that are the same as those exemplified as "unsubstituted alkyl groups having 1 to 10 carbon atoms" can be listed as "alkyl groups having 1 to 10 carbon atoms."

[0050] Examples of substituents for "alkyl groups having 1 to 10 carbon atoms" include halogen atoms such as fluorine, chlorine, and bromine; cyano groups; and groups represented by the formula OG. The number of atoms (excluding hydrogen atoms) of the substituents for "alkyl groups having 1 to 10 carbon atoms" is typically 1 to 30, preferably 1 to 20. Here, G represents a protecting group for the hydroxyl group. There are no particular limitations on the protecting group for the hydroxyl group, and known protecting groups for the hydroxyl group can be listed. For example, examples include acyl groups; silyl groups such as trimethylsilyl, triethylsilyl, tributyldimethylsilyl, and tributyldiphenylsilyl; acetal groups such as methoxymethyl, methoxyethoxymethyl, 1-ethoxyethyl, tetrahydropyran-2-yl, and tetrahydrofuran-2-yl; alkoxycarbonyl groups such as tributoxycarbonyl; and ether groups such as methyl, ethyl, tributyl, octyl, allyl, triphenylmethyl, benzyl, p-methoxybenzyl, fluorenyl, trimethylol, and diphenylmethyl.

[0051] Examples of "an aromatic group having 6 to 12 unsubstituted carbon atoms" include phenyl, 1-naphthyl, and 2-naphthyl. The number of carbon atoms in the "aromatic group having 6 to 12 unsubstituted carbon atoms" represented by R1 is preferably 6.

[0052] The number of carbon atoms in the "aromatic group having 6 to 12 carbon atoms with substituents" represented by R1 is preferably 6. Furthermore, this number of carbon atoms refers to the number of carbon atoms excluding the portion with substituents (the aromatic group portion). Therefore, when R1 is "aromatic group having 6 to 12 carbon atoms with substituents," the number of carbon atoms in R1 may exceed 12. The aromatic group that is "aromatic group having 6 to 12 carbon atoms with substituents" can be the same as those exemplified as "aromatic group having 6 to 12 unsubstituted carbon atoms."

[0053] Examples of substituents for "aromatic groups having 6 to 12 carbon atoms" include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, tributyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, etc.; halogen atoms such as fluorine, chlorine, bromine, etc.; alkoxy groups such as methoxy, ethoxy, etc. The number of atoms of the substituents for "aromatic groups having 6 to 12 carbon atoms" (excluding hydrogen atoms) is usually 1 to 30, preferably 1 to 20.

[0054] From the viewpoint that structurally stable polysilsesquioxane compounds can be easily obtained, and that the adhesive has more stable performance, R1 is preferably selected from at least one of the group consisting of unsubstituted alkyl groups having 1 to 10 carbon atoms, alkyl groups having 1 to 10 carbon atoms containing fluorine atoms, and unsubstituted aromatic groups having 6 to 12 carbon atoms. By using a polysilsesquioxane compound in which R1 is an unsubstituted alkyl group having 1 to 10 carbon atoms, it is easy to obtain an adhesive that provides a cured product with better heat resistance and adhesion. By using a polysilsesquioxane compound in which R1 is an alkyl group having 1 to 10 carbon atoms containing fluorine atoms, it is easy to obtain adhesives and cured products with long de-adhesion time and low refractive index, and therefore, it is easy to apply to optical semiconductor devices that require low refractive index. As alkyl groups having fluorine atoms and 1 to 10 carbon atoms, examples include those represented by the formula: CmH(2m-n+1)Fn (where m is an integer from 1 to 10; n is an integer greater than or equal to 1 and less than (2m+1)). 3,3,3-trifluoropropyl is preferred. By using polysilicon silsesquioxane compounds where R1 is an unsubstituted aromatic group with 6 to 12 carbon atoms, adhesives and cured products with high refractive indices can be readily obtained, making them readily applicable to optical semiconductor devices requiring high refractive indices.

[0055] The proportion of the repeating unit (i.e., the T site described below) in the polysilicon silsesquioxane compound, relative to all repeating units, is typically 50–100 mol%, more preferably 70–100 mol%, further preferably 90–100 mol%, and particularly preferably 100 mol%. By using a polysilicon silsesquioxane compound with the above-described proportion of repeating units (T sites) represented by formula (a-4), adhesives that readily exhibit heat resistance, adhesion, and refractive index properties can be obtained. If, for example, the assignment of NMR peaks and the integration of areas are feasible, the proportion of the repeating unit (T site) in the polysilicon silsesquioxane compound represented by formula (a-4) can be determined by measuring 29Si-NMR and 1H-NMR.

[0056] Polysilsesquioxane compounds are soluble in various organic solvents, including ketone solvents such as acetone; aromatic hydrocarbon solvents such as benzene; sulfur-containing solvents such as dimethyl sulfoxide; ether solvents such as tetrahydrofuran; ester solvents such as ethyl acetate; halogen-containing solvents such as chloroform; and mixtures of two or more of the above solvents. Therefore, using these solvents, it is possible to determine the 29Si-NMR of polysilsesquioxane compounds in solution.

[0057] The repeating unit represented by the above formula (a-4) is preferably the repeating unit represented by the following formula (a-5).

[0058] [Chemical Formula 5]

[0059] As shown in formula (a-5), the polysilicon silsesquioxane compound has a partial structure of three oxygen atoms bonded to a silicon atom, generally referred to as the T site, and an additional group (R1) bonded to this silicon atom.

[0060] In formula (a-5), R1 has the same meaning as R1 in formula (a-4) above. * represents a Si atom, a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, and at least one of the three * is a Si atom. Examples of alkyl groups having 1 to 10 carbon atoms as * include methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, isobutyl, tertiary butyl, etc. The plurality of * can be the same as each other or different from each other.

[0061] Furthermore, polysilsesquioxane compounds are thermosetting compounds, meaning they can undergo condensation reactions by heating and / or by hydrolysis. Therefore, at least one of the * in the above formula (a-5) of the plurality of repeating units (T sites) of the polysilsesquioxane compound is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom. Also, when the polysilsesquioxane compound is soluble in the solvent used for determination, the presence or absence of hydrogen atoms or alkyl groups having 1 to 10 carbon atoms at the * in the above formula (a-5), and whether all three * in the above formula (a-5) are repeating units with Si atoms, can be confirmed by measuring 29Si-NMR. Furthermore, if the assignment of the 29Si-NMR peaks and the integration of the areas are feasible, the total number of repeating units (T sites) represented by formula (a-4) in the polysilicon silsesquioxane compound can be calculated relative to the total number of repeating units (T sites) represented by formula (a-4) in the polysilicon silsesquioxane compound. From the viewpoint of easily obtaining an adhesive that provides a cured product with superior heat resistance, the total number of repeating units (T sites) represented by formula (a-4) in the polysilicon silsesquioxane compound represented by formula (a-5) represented by formula (a-4) in formula (a-5) is preferably 30–95 mol%, and more preferably 40–90 mol%.

[0062] The polysilsesquioxane compound may be a homopolymer having one R1 or a copolymer having two or more R1s.

[0063] When the polysilicon silsesquioxane compound is a copolymer, it can be any of a random copolymer, block copolymer, graft copolymer, alternating copolymer, etc., but from the viewpoint of ease of manufacture, a random copolymer is preferred. Furthermore, the structure of the polysilicon silsesquioxane compound can be any of a ladder structure, a double-deck structure, a cage structure, a partially cracked cage structure, a cyclic structure, or a random structure.

[0064] In this invention, the polysilsesquioxane compound can be used alone or in combination of two or more.

[0065] There is no particular limitation on the method of manufacturing polysilsesquioxane compounds. For example, at least one of the silane compounds (1) represented by the following formula (a-6) can be condensed to produce polysilsesquioxane compounds.

[0066] [Chemical Formula 6]

[0067] (In the formula, R1 represents the same meaning as R1 in the above formula (a-4). R2 represents an alkyl group having 1 to 10 carbon atoms, X1 represents a halogen atom, and p represents an integer from 0 to 3. Multiple R2s may be the same as or different from each other, and multiple X1s may be the same as or different from each other.) Alkyl groups having 1 to 10 carbon atoms as R2 can be the same as those exemplified as the alkyl groups having 1 to 10 carbon atoms * in the above formula (a-5). Halogen atoms as X1 can include chlorine atoms and bromine atoms, etc.

[0068] Specific examples of silane compounds (1) include alkyl trialkoxysilane compounds such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and ethyltripropoxysilane; alkyl halogenoalkoxysilane compounds such as methylchlorodimethoxysilane, methylchlorodiethoxysilane, methyldichloromethoxysilane, methylbromodimethoxysilane, ethylchlorodimethoxysilane, ethylchlorodiethoxysilane, ethyldichloromethoxysilane, and ethylbromodimethoxysilane; and alkyl trihalogenosilane compounds such as methyltrichlorosilane, methyltribromosilane, ethyltrichlorosilane, and ethyltribromosilane.

[0069] Substituted alkyltrialkoxysilane compounds such as 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 2-cyanoethyltrimethoxysilane, 2-cyanoethyltriethoxysilane; Substituted alkylhalogenated alkoxysilane compounds such as 3,3,3-trifluoropropylchlorodimethoxysilane, 3,3,3-trifluoropropyldichloromethoxysilane, 3,3,3-trifluoropropyldichloroethoxysilane, 2-cyanoethylchlorodimethoxysilane, 2-cyanoethyldichloromethoxysilane, 2-cyanoethyldichloroethoxysilane; Substituted alkyl trihalomethane compounds such as 3,3,3-trifluoropropyltrichlorosilane and 2-cyanoethyltrichlorosilane;

[0070] Phenyltrimethoxysilane compounds, such as phenyltrimethoxysilane and 4-methoxyphenyltrimethoxysilane, with or without substituents; phenylhaloalkoxysilane compounds, such as phenylchlorodimethoxysilane, phenyldichloromethoxysilane, 4-methoxyphenylchlorodimethoxysilane, 4-methoxyphenyldichloromethoxysilane, etc., with or without substituents; phenyltrihalide silane compounds, such as phenyltrichlorosilane and 4-methoxyphenyltrichlorosilane, etc., with or without substituents, etc. These silane compounds (1) can be used alone or in combination of two or more.

