Adhesive paste, method for using adhesive paste, and method for manufacturing a semiconductor device

Abstract

The present invention is an adhesive paste, containing a thermosetting organopolysiloxane compound and a liquid constituent that satisfies requirement 1 and requirement 2, wherein the content ratio of the liquid constituent relative to the total mass of the adhesive paste is at least 15% by mass and the tack-free time of the adhesive paste is at least 20 minutes. The present invention provides an adhesive paste: that allows a semiconductor element to be mounted favorably even after a long period of time has elapsed since application of the paste onto an object to be coated (excellent chip mountability); and that, in a hardened form obtained by heating at a high temperature, has outstanding adhesiveness. Furthermore, the present invention provides an adhesive paste that has an outstanding balance between chip mountability and the adhesiveness of a hardened form