[0071] The method for condensing the above-mentioned silane compound (1) is not particularly limited. For example, a method can be given in which a predetermined amount of condensation catalyst is added to the silane compound (1) in a solvent or in a solvent-free state, and the mixture is stirred at a predetermined temperature. More specifically, the following methods can be given: (a) a method in which a predetermined amount of acid catalyst is added to the silane compound (1) and the mixture is stirred at a predetermined temperature; (b) a method in which a predetermined amount of base catalyst is added to the silane compound (1) and the mixture is stirred at a predetermined temperature; (c) a method in which a predetermined amount of acid catalyst is added to the silane compound (1), the mixture is stirred at a predetermined temperature, an excess of base catalyst is added to make the reaction system alkaline, and the mixture is stirred at a predetermined temperature, etc. Among these, method (a) or method (c) is preferred because the desired polysilicon silsesquioxane compound can be obtained efficiently.

[0072] The polymerization catalyst used can be either an acid catalyst or a base catalyst. Furthermore, two or more polymerization catalysts can be used in combination, but it is preferable to use at least an acid catalyst. Examples of acid catalysts include inorganic acids such as phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, and nitrates; and organic acids such as citric acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid. Preferably, it is selected from at least one of phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, citric acid, acetic acid, and methanesulfonic acid.

[0073] As a base catalyst, examples include ammonia; organic bases such as trimethylamine, triethylamine, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, pyridine, 1,8-diazabicyclo[5.4.0]-7-undecene, aniline, picoline, 1,4-diazabicyclo[2.2.2]octane, and imidazole; organic salt hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; and metal alkoxides such as sodium methoxy, sodium ethoxy, sodium tributoxy, and potassium tributoxy. Alkoxide; metal hydrides of sodium hydride, calcium hydride, etc.; metal hydroxides of sodium hydroxide, potassium hydroxide, calcium hydroxide, etc.; metal carbonates of sodium carbonate, potassium carbonate, magnesium carbonate, etc.; metal bicarbonates of sodium bicarbonate, potassium bicarbonate, etc.

[0074] The amount of condensation polymerization catalyst used, relative to the total moles (mol) of silane compound (1), is typically in the range of 0.05 to 10 mol%, preferably in the range of 0.1 to 5 mol%.

[0075] When using a solvent during condensation polymerization, the solvent used can be appropriately selected according to the type of silane compound (1). For example, water; aromatic hydrocarbons such as benzene, toluene, and xylene; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, and tertiary butanol. These solvents can be used alone or in combination. Furthermore, when using the method described in (c) above, after the condensation polymerization reaction is carried out in an aqueous system in the presence of an acid catalyst, an organic solvent and an alkaline catalyst (such as ammonia) can be added to the reaction solution, and the condensation polymerization reaction can be further carried out under neutral or alkaline conditions.

[0076] The amount of solvent used is typically 0.001 liters or more and 10 liters or less per mol of the total amount of silane compound (1); preferably 0.01 liters or more and 0.9 liters or less.

[0077] The temperature for condensation polymerization of the silane compound (1) is generally in the range of 0°C to the boiling point of the solvent used, preferably 20°C or higher and 100°C or lower; more preferably 30°C or higher and 95°C or lower. If the reaction temperature is too low, the condensation polymerization reaction may not proceed sufficiently. On the other hand, if the reaction temperature is too high, it is difficult to suppress gelation. The reaction is usually completed within 30 minutes to 30 hours.

[0078] Furthermore, depending on the type of monomer used, it may be difficult to achieve a high molecular weight. For example, monomers with alkyl groups containing fluorine atoms tend to have lower reactivity than monomers with R1 being a general alkyl group. In such cases, by reducing the amount of catalyst and conducting the reaction under mild conditions for a longer period of time, it becomes easier to obtain polysilicon silsesquioxane compounds with the target molecular weight.

[0079] After the reaction is complete, if an acid catalyst is used, an alkaline aqueous solution such as sodium bicarbonate is added to the reaction solution; if an alkaline catalyst is used, an acid such as hydrochloric acid is added to the reaction solution to neutralize it. The salt generated at this time is removed by filtration, washing with water, etc., and the target polysilsesquioxane compound is obtained.

[0080] When polysilicon silsesquioxane compounds are manufactured by the above method, the portion of the silane compound (1) that has not undergone hydrolysis and subsequent condensation reaction remains in the polysilicon silsesquioxane compound.

[0081] (A) When the component is a polysilicon silsesquioxane compound obtained by, for example, the condensation polymerization of a silane compound (1), curing is carried out by a condensation reaction. Therefore, the adhesive of the present invention is different from general heat-curing type organosilicone adhesives that are cured by an addition reaction in the presence of a noble metal catalyst such as a platinum catalyst. Therefore, the adhesive of the present invention containing a polysilicon silsesquioxane compound does not substantially contain a noble metal catalyst, or the content of the noble metal catalyst is very low. Here, "does not substantially contain a noble metal catalyst, or the content of the noble metal catalyst is very low" means "except that no component that can be interpreted as a noble metal catalyst is intentionally added, and the content of the noble metal catalyst, converted by the mass of the catalyst metal element relative to the amount of the active ingredient in the adhesive, is, for example, less than 1 ppm by mass". Also, here, "active ingredient" means "components other than the solvent (S) (described later) contained in the adhesive". From the perspectives of stable manufacturing of blending deviations, preservation stability, and the fact that precious metal catalysts are high-priced substances, it is preferable that the paste does not contain precious metal catalysts or contains very little precious metal catalyst.

[0082] [Liquid Component (L)] The liquid component (L) constituting the adhesive of the present invention (hereinafter sometimes referred to as "(L) component") is something that satisfies the following requirements 1 and 2. [Requirement 1] Its viscosity at 25°C is 20,000 mPa·s or less. [Requirement 2] It is a silane compound. Because it is a silane compound, the liquid component (L) is easily and well mixed with component (A), and a stable adhesive can be easily obtained. Examples of liquid components (L) that satisfy the above requirements 1 and 2 include difunctional silane compounds, trifunctional silane compounds, and silicone oils.

[0083] The viscosity of the liquid component (L) at 25°C is 20,000 mPa·s or less, preferably 10,000 mPa·s or less, more preferably 7,000 mPa·s or less, and especially preferably 5,000 mPa·s or less. Since adhesives containing a liquid component (L) with a viscosity at 25°C below the aforementioned upper limit do not readily evaporate at room temperature (20°C ± 15°C), adhesives with a longer detack time can be easily obtained. On the other hand, since adhesives containing a liquid component (L) with a viscosity at 25°C greater than the aforementioned upper limit have a higher viscosity, there is a risk of shortening the detack time of the adhesive; however, by bringing it below the aforementioned upper limit, this risk can be reduced. Furthermore, by using a liquid component (L) with a viscosity below the aforementioned upper limit at 25°C, it is easy to obtain an adhesive paste that exhibits excellent processability during the coating process and provides superior adhesion, heat resistance, and crack inhibition of the cured product under either high-temperature or low-temperature heating conditions. Here, "superior crack inhibition of the cured product" means that "when the adhesive paste is heated to obtain a cured product, cracking of the cured product does not occur with temperature changes."

[0084] As difunctional silane compounds, examples include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, etc.

[0085] As a difunctional silane compound, commercially available products can also be used. Examples of commercially available products include the KBM series such as KBM-22, KBM-202SS, and KBM-402, and the KBE series such as KBE-22, KBE-402, and KBE-502 (all manufactured by Shin-Etsu Chemical Co., Ltd.). Among these, from the viewpoint of easy mixing with other active ingredients and easy obtaining of a stable adhesive paste, KBM-202SS is preferred.

[0086] As a trifunctional silane compound, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyldiethoxymethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxy Silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3) (-Dimethyl-Butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-propyltriethoxysilane, 2-trimethoxysilylethylsuccinic anhydride, 2-triethoxysilylethylsuccinic anhydride, 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-mercaptopropyltrimethoxysilane, etc.

[0087] Commercially available products can also be used as trifunctional silane compounds. Examples of commercially available products include, for instance, the KBM series such as KBM-103, KBM-303, KBM-503, and KBM-5103; the KBE series such as KBE-13, KBE-103, and KBE-9007N; and X-12-967C (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.). Among these, from the viewpoint of easy mixing with other active ingredients and easy obtaining of adhesive paste with stable performance, X-12-967C, KBM-103, KBM-503, KBM-5103, and KBE-9007N are preferred, and X-12-967C, KBM-5103, and KBE-9007N are particularly preferred.

[0088] Examples of polyfunctional silane compounds include compounds that have a nitrogen atom in their molecule and have four or more alkoxy groups bonded to silicon atoms; and compounds with an organic main chain and having organic functional groups and four or more alkoxy groups bonded to silicon atoms. The term "having four or more alkoxy groups bonded to silicon atoms" refers to a total number of four or more alkoxy groups bonded to the same silicon atom and alkoxy groups bonded to different silicon atoms.

[0089] Examples of polyfunctional silane compounds that have nitrogen atoms in the molecule and more than four alkoxy groups bonded to silicon atoms include isocyanurate compounds and urea compounds.

[0090] As isocyanurate compounds, compounds represented by the following formula (1-1) can be listed, and as urea compounds, compounds represented by the following formula (1-2) can be listed.

[0091] [Chemical Formula 7]

[0092] In the formula, Ra represents an alkoxy group having 1 to 6 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, or tributoxy. Multiple Ra groups may be identical or different from each other. t1 to t5 each independently represent an integer from 1 to 10, preferably an integer from 1 to 6, and especially preferably 3.

[0093] Specific examples of compounds represented by formula (1-1) include 1,3,5-N-trimethoxysilylpropyl isocyanurate, 1,3,5-N-trimethoxysilylpropyl isocyanurate, 1,3,5-N-trimethoxysilylpropyl isocyanurate, 1,3,5-N-trimethoxysilylpropyl isocyanurate, 1,3,5-N-trimethoxysilylpropyl isocyanurate, 1,3,5-N-tributoxysilylpropyl isocyanurate, and other 1,3,5-N-trimethoxysilylpropyl isocyanurate [(tri(carbon number 1 to 6)alkoxy)silyl(carbon number 1 to 10)alkyl]isocyanurate; 1,3,5-N-Tris(3-dimethoxymethylsilylpropyl)isocyanurate, 1,3,5-N-Tris(3-dimethoxyethylsilylpropyl)isocyanurate, 1,3,5-N-Tris(3-dimethoxyisopropylsilylpropyl)isocyanurate, 1,3,5-N-Tris(3-dimethoxyn-propylsilylpropyl)isocyanurate, 1,3,5-N-Tris(3-dimethoxyphenylsilylpropyl)isocyanurate, 1,3,5-N-Tris(3-diethoxy)isocyanurate 1,3,5-N-Tris(3-diethoxyethylsilylpropyl) isocyanurate, 1,3,5-N-Tris(3-diethoxyisopropylsilylpropyl) isocyanurate, 1,3,5-N-Tris(3-diethoxyn-propylsilylpropyl) isocyanurate, 1,3,5-N-Tris(3-diethoxyphenylsilylpropyl) isocyanurate, 1,3,5-N-Tris(3-diisopropoxymethylsilylpropyl) isocyanuric acid Ester, 1,3,5-N-Tris(3-diisopropoxyethylsilylpropyl)isocyanurate, 1,3,5-N-Tris(3-diisopropoxyisopropylsilylpropyl)isocyanurate, 1,3,5-N-Tris(3-diisopropoxyn-propylsilylpropyl)isocyanurate, 1,3,5-N-Tris(3-diisopropoxyphenylsilylpropyl)isocyanurate, 1,3,5-N-Tris(3-dibutoxymethylsilylpropyl)isocyanurate, 1,3,5-N- Examples of isocyanurates include 1,3,5-N-tris(3-dibutoxyethylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dibutoxyisopropylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dibutoxy-n-propylsilylpropyl)isocyanurate, and 1,3,5-N-tris(3-dibutoxyphenylsilylpropyl)isocyanurate, as well as 1,3,5-N-tris[(di(alkoxy)silyl(carbon number 1 to 10)alkyl]isocyanurate.

[0094] Specific examples of compounds represented by formula (1-2) include N,N'-bis(3-trimethoxysilylpropyl)urea, N,N'-bis(3-triethoxysilylpropyl)urea, N,N'-bis(3-tripropoxysilylpropyl)urea, N,N'-bis(3-tributoxysilylpropyl)urea, N,N'-bis(2-trimethoxysilylethyl)urea, and N,N'-bis[(tri(1 to 6 carbon atoms)alkoxysilyl)(1 to 10 carbon atoms)alkyl]urea; N,N'-bis(3-dimethoxymethylsilylpropyl)urea, N,N'-bis(3-dimethoxyethylsilylpropyl)urea, N,N'-bis(3-diethoxymethylsilylpropyl)urea, etc., including N,N'-bis[(di(1-6 carbon atoms)alkoxy(1-6 carbon atoms)alkylsilyl(1-10 carbon atoms)alkyl)urea; N,N'-bis(3-dimethoxyphenylsilylpropyl)urea, N,N'-bis(3-diethoxyphenylsilylpropyl)urea, etc., including N,N'-bis[(di(1-6 carbon atoms)alkoxy(6-20 carbon atoms)aromaticsilyl(1-10 carbon atoms)alkyl)urea, etc.

[0095] Commercially available products may also be used as compounds having a nitrogen atom in the molecule and having four or more alkoxy groups bonded to silicon atoms in the molecule. Examples of commercially available products include, for instance, KBM-9659 (manufactured by Shin-Etsu Chemical Co., Ltd.). Among these, KBM-9659 is preferred from the viewpoint that it is easy to mix well with other active ingredients and that it is easy to obtain a stable adhesive paste.

[0096] Commercially available products may also be used as compounds with an organic main chain structure and having organic functional groups and four or more alkoxy groups bonded to silicon atoms. Examples of commercially available products include X-12-1048, X-12-981S, and X-12-1159L (all manufactured by Shin-Etsu Chemical Co., Ltd.). Among these, X-12-1159L is preferred from the viewpoint that it is easy to mix well with other active ingredients and that it is easy to obtain a stable adhesive paste.

[0097] As a silicone oil, it can be a linear silicone oil or a modified silicone oil. Linear silicone oil is a linear polymer compound formed by siloxane bonds, and examples include dimethyl silicone oil, methyl phenyl silicone oil, and methyl hydrogen silicone oil.

[0098] Modified silicone oils have organic groups introduced into the side chains, ends, etc. of polysiloxanes. Based on the bonding position of the introduced organic groups, modified silicone oils can be classified as side-chain type, two-terminal type, single-terminal type, and side-chain two-terminal type. Furthermore, based on the nature of the introduced organic groups, they can be classified as reactive silicone oils and non-reactive silicone oils. Examples of organic groups include amino groups, epoxy groups, methacrylate groups, acrylic groups, silanol groups, and carboxyl groups.

[0099] Commercially available silicone oils can also be used. Examples of commercially available linear silicone oils include, for example, the KF-96L series, KF-50 series, and KF-99 series (all manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of commercially available modified silicone oils include, for example, the KF series such as KF-868 with monoamines introduced into the side chain, X-22-2445 with acrylic groups introduced into both ends, and the X-22-173 series such as X-22-173BX with epoxy groups introduced into one end (all manufactured by Shin-Etsu Chemical Co., Ltd.), and XF42-334 (manufactured by Momentive Performance Materials Japan Co., Ltd.). From the viewpoint of easy mixing with other active ingredients and easy obtaining of a stable adhesive paste, modified silicone oils are preferred, and X-22-2445 and XF42-334 are particularly preferred.

[0100] Among these liquid components (L), from the viewpoint of easily obtaining an adhesive with a longer detack time, difunctional silane compounds, trifunctional silane compounds, and silicone oils are preferred, with difunctional silane compounds and silicone oils being particularly preferred. Furthermore, from the viewpoint of easily obtaining an adhesive with excellent adhesion strength of the cured product obtained by heating at low temperatures, trifunctional silane compounds and silicone oils are particularly preferred. The liquid component (L) can be used alone or in combination of two or more.

[0101] The content of the liquid component (L) relative to the total mass of the adhesive is 15% by mass or more; preferably 17% by mass or more and less than 50% by mass, more preferably 19% by mass or more and less than 40% by mass, and especially preferably 21% by mass or more and less than 35% by mass. By making the content of the liquid component (L) relative to the total mass of the adhesive within the above range, the effect of using the liquid component (L) can be further enhanced.

[0102] [Other Components] The adhesive of the present invention is a substance containing a thermosetting organic polysiloxane compound (A) and a liquid component (L), but it may also contain the components shown below. (1) Solvent (S) The solvent (S) contained in the adhesive of the present invention is not particularly limited as long as it can dissolve or disperse the components of the adhesive of the present invention. As the solvent (S), it is preferable to contain an organic solvent (SL) with a boiling point of 100°C or higher and lower than 254°C. Here, "boiling point" means "boiling point at 1013 hPa" (the same applies throughout this specification). The boiling point of the organic solvent (SL) is 100°C or higher and lower than 254°C; preferably 100°C or higher and lower than 200°C; more preferably 105°C or higher and lower than 185°C; and particularly preferably 110°C or higher and lower than 170°C.

[0103] Compared to high-boiling-point organic solvents with boiling points above 254°C and below 300°C, such organic solvents (SL) evaporate more efficiently when heated at low temperatures. Therefore, by using organic solvent (SL) as solvent (S), it is easy to obtain an adhesive paste with a mass reduction rate of less than 14% after 2 hours at 170°C to 2 hours at 100°C (described later). Furthermore, compared to low-boiling-point organic solvents with boiling points below 100°C, such organic solvents (SL) evaporate more slowly. As a result, adhesive pastes containing organic solvents (SL) evaporate more efficiently when heated at low temperatures without leaving a large amount of solvent residue, thus easily achieving sufficient adhesive strength. In addition, even when heated at low temperatures, the concentration of the active ingredient in the adhesive paste increases rapidly, making it easy to cure. Therefore, even after being applied to a substrate and left for a long time, semiconductor devices can be well mounted, and the cured product exhibits excellent adhesion.

[0104] Specific examples of organic solvents (SL) include diethylene glycol monobutyl ether acetate (boiling point 247°C), dipropylene glycol n-butyl ether (boiling point 229°C), dipropylene glycol methyl ether acetate (boiling point 209°C), diethylene glycol butyl methyl ether (boiling point 212°C), dipropylene glycol n-propyl ether (boiling point 212°C), tripropylene glycol dimethyl ether (boiling point 215°C), triethylene glycol dimethyl ether (boiling point 216°C), diethylene glycol monoethyl ether acetate (boiling point 218°C), diethylene glycol n-butyl ether (boiling point 230°C), ethylene glycol monophenyl ether (boiling point 245°C), and tripropylene glycol methyl ether (boiling point 242°C). Propylene glycol phenyl ether (boiling point 243℃), triethylene glycol monomethyl ether (boiling point 249℃), benzyl alcohol (boiling point 204.9℃), phenylethanol (boiling point 219~221℃), ethylene glycol monobutyl ether acetate (boiling point 192℃), ethylene glycol monoethyl ether (boiling point 134.8℃), ethylene glycol monomethyl ether (boiling point 124.5℃), propylene glycol monomethyl ether acetate (boiling point 146℃), cyclopentanone (boiling point 130℃), cyclohexanone (boiling point 157℃), cycloheptanone (boiling point 180℃), cyclooctanone (boiling point 195~197℃), cyclohexanol (boiling point 161℃), cyclohexadienone (boiling point 104~104.5℃), etc. Among these, diethylene glycol monoethyl ether acetate and cyclohexanone are preferred organic solvents (SLs) from the viewpoint of maximizing their effectiveness and facilitating good mixing of the active ingredients; cyclohexanone is even more preferred. Organic solvents (SLs) can be used alone or in combination of two or more.

[0105] The content of organic solvent (SL) in the adhesive paste of the present invention is preferably 10% by mass or more and 50% by mass or less relative to the total mass of the adhesive paste; more preferably 13% by mass or more and 40% by mass or less; and particularly preferably 15% by mass or more and 30% by mass or less. By making the content of organic solvent (SL) relative to the total mass of the adhesive paste within the above range, the processability in the step of filling the syringe or the coating step of the adhesive paste is excellent, and the effect of using organic solvent (SL) can be further utilized. Here, "excellent processability in the step of filling the syringe with adhesive paste" means "able to fill the syringe in an appropriate amount without air bubbles".

[0106] The adhesive of the present invention may contain solvents other than organic solvents (SL). Preferably, the organic solvent (SH) has a boiling point of 254°C or higher and 300°C or lower. As for the organic solvent (SH), it is not particularly limited as long as it has a boiling point of 254°C or higher and 300°C or lower and can dissolve or disperse the components of the adhesive of the present invention. By combining organic solvent (SL) with solvents other than organic solvent (SL), the temperature range for obtaining a cured product by heating the adhesive can be more precisely adjusted, and the impact of heating on heat-sensitive components such as optical components and sensor chips can be reduced.

[0107] Specifically, examples of organic solvents (SH) include tripropylene glycol n-butyl ether (boiling point 274°C), 1,6-hexanediol diacrylate (boiling point 260°C), diethylene glycol dibutyl ether (boiling point 256°C), triethylene glycol butyl methyl ether (boiling point 261°C), polyethylene glycol dimethyl ether (boiling point 264–294°C), tetraethylene glycol dimethyl ether (boiling point 275°C), and polyethylene glycol monomethyl ether (boiling point 290–310°C). Among these, from the viewpoint that it is easier to obtain the effect of using organic solvent (SL) and organic solvent (SH) in combination, tripropylene glycol n-butyl ether and 1,6-hexanediol diacrylate are preferred as organic solvents (SH).

[0108] When organic solvents (SL) and organic solvents (SH) are used in combination, the following combinations are preferred: diethylene glycol monoethyl ether acetate (organic solvent (SL)) and tripropylene glycol n-butyl ether (organic solvent (SH)); cyclohexanone (organic solvent (SL)) and tripropylene glycol n-butyl ether (organic solvent (SH)); diethylene glycol monoethyl ether acetate (organic solvent (SL)) and 1,6-hexanediol diacrylate (organic solvent (SH)); cyclohexanone (organic solvent (SL)) and 1,6-hexanediol diacrylate (organic solvent (SH)).

[0109] The organic solvent (SL) preferably accounts for 60% or more by mass of the total solvent (S), more preferably 65% ​​or more by mass, and especially preferably 70% or more by mass. By making the total organic solvent (SL) of the total solvent (S) fall within the above range, the effect of using the organic solvent (SL) can be further enhanced.

[0110] The adhesive paste of the present invention preferably contains a solvent (S) in an amount where the concentration of solid components is 50% by mass or more and 90% by mass or less; more preferably, it contains a solvent (S) in an amount where the concentration of solid components is 70% by mass or more and 90% by mass or less. When the concentration of solid components is within this range, the active ingredients can be easily and well mixed, resulting in excellent processability in the step of filling the adhesive paste into the syringe or the coating step, and further enhancing the effect of using organic solvents (SL). In addition, during wafer bonding, voids can be suppressed between the adhesive paste and the substrate or the object to which it is bonded, thereby improving the reliability of the package.

[0111] (2) Microparticles (B) The adhesive paste of the present invention may contain microparticles as component (B). Examples of microparticles include microparticles (B1) with an average primary particle size of 5 nm or more and 40 nm or less (hereinafter sometimes referred to as "(B1) component") and microparticles (B2) with an average primary particle size of more than 0.04 μm and 8 μm or less (hereinafter sometimes referred to as "(B2) component").

[0112] By containing microparticles (B1), it is easy to obtain an adhesive paste that exhibits excellent processability in the coating process and provides superior adhesion and heat resistance under both high-temperature and low-temperature heating conditions. From the viewpoint of easily obtaining this effect, the average primary particle size of the microparticles (B1) is preferably 5 nm or more and 30 nm or less; more preferably 5 nm or more and 20 nm or less. The average primary particle size of the microparticles (B1) can be determined by observing the shape of the microparticles using a transmission electron microscope.

[0113] The specific surface area of ​​the microparticles (B1) is preferably 10 m² / g or more and 500 m² / g or less; more preferably 20 m² / g or more and 300 m² / g or less. With a specific surface area within the above range, it is easy to obtain an adhesive with better processability in the coating step. The specific surface area can be determined using the BET multi-point method.

[0114] The shape of the microparticle (B1) can be any of the following: spherical, chain-like, needle-like, plate-like, sheet-like, rod-like, fibrous, etc., but spherical is preferred. Here, "spherical" means "in addition to true spherical, it also includes approximately spherical polyhedral shapes that can approximate ellipsoids, egg-shaped, konpeito-like, cocoon-like, etc."

[0115] The constituent components of the microparticle (B1) are not particularly limited, and may include metals; metal oxides; minerals; metal carbonates; metal sulfates; metal hydroxides; metal silicates; inorganic components; organic components; silicones, etc. Furthermore, the microparticles (B1) used may be surface-modified substances.

[0116] The term "metal" refers to elements in the periodic table that belong to Group 1 (excluding hydrogen (H)), Groups 2-11, Group 12 (excluding mercury (Hg)), Group 13 (excluding boron (B)), Group 14 (excluding carbon (C) and silicon (Si)), Group 15 (excluding nitrogen (N), phosphorus (P), arsenic (As) and antimony (Sb)) or Group 16 (excluding oxygen (O), sulfur (S), selenium (Se), tellurium (Te) and polonium (Po)).

[0117] Examples of metal oxides include, for example, titanium oxide, aluminum oxide, boehmite, chromium oxide, nickel oxide, copper oxide, zirconium oxide, indium oxide, zinc oxide, and their composite oxides. Microparticles of metal oxides also include sol particles formed from these metal oxides.

[0118] As minerals, examples include smectite and bentonite. Examples of smectites include montmorillonite, beidellite, hectorite, saponite, Stevensite, nontronite, and sauconite.

[0119] Examples of metal carbonates include calcium carbonate and magnesium carbonate; examples of metal sulfates include calcium sulfate and barium sulfate; examples of metal hydroxides include aluminum hydroxide; and examples of metal silicates include aluminum silicate, calcium silicate, and magnesium silicate. Furthermore, examples of inorganic components include silicon oxide. Silicon oxide can be categorized into dry silicon oxide, wet silicon oxide, and surface-modified silicon oxide. Examples of organic components include acrylic polymers.

[0120] Silicone refers to a synthetic polymer compound with a main framework formed by siloxane bonds. Examples include dimethylpolysiloxane, diphenylpolysiloxane, and methylphenylpolysiloxane.

[0121] Microparticles (B1) can be used alone or in combination of two or more. In this invention, from the viewpoint of easily obtaining an adhesive with excellent transparency, silicon oxide, metal oxide, and minerals are preferred, with silicon oxide being more preferred.

[0122] From the viewpoint that it is easier to mix as an adhesive and that it is easier to obtain an adhesive with better processability in the coating process, surface-modified silicon oxide is preferred, and hydrophobic surface-modified silicon oxide is even more preferred. Examples of hydrophobic surface-modified silicon oxides include trialkylsilyl groups with 1 to 20 carbon atoms such as trimethylsilyl groups; alkylsilyl groups with 1 to 20 carbon atoms such as dimethylsilyl groups and alkylsilyl groups with 1 to 20 carbon atoms such as octylsilyl groups; silicon oxides whose surfaces are treated with silicone oil; etc. Hydrophobic surface-modified silicon oxide can be obtained by, for example, by surface modification of silicon oxide particles with a silane coupling agent having a three-carbon number of 1 to 20, an alkylsilane having a two-carbon number of 1 to 20, or an alkylsilane having a carbon number of 1 to 20, or by treating silicon oxide particles with silicone oil.

[0123] In the case where the adhesive paste of the present invention contains microparticles (B1) [(B1) component], the content of the (B1) component is not particularly limited, and its content is expressed as the mass ratio of (A) component to (B1) component [(A) component: (B1) component], preferably 100:0.1 to 100:90; more preferably 100:0.2 to 100:60; more preferably 100:0.3 to 100:50; more preferably 100:0.5 to 100:40; more preferably 100:0.8 to 100:30. By using the (B1) component within the above range, the effect of adding the (B1) component can be further enhanced.

[0124] By containing microparticles (B2), it is easy to obtain an adhesive paste that exhibits excellent processability during the coating process and provides superior adhesion and heat resistance under both high-temperature and low-temperature heating conditions. From the viewpoint of more easily obtaining this effect, the average primary particle size of the microparticles (B2) is preferably greater than 0.06 μm and less than 7 μm; more preferably greater than 0.3 μm and less than 6 μm; and even more preferably greater than 1 μm and less than 4 μm.

[0125] The average primary particle size of microparticles (B2) can be determined by measuring the particle size distribution using laser diffraction and scattering methods using a laser diffraction / scattering particle size distribution measuring device (e.g., manufactured by Horiba Manufacturing Co., Ltd.; trade name "LA-920").

[0126] The shape of the microparticle (B2) may be the same as that exemplified as the shape of the microparticle (B1), but spherical shape is preferred. Furthermore, the constituent components of the microparticle (B2) may be the same as those exemplified as the constituent components of the microparticle (B1). The microparticle (B2) may be used alone or in combination of two or more.

[0127] From the viewpoint that microparticles (B2) are easier to mix as adhesive pastes and easier to obtain cured products with excellent adhesion and heat resistance, it is preferable to select at least one microparticle from the group consisting of metal oxides, silicon oxides and silicone coated with silicone; silicon oxides and silicone are more preferred.

[0128] In the case where the adhesive paste of the present invention contains microparticles (B2) [(B2) component], the content of the (B2) component is not particularly limited, and its content is expressed as the mass ratio of (A) component to (B2) component [(A) component: (B2) component], preferably 100:0.1 to 100:40; more preferably 100:0.2 to 100:30; more preferably 100:0.3 to 100:20; more preferably 100:0.5 to 100:15; more preferably 100:0.8 to 100:12. By using the (B2) component within the above range, the effect of adding the (B2) component can be further enhanced.

[0129] (3) Other additives: Without prejudice to the purpose of the present invention, the adhesive paste of the present invention may contain other ingredients besides the above-mentioned ingredients (A), (L) and (B) [(C) ingredient]. Examples of ingredients (C) include antioxidants, ultraviolet absorbers, photostable agents, etc.

[0130] Antioxidants are added to prevent oxidative deterioration during the heating process. Examples of antioxidants include phosphorus-based antioxidants, phenolic antioxidants, and sulfur-based antioxidants.

[0131] Examples of phosphorus-based antioxidants include phosphites and oxaphosphaphenanthrene oxides. Examples of phenolic antioxidants include monophenols, bisphenols, and high molecular weight phenols. Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and di(octadecyl) 3,3'-thiodipropionate.

[0132] These antioxidants may be used alone or in combination of two or more. The amount of antioxidant used, relative to component (A), is typically less than 10% by mass.

[0133] Ultraviolet absorbers are added to improve the lightfastness of the resulting adhesive. Examples of ultraviolet absorbers include salicylic acid derivatives, benzophenone derivatives, benzotriazole derivatives, and hindered amine derivatives. These ultraviolet absorbers can be used alone or in combination of two or more. The amount of antioxidant used is typically less than 10% by mass relative to component (A).

[0134] The light stabilizer is added to improve the lightfastness of the resulting adhesive. Examples of light stabilizers include hindered amines such as poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-tris(2,2,6,6-tetramethyl-4-piperidine)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidine)imino}]. These light stabilizers can be used alone or in combination of two or more. The total amount of component (C) used is typically 20% by mass or less relative to component (A).

[0135] The adhesive paste of the present invention can be manufactured, for example, by a manufacturing method having the following steps (A1) and (A2): Step (A1): performing condensation polymerization on at least one of the compounds represented by formula (a-6) in the presence of a condensation polymerization catalyst to obtain a polysilicon silsesquioxane compound; Step (A2): dissolving the polysilicon silsesquioxane compound obtained in step (A1) in a solvent (S), and adding the above-mentioned liquid component (L) to a solution containing the obtained polysilicon silsesquioxane compound in such a way that it is 15% by mass or more relative to the total mass of the adhesive paste.

[0136] In step (AI), as a method for condensing at least one of the compounds represented by formula (a-6) in the presence of a condensation polymerization catalyst to obtain a polysilicon silsesquioxane compound, the same method as exemplified in the relevant paragraph of item 1) Adhesive Paste can be listed. Furthermore, the solvent (S) and liquid component (L) used in step (AII) can be the same as those exemplified in the relevant paragraph of item 1) Adhesive Paste.

[0137] In step (AII), as a method for dissolving the polysilsesquioxane compound in the solvent (S), examples include mixing the polysilsesquioxane compound with the liquid component (L), and, if necessary, the aforementioned components (B) and (C), with the solvent (S), followed by defoaming and dissolution. There are no particular limitations on the mixing method or the defoaming method; conventional methods can be used. There are no particular limitations on the order of mixing. According to the manufacturing method having the above steps (AI) and (AII), the adhesive paste of the present invention can be manufactured efficiently and easily.

[0138] The adhesive paste of the present invention, after being heated at 170°C for 2 hours, preferably has a mass reduction rate of less than 55% after heating at 170°C for 2 hours; more preferably 10% or more and less than 45%; and particularly preferably 15% or more and less than 30%. Since the volume of the adhesive paste decreases as the mass decreases, if the mass reduction rate at 170°C for 2 hours is above the above-mentioned upper limit, there is a risk that horizontally mounted wafers may tilt after the adhesive paste has cured. If it is less than the above-mentioned upper limit, this risk can be reduced.

[0139] Furthermore, in the adhesive paste of the present invention, after heating the adhesive paste at 100°C for 2 hours, the mass reduction rate of the adhesive paste before and after heating at 100°C for 2 hours is preferably 10% or more; more preferably 12% or more and less than 50%; and particularly preferably 13% or more and less than 45%. By making the mass reduction rate at 100°C for 2 hours at or above the aforementioned lower limit value, the cured product obtained by heating at low temperature can be made to have better adhesion. On the other hand, if the mass reduction rate at 100°C for 2 hours is at or above the aforementioned upper limit value, since the effective components that perform the adhesive function of the cured product obtained by heating at low temperature are reduced, there is a risk that high adhesive strength cannot be exhibited. If it is less than the aforementioned upper limit value, this risk can be reduced.

[0140] Furthermore, the mass reduction rate of the adhesive paste of the present invention from 170°C for 2 hours to 100°C for 2 hours is preferably less than 14%, more preferably less than 12%, and particularly preferably more than 1% and less than 10%. By making the mass reduction rate from 170°C for 2 hours to 100°C for 2 hours less than the above-mentioned upper limit, the solvent can be effectively evaporated as in the case of heating at low temperatures as in the case of heating at high temperatures. This allows the cured product obtained by heating at low temperatures to have better adhesion. Therefore, the temperature range for heating and curing the adhesive paste can be adjusted, and the impact of heating on optical components, sensor chips, etc., can be reduced. The mass reduction rates of 170°C for 2 hours and 100°C for 2 hours can be measured by the method described in the examples.

[0141] The adhesive is heated to evaporate the solvent (S) and cure it, thereby obtaining a cured product. The heating temperature for curing is usually 80 to 190°C, preferably 80 to 120°C or 150 to 190°C. Furthermore, the heating time for curing is usually 30 minutes to 10 hours, preferably 30 minutes to 5 hours, and more preferably 30 minutes to 3 hours.

[0142] The cured product obtained by curing the adhesive paste of the present invention exhibits excellent adhesion. The excellent adhesion of the cured product obtained by curing the adhesive paste of the present invention can be confirmed, for example, as described below. Specifically, the adhesive paste of the present invention is applied to the mirror surface of a square silicon wafer with a side length of 1 mm (area of ​​1 mm²), the coated surface is placed on a silver-plated copper plate, and pressure bonding is performed (adhesive paste thickness after pressure bonding: approximately 2 μm), followed by heat treatment (e.g., at 100°C for 2 hours, or at 170°C for 2 hours) to cure it. It is then placed on the testing platform of a bond tester pre-adjusted to predetermined temperatures (23°C, 100°C) for 60 seconds. A horizontal (shear direction) stress is applied to the bonding surface at a speed of 200 μm / s from a height of 100 μm above the bonded object, and the bonding strength (N / mm²) between the test piece and the bonded object is measured.

[0143] The adhesion strength of the cured product obtained by curing the adhesive paste of the present invention is preferably 7 N / mm□ or higher at 23°C, more preferably 10 N / mm□ or higher, further preferably 13 N / mm□ or higher, and especially preferably 15 N / mm□ or higher. Furthermore, the adhesion strength of the cured product obtained by curing the adhesive paste of the present invention is preferably 7 N / mm□ or higher at 100°C, more preferably 10 N / mm□ or higher, further preferably 13 N / mm□ or higher, and especially preferably 15 N / mm□ or higher. In this specification, "1 mm□" refers to "1 mm square," that is, "1 mm × 1 mm (a square with a side length of 1 mm)."

[0144] Due to the above-mentioned characteristics, the adhesive paste of the present invention is suitable for use as an adhesive for fixing semiconductor elements.

[0145] 2) Method of using adhesive paste and method of manufacturing semiconductor device using adhesive paste The method of manufacturing semiconductor device using adhesive paste of the present invention as adhesive for fixing semiconductor element is a method having the following steps (BI) and (BII): Step (BI): applying adhesive paste to the bonding surface of one or both of the semiconductor element and the support substrate and performing pressure bonding; Step (BII): heating and curing the adhesive paste of the pressure bonding body obtained in step (BI) to fix the semiconductor element on the support substrate.

[0146] Examples of semiconductor elements include light-emitting elements such as lasers and light-emitting diodes (LEDs), light-receiving elements such as solar cells, transistors, sensors such as temperature sensors and pressure sensors, and integrated circuits. Among these, from the viewpoint that it is easier to achieve the effect of using the adhesive of the present invention, light-emitting semiconductor devices are preferred.

[0147] As materials for supporting substrates used to bond semiconductor elements, examples include glass such as soda-lime glass and heat-resistant hard glass; ceramics; sapphire; alloys of iron, copper, aluminum, gold, silver, platinum, chromium, titanium, and such metals, and stainless steel (SUS302, SUS304, SUS304L, SUS309, etc.); and synthetic resins such as polyethylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polyurethane, polyetheretherketone, polyetherurethane, polyphenylene sulfide, polyetherimide, polyimide, polyamide, acrylic resin, nobornene resin, cycloolefin resin, and glass epoxy resin.

[0148] The adhesive of the present invention is preferably filled into a syringe. By filling the syringe with the adhesive, its processability in the coating step is improved. The syringe material can be any of synthetic resin, metal, or glass, but synthetic resin is preferred. The capacity of the syringe is not particularly limited and can be appropriately determined according to the amount of adhesive filled or coated. Furthermore, commercially available syringes can also be used. Examples of commercially available products include, for example, the SS-01T series (manufactured by TERUMO Corporation) and the PSY series (manufactured by Musashi Engineering Corporation).

[0149] In the semiconductor device manufacturing method of the present invention, an syringe filled with adhesive paste is vertically lowered to approach a support substrate. After a predetermined amount of adhesive paste is dispensed from the tip of the syringe, the syringe rises and leaves the support substrate, while the support substrate moves laterally. Then, by repeating this operation, adhesive paste is continuously applied to the support substrate. Subsequently, a semiconductor device is mounted on the applied adhesive paste and pressure-bonded to the support substrate.

[0150] There is no particular limitation on the amount of adhesive paste applied, as long as it is sufficient to firmly bond the semiconductor device and the support substrate to be bonded by curing. Typically, the thickness of the adhesive paste film is 0.5 μm or more and 5 μm or less, preferably 1 μm or more and 3 μm or less.

[0151] Subsequently, the semiconductor device is fixed on the support substrate by heating and curing the adhesive paste of the obtained pressure adhesive. The heating temperature and heating time are as described in the relevant section of 1) Adhesive Paste.

[0152] In the semiconductor device obtained by the manufacturing method of the semiconductor device of the present invention, the semiconductor element is well mounted on the adhesive paste, and the semiconductor element is fixed with high adhesive strength. [Example]

[0153] In the following description, embodiments will be provided to illustrate the present invention in more detail. However, the present invention is not limited to the following embodiments. Unless otherwise stated, the parts and percentages in each embodiment are based on mass.

[0154] [Determination of Average Molecular Weight] The mass-average molecular weight (Mw) and number-average molecular weight (Mn) of the thermosetting organopolysiloxane compound (A) obtained in the manufacturing example were set as standard polystyrene conversion values, and were determined using the following apparatus and conditions. Apparatus name: HLC-8220GPC, manufactured by Tosoh Corporation Chromatography column: TSKgel GMHXL, TSKgel GMHXL and TSKgel 2000HXL connected in sequence Solvent: Tetrahydrofuran Injection volume: 20 μl Measurement temperature: 40℃ Flow rate: 1 ml / min Detector: Differential refractometer

[0155] [Determination of Infrared Spectroscopy] The IR spectrum of the thermosetting organopolysiloxane compound (A) obtained in the manufacturing example was measured using a Fourier transform infrared spectrophotometer (manufactured by PerkinElmer; Spectrum 100).

[0156] [Viscosity Evaluation] The viscosity was measured at 25°C with a shear rate of 1 s⁻¹ using a cone plate with a radius of 50 mm and a cone angle of 0.5° in a rheometer (manufactured by Anton Paar, product name "MCR301").

[0157] (Manufacturing Example 1) 71.37 g (400 mmol) of methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was placed in a 300 ml round-bottom flask. While stirring, an aqueous solution (0.25 mol% relative to the total silane compound) was added, consisting of 0.10 g of 35% hydrochloric acid dissolved in 21.6 ml of distilled water. The entire solution was stirred at 30°C for 2 hours, then heated to 70°C and stirred for 5 hours. Afterward, the reaction solution was brought to room temperature (23°C), and 140 g of propyl acetate was added. 0.12 g of 28% ammonia water (0.5 mol% relative to the total silane compound) was added while stirring, and the solution was heated to 70°C and stirred for another 3 hours. Pure water was added to the reaction solution, and the mixture was separated. This operation was repeated until the pH of the aqueous layer reached 7.0. The organic layer was concentrated using an evaporator, and the concentrate was vacuum dried to obtain 55.7 g of a thermosetting organopolysiloxane compound (A1). The thermosetting organopolysiloxane compound (A1) has a mass-average molecular weight (Mw) of 7,800 and a molecular weight distribution (Mw / Mn) of 4.52. Furthermore, the IR spectral data of the thermosetting organopolysiloxane compound (A1) are shown below: Si-CH3: 1272 cm⁻¹, 1409 cm⁻¹, Si-O: 1132 cm⁻¹

[0158] (Manufacturing Example 2) 17.0 g (77.7 mmol) of 3,3,3-trifluoropropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and 32.33 g (181.3 mmol) of methyltriethoxysilane were placed in a 300 ml round-bottom flask. While stirring, an aqueous solution (0.65 mmol of HCl; 0.25 mol relative to the total amount of the silane compound) was added, formed by dissolving 0.0675 g of 35% hydrochloric acid in 14.0 ml of distilled water. The entire solution was stirred at 30°C for 2 hours, and then heated to 70°C and stirred for 20 hours. While continuing to stir the contents, a mixed solution of 0.0394 g of 28% ammonia water (0.65 mmol of NH3) and 46.1 g of propyl acetate was added to adjust the pH of the reaction solution to 6.9, and the solution was stirred at 70°C for 40 minutes. After cooling the reaction solution to room temperature (23°C), 50 g of propyl acetate and 100 g of water were added, and the mixture was separated to obtain an organic layer containing the reaction products. Magnesium sulfate was added to this organic layer for drying. After filtering to remove the magnesium sulfate, the organic layer was concentrated using an evaporator, and the concentrate was vacuum dried to obtain 22.3 g of a thermosetting organopolysiloxane compound (A2). The thermosetting organopolysiloxane compound (A2) has a mass-average molecular weight (Mw) of 5,500 and a molecular weight distribution (Mw / Mn) of 3.40. Furthermore, the IR spectral data of the thermosetting organopolysiloxane compound (A2) are shown below: Si-CH3: 1272 cm⁻¹, 1409 cm⁻¹, Si-O: 1132 cm⁻¹, CF: 1213 cm⁻¹

[0159] (Manufacturing Example 3) 28.91 g (145.8 mmol) of phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was placed in a 300 ml round-bottom flask. While stirring, an aqueous solution (0.25 mol% relative to the total silane compound) was added, formed by dissolving 0.0376 g of 35% hydrochloric acid in 7.874 ml of distilled water. The entire solution was stirred at 30°C for 2 hours, then heated to 70°C and stirred for 5 hours. Afterward, the reaction solution was brought back to room temperature (23°C), and 50 g of propyl acetate and 100 g of water were added. The mixture was separated to obtain an organic layer containing the reaction products. Magnesium sulfate was added to this organic layer for drying. After filtering to remove the magnesium sulfate, the organic layer was concentrated using an evaporator, and the concentrate was dried under vacuum to obtain 17.0 g of a thermosetting organopolysiloxane compound (A3). The thermosetting organopolysiloxane compound (A3) has a mass-average molecular weight (Mw) of 1,100 and a molecular weight distribution (Mw / Mn) of 1.2. Furthermore, the IR spectral data of the thermosetting organopolysiloxane compound (A3) are shown below: Si-C6H5: 698 cm⁻¹, Si-O: 1132 cm⁻¹

[0160] (Manufacturing Example 4) 72.275 g (364.5 mmol) of phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was placed in a 300 ml round-bottom flask. While stirring, an aqueous solution (0.25 mol% relative to the total amount of the silane compound) was added, formed by dissolving 0.0938 g of 35% hydrochloric acid in 19.683 ml of distilled water. The entire solution was stirred at room temperature (25°C) for 12 minutes. 0.0548 g of 28% ammonia solution (0.25 mmol relative to the amount of phenyltrimethoxysilane) was added, and the solution was stirred at room temperature for 2 hours. 200 g of propyl acetate and 400 g of water were added, and the mixture was separated to obtain an organic layer containing the reaction products. Magnesium sulfate was added to this organic layer for drying. After filtering to remove magnesium sulfate, the organic layer was concentrated using an evaporator, and the concentrate was vacuum dried to obtain 64.94 g of a viscous liquid polysilsesquioxane (L5). The liquid polysilsesquioxane (L5) had a mass-average molecular weight (Mw) of 740 and a molecular weight distribution (Mw / Mn) of 1.48.

[0161] The compounds used in the examples and comparative examples are shown below. [(A) Components] Thermosetting organopolysiloxane compound (A1): The organopolysiloxane compound obtained in Manufacturing Example 1 (solid at 25°C) Thermosetting organopolysiloxane compound (A2): The organopolysiloxane compound obtained in Manufacturing Example 2 (solid at 25°C) Thermosetting organopolysiloxane compound (A3): The organopolysiloxane compound obtained in Manufacturing Example 3 (solid at 25°C)

[0162] [Liquid Components (L)] (L1) Difunctional silane compound: Dimethoxydiphenylsilane; manufactured by Shin-Etsu Chemical Industry Co., Ltd.; product name "KBM-202SS" (viscosity 8 mPa·s) (L2) Trifunctional silane compound (L2-1) 3-(Trimethoxysilyl)propylsuccinic anhydride; manufactured by Shin-Etsu Chemical Industry Co., Ltd.; product name "X-12-967C" (viscosity 30 mPa·s) (L2-2) 3-Methylpropenoxypropyltrimethoxysilane; manufactured by Shin-Etsu Chemical Industry Co., Ltd.; product name "KBM-503" (viscosity 8 mPa·s) (L2-3) 3-Propyleneoxypropyltrimethoxysilane; manufactured by Shin-Etsu Chemical Industry Co., Ltd.; product name "KBM-5103" (viscosity 15 mPa·s) (L2-4) 3-Propyltriethoxysilane: Manufactured by Shin-Etsu Chemical Industry Co., Ltd.; Product name "KBE-9007N" (viscosity 10 mPa·s) (L2-5) Phenylacetyltrimethoxysilane: Manufactured by Shin-Etsu Chemical Industry Co., Ltd.; Product name "KBM-103" (viscosity 10 mPa·s) (L3) Polyfunctional silane compound (L3-1) 1,3,5-N-Tris(3-(trimethoxysilyl)propyl)isocyanurate: Manufactured by Shin-Etsu Chemical Industry Co., Ltd.; Product name "KBM-9659" (viscosity 800 mPa·s) (L3-2) Polyfunctional silane compound with an organic backbone structure containing methoxy and isocyanurate groups: Manufactured by Shin-Etsu Chemical Industry Co., Ltd.; Product name "X-12-1159L" (viscosity 4,000 mPa·s) (L4) Silicone oil (L4-1) Acrylic-terminated modified silicone oil: manufactured by Shin-Etsu Chemical Industry Co., Ltd.; product name "X-22-2445" (viscosity 60 mPa·s) (L4-2) Alkyl-aralkyl modified silicone oil: manufactured by Momentive Performance Materials Japan Co., Ltd.; product name "XF42-334" (viscosity 1000 mPa·s) [Liquid components other than liquid components (L) (L5)] Liquid polysilsesquioxane: Polysilsesquioxane obtained in Manufacturing Example 4 (viscosity 197,000 mPa·s)

[0163] [Solvents (S)] (1) Organic solvents (SL) Diethylene glycol monoethyl ether acetate (EDGAC): Manufactured by Tokyo Chemical Industry Co., Ltd. (boiling point 218°C) Cyclohexanone: Manufactured by Tokyo Chemical Industry Co., Ltd. (boiling point 157°C) (2) Organic solvents (SH) Tripropylene glycol n-butyl ether (TPnB): Manufactured by Dow Chemical Company (boiling point 274°C) (3) Other acetones: Manufactured by Tokyo Chemical Industry Co., Ltd. (boiling point 56°C)

[0164] [(B) Composition] Microparticles (B1): Silicon oxide microparticles (manufactured by Aerosil Corporation, Japan, trade name "AEROSIL RX300", average primary particle size: 7 nm, specific surface area: 210 m2 / g) Microparticles (B2): Silicone (manufactured by Nikko-Rika Corporation, trade name "MSP-SN08", average primary particle size: 0.8 μm, shape: spherical)

[0165] (Example 1) 28 parts of EGAC (SL), 10 parts of (L3-1), 3 parts of (L2-1), and 35 parts of (L1) were added to 100 parts of thermosetting organopolysiloxane compound (A1). The entire solution was thoroughly mixed and defoamed to obtain an adhesive paste 1 with a solid content concentration of 84%.

[0166] (Examples 2-24, Comparative Examples 1-3) The types and mixing ratios of the compounds (each component) were changed according to Table 1 below. Otherwise, adhesive pastes 2-24 and adhesive pastes 1r-3r were prepared in the same manner as in Example 1. In Examples 23 and 24, microparticles (B1) and microparticles (B2) were added before adding EGAC (SL) and each liquid component (L1-L3).

[0167] The following tests were conducted using adhesive pastes 1-24 and adhesive pastes 1r-3r obtained in the examples and comparative examples. The results are shown in Table 2 below.

[0168] [Evaluation of Adhesion Removal Time] The adhesive paste obtained in the examples and comparative examples was applied to a stainless steel plate (SUS304, surface No. 600 polished) with a diameter of 0.5 mm and left to stand under standard conditions (temperature: 23℃±1℃, relative humidity: 50±5%). After a certain period of time, the applied adhesive paste was scraped in half with a needle, and the needle mark was observed to see if it disappeared within 10 seconds. If the needle mark disappeared within 10 seconds, the plate was left to stand until the needle mark no longer disappeared within 10 seconds. The same observation was repeated every 2 minutes from the start of the measurement until 10 minutes, and then every 5 minutes from the start of the measurement until 10 minutes. Finally, the standing time N (minutes) until the needle mark no longer disappeared within 10 seconds was measured.

[0169] [Wafer Mountability Evaluation] The adhesive paste obtained in the Examples and Comparative Examples was applied to an electroless silver-plated copper plate (average roughness Ra of the silver-plated surface: 0.025 μm) with a diameter of 0.5 mm, and placed under standard conditions (temperature: 23℃±1℃, relative humidity: 50±5%). After 30 minutes, a square silicon wafer with a side length of 1 mm (area of ​​1 mm2) was mounted, and the wafer tilt was observed. If the wafer could be mounted without tilting, it was rated as "Good"; if problems such as wafer tilting occurred, it was rated as "Poor".

[0170] [Adhesion Strength Evaluation (1)] The adhesive paste obtained in the Examples and Comparative Examples was applied to the mirror surface of a square silicon wafer with a side length of 1 mm (area of ​​1 mm2) and left to stand in a standard environment (temperature: 23℃±1℃; relative humidity: 50±5%). After 30 minutes, the coated surface was placed on the substrate [a silver-plated copper plate without electroplating (average roughness Ra of the silver-plated surface: 0.025 μm)] and pressure bonding was performed so that the thickness of the adhesive paste after pressure bonding was about 2 μm. Afterwards, it was heat-treated at 170℃ for 2 hours to cure it, and the substrate with the test piece attached was obtained. The substrate with the test piece attached is placed on the test stand of an adhesive strength tester (Dage Series 4000) at 100°C for 60 seconds. A horizontal (shear direction) stress is applied to the bonding surface at a height of 100 μm from the substrate at a speed of 200 μm / s. The bonding strength (N / mm□) between the test piece and the substrate at 100°C is then measured.

[0171] [Adhesion strength evaluation (2)] In the adhesion strength evaluation (1), the temperature conditions for curing by heat treatment were changed to 100°C, and the heating temperature and measurement temperature of the adhesion strength tester were changed to 23°C. Otherwise, the adhesion strength (N / mm□) between the test piece and the substrate was measured in the same manner as in the adhesion strength evaluation (1).

[0172] [Determination of mass reduction rate] 15 mg of the adhesive obtained in the examples and comparative examples was placed in a differential thermal and thermogravimetric analyzer (manufactured by Shimadzu Corporation; product name "DTG-60"). The starting temperature was 40°C, the heating rate was 10°C / min, and it was heated at 100°C for 2 hours. The mass of the adhesive before and after heating was measured, and the mass reduction rate before and after heating was calculated as 100°C 2h (%) [{[(mass of adhesive before heating) - (mass of adhesive after heating at 100°C for 2 hours)] / (mass of adhesive before heating)}×100]. Furthermore, the heating conditions were changed to heating at 170°C for 2 hours. Except for the mass reduction rate 100°C 2h (%) determination method, the mass reduction rate of adhesive before and after heating as 170°C 2h (%) [{[(mass of adhesive before heating) - (mass of adhesive after heating at 170°C for 2 hours)] / (mass of adhesive before heating)}×100]. In addition, the mass reduction rate 170℃ 2h - mass reduction rate 100℃ 2h (%) was calculated by measuring the mass reduction rate.

[0173] [Table 1] (A)Ingredients Liquid ingredients (L) Liquid ingredients other than liquid ingredients (L) (B) Ingredients Solvent (S) The proportion of organic solvent (SL) relative to the total mass of the adhesive paste The proportion of liquid components (L) relative to the total mass of the adhesive paste Solid component concentration The proportion of organic solvent (SL) in the solvent (S) The proportion of (L) components excluding (L3) relative to the total mass of the adhesive paste. 2 functions 3 functions polysaccharidosis Silicon oil Organic solvents (SL) Organic solvents (SH) other A1 A2 A3 L1 L2-1 L2-2 L2-3 L2-4 L2-5 L3-1 L3-2 L4-1 L4-2 L5 B1 B2 Cyclohexanone EDGAC TPnB acetone (parts by weight) (mass ratio) (%) (%) (%) (%) (%) (%) Example 1 100 0 0 35 3 0 0 0 0 10 0 0 0 0 0 0 0 100 0 0 16 27 84 100 twenty two Example 2 100 0 0 0 3 35 0 0 0 10 0 0 0 0 0 0 100 0 0 0 16 27 84 100 twenty two Example 3 100 0 0 0 3 0 0 0 0 10 35 0 0 0 0 0 100 0 0 0 16 27 84 100 2 Example 4 100 0 0 0 3 0 0 0 0 10 0 35 0 0 0 0 100 0 0 0 16 27 84 100 twenty two Example 5 0 100 0 35 3 0 0 0 0 10 0 0 0 0 0 0 0 100 0 0 16 27 84 100 twenty two Example 6 0 100 0 0 3 35 0 0 0 10 0 0 0 0 0 0 0 100 0 0 16 27 84 100 twenty two Example 7 0 100 0 0 3 0 35 0 0 10 0 0 0 0 0 0 0 100 0 0 16 27 84 100 twenty two Example 8 0 100 0 0 3 0 0 0 0 10 0 35 0 0 0 0 0 100 0 0 16 27 84 100 twenty two Example 9 0 100 0 0 3 0 0 0 0 10 0 0 35 0 0 0 0 100 0 0 16 27 84 100 twenty two Example 10 0 100 0 35 3 0 0 0 0 10 0 0 0 0 0 0 100 0 0 0 16 27 84 100 twenty two Example 11 0 0 100 35 3 0 0 0 0 10 0 0 0 0 0 0 0 100 0 0 16 27 84 100 twenty two Example 12 0 0 100 0 3 35 0 0 0 10 0 0 0 0 0 0 100 0 0 0 16 27 84 100 twenty two Example 13 0 0 100 0 3 0 0 35 0 10 0 0 0 0 0 0 100 0 0 0 16 27 84 100 twenty two Example 14 0 0 100 0 3 0 0 0 35 10 0 0 0 0 0 0 100 0 0 0 16 27 84 100 twenty two Example 15 0 0 100 0 3 0 0 0 0 10 35 0 0 0 0 0 100 0 0 0 16 27 84 100 2 Example 16 0 0 100 0 3 0 0 0 0 10 0 35 0 0 0 0 100 0 0 0 16 27 84 100 twenty two Example 17 0 0 100 0 3 0 0 0 0 10 0 0 35 0 0 0 100 0 0 0 16 27 84 100 twenty two Example 18 100 0 0 0 3 0 0 0 0 10 0 10 0 0 0 0 0 0 100 0 0 16 84 0 9 Example 19 100 0 0 0 3 0 0 0 0 10 0 10 0 0 0 0 100 0 0 0 16 16 84 100 9 Example 20 100 0 0 35 3 0 0 0 0 10 0 0 0 0 0 0 0 25 75 0 4 27 84 25 twenty two Example 21 100 0 0 35 3 0 0 0 0 10 0 0 0 0 0 0 0 75 25 0 12 27 84 75 twenty two Example 22 100 0 0 35 3 0 0 0 0 10 0 0 0 0 0 0 0 100 0 0 40 19 60 100 15 Example 23 100 0 0 35 3 0 0 0 0 10 0 0 0 0 twenty five 10 0 100 0 0 16 twenty two 84 100 17 Actual example 24 100 0 0 35 3 0 0 0 0 10 0 0 0 0 30 20 0 100 0 0 16 20 84 100 16 Comparative Example 1 100 0 0 0 3 0 0 0 0 10 0 0 0 0 0 0 0 0 0 100 0 10 84 0 2 Comparative Example 2 100 0 0 0 3 0 0 0 0 10 0 0 0 35 0 0 100 0 0 0 16 7 84 100 2 Comparative Example 3 100 0 0 0 3 0 0 0 0 10 0 0 0 0 0 0 100 0 0 0 16 10 84 100 2

[0174] [Table 2] De-sticking time Chip mountability Next, intensity (1) Next, intensity (2) Reduction rate 100℃ 2h Reduction rate 170℃ 2h Quality reduction rate 170℃ 2h - Weight reduction rate 100℃ 2h (minute) (N / mm□) (N / mm□) (%) (%) (%) Example 1 80 good 20 12 20 twenty three 3 Example 2 40 good 18 13 18 twenty two 4 Example 3 30 good 19 15 19 twenty three 4 Example 4 40 good 19 15 17 20 3 Example 5 90 good 19 11 20 twenty four 4 Example 6 80 good 16 15 20 twenty two 2 Example 7 80 good 18 16 19 twenty three 4 Example 8 130 good twenty two 15 18 20 2 Example 9 120 good twenty one 13 18 twenty one 3 Example 10 30 good 17 13 18 20 2 Example 11 70 good 18 10 20 twenty two 2 Example 12 90 good 17 12 twenty one twenty three 2 Example 13 110 good 20 18 19 twenty two 3 Example 14 80 good 17 17 twenty one twenty four 3 Example 15 25 good 18 12 20 twenty four 4 Example 16 60 good 16 14 20 twenty three 3 Example 17 90 good twenty one 11 19 twenty three 4 Example 18 120 good 15 0 2 18 16 Example 19 30 good 16 11 19 twenty two 3 Example 20 120 good 17 6 7 twenty two 15 Example 21 90 good 19 9 15 twenty three 8 Example 22 40 good 20 10 40 42 2 Example 23 70 good 18 14 18 twenty one 3 Example 24 50 good twenty one 13 20 twenty two 2 Comparative Example 1 2 bad Unable to measure due to improper installation Unable to measure due to improper installation 19 20 1 Comparative Example 2 10 bad Unable to measure due to improper installation Unable to measure due to improper installation 17 twenty one 4 Comparative Example 3 10 bad Unable to measure due to improper installation Unable to measure due to improper installation 18 20 2

[0175] The following can be understood from Tables 1 and 2. The adhesives of Examples 1-24 have long detack times, excellent wafer mounting properties, and excellent adhesion strength of the cured products obtained by heating the adhesives at high temperatures. Compared to adhesives containing polyfunctional silane compounds as liquid components (L), adhesives containing difunctional silane compounds, trifunctional silane compounds, and silicone oil as liquid components (L) have longer detack times, allowing for longer wafer mounting (Examples 2-4, 12-17). Furthermore, compared to adhesives containing difunctional silane compounds as liquid components (L), adhesives containing trifunctional silane compounds and silicone oil as liquid components (L) exhibit superior adhesion strength of the cured products obtained by heating the adhesives at low temperatures (Examples 5-9). In other words, by selecting the liquid component (L), taking into account the de-tack time (the time after the adhesive is applied to the object) and the temperature range of the cured product obtained by heating the adhesive, the most suitable adhesive can be obtained.

[0176] When an organic solvent (SL) with a low boiling point is included as a solvent (S), the detack time of the adhesive paste is shortened, and the adhesion strength of the cured product obtained by heating the adhesive paste at a low temperature is excellent (Examples 5 and 10). Furthermore, compared to an adhesive paste containing only an organic solvent (SH) as a solvent (S), the detack time of the adhesive paste containing only an organic solvent (SL) as a solvent (S) is shortened, but the adhesion strength of the cured product obtained by heating the adhesive paste at a low temperature is excellent (Examples 18 and 19). In addition, when a mixed solvent containing both organic solvent (SL) and organic solvent (SH) is included as a solvent (S), the adhesive paste containing a higher proportion of organic solvent (SH) has a longer detack time. On the other hand, the adhesive paste containing a higher proportion of organic solvent (SL) has a shorter detack time, and the adhesion of the cured product obtained by heating the adhesive paste under either high-temperature or low-temperature heating conditions is excellent (Examples 20 and 21). In other words, by selecting organic solvents (SL) and organic solvents (SH), and considering the de-tack time (the time after the adhesive is applied to the object) and the temperature range of the cured product obtained by heating the adhesive, the most suitable adhesive can be obtained.

[0177] Adhesives with a higher concentration of solid components (correspondingly, a higher proportion of (L) component relative to the total mass of the adhesive paste) have a longer detack time and excellent adhesion when cured by heating the adhesive paste at low temperatures (Examples 1 and 22). Compared to adhesives (B) without microparticles, adhesives containing microparticles (B) still have a longer detack time and excellent wafer mounting properties, even though the proportion of (L) component relative to the total mass of the adhesive paste is lower. Furthermore, cured products with good adhesion can be provided even under either high-temperature or low-temperature heating conditions (Examples 23 and 24). Even when the type of thermosetting organopolysiloxane compound (A) (the type of polysiloxane compound side chain) is changed, the detack time remains longer, the wafer mounting properties remain excellent, and the adhesion strength of cured products obtained by heating the adhesive paste under either high-temperature or low-temperature heating conditions is excellent (Examples 1, 5, 11, etc.).

[0178] On the other hand, in Comparative Example 1, the adhesive paste 1r has a shorter de-adhesion time because the liquid component (L) accounts for less than 10% of the total mass of the adhesive paste, which is not conducive to wafer mounting in a short time. Furthermore, after mounting the silicon wafer, a wafer tilting defect occurs, and due to poor wafer mounting properties, the bonding strength cannot be measured. In Comparative Example 2, the adhesive paste 2r contains a high-viscosity liquid component (L). Because the viscosity of the adhesive paste is higher, the de-adhesion time is shorter, which is not conducive to wafer mounting in a short time. Furthermore, after mounting the silicon wafer, a wafer tilting defect occurs, and due to poor wafer mounting properties, the bonding strength cannot be measured. In Comparative Example 3, the adhesive paste 3r contains only an organic solvent (SL) as a solvent (S), and the liquid component (L) accounts for less than 10% of the total mass of the adhesive paste, resulting in a shorter de-adhesion time, which is not conducive to wafer mounting in a short time. Furthermore, after mounting the silicon wafer, a defect occurs where the wafer tilts. Due to the poor wafer mounting properties, the bonding strength cannot be measured. [Simplified Explanation of the Diagram]

[0020] None.

Claims

1. An adhesive paste comprising a thermosetting organopolysiloxane compound (A) and a liquid component (L) satisfying the following requirements 1 and 2, wherein the liquid component (L) is at least one selected from the group consisting of trifunctional silane compounds, difunctional silane compounds and silicone oil, and the content of the liquid component (L) is 15% by mass or more and less than 50% by mass relative to the total mass of the adhesive paste, and the detack time of the adhesive paste is 20 minutes or more: [Requirement 1] The viscosity at 25°C is 20,000 mPa·s or less; [Requirement 2] It is a silane compound.

2. The adhesive as claimed in claim 1, wherein the thermosetting organopolysiloxane compound (A) is a polysilicon silsesquioxane compound.

3. The adhesive paste as described in claim 1 or 2 further contains a solvent (S), wherein the solvent (S) contains an organic solvent (SL) with a boiling point of 100°C or higher and less than 254°C.

4. The adhesive paste as described in claim 3, wherein the organic solvent (SL) is a substance with a boiling point of 100°C or higher and less than 200°C.

5. The adhesive paste as described in claim 3, wherein the content of the aforementioned organic solvent (SL) is 10% by mass or more and 50% by mass or less relative to the total mass of the adhesive paste.

6. The adhesive paste as described in claim 1 or 2 further contains the following component (B): (B) component: microparticles.

7. The adhesive paste as described in claim 1 or 2, wherein, The concentration of solid components is above 50% by mass and below 90% by mass.

8. The adhesive paste as described in claim 1 or 2, wherein, After heating the adhesive paste at 170°C for 2 hours, the mass reduction rate of the adhesive paste before and after heating at 170°C for 2 hours was less than 55%.

9. The adhesive paste as described in claim 1 or 2, wherein, When the adhesive paste is heated at 170°C for 2 hours, the mass reduction rate of the adhesive paste before and after heating is set as mass reduction rate 170°C 2h. When the adhesive paste is heated at 100°C for 2 hours, the mass reduction rate of the adhesive paste before and after heating is set as mass reduction rate 100°C 2h. The mass reduction rate 170°C 2h - mass reduction rate 100°C 2h is less than 14%.

10. The adhesive paste as described in claim 1 or 2, wherein, When the adhesive paste is heated at 100°C for 2 hours, the mass reduction rate of the adhesive paste before and after heating is more than 17% at 100°C for 2 hours.

11. The adhesive paste as described in claim 1 or 2, wherein, The adhesion strength of the cured product obtained by heating the adhesive paste at 100°C for 2 hours is above 10 N / mm at 100°C.

12. The adhesive paste as described in claim 1 or 2, wherein, It does not actually contain any precious metal catalysts.

13. The adhesive paste as described in claim 1 or 2 is an adhesive for semiconductor device fixing materials.

14. A method of use in which the adhesive paste described in any one of claims 1 to 13 is used as an adhesive for semiconductor element fixing material.

15. A method for manufacturing a semiconductor device, comprising the following steps (BI) and (BII): Step (BI): applying the adhesive paste to the bonding surface of one or both of the semiconductor device and the support substrate and applying pressure bonding; Step (BII): heating and curing the adhesive paste obtained in step (BI) to fix the semiconductor device onto the support substrate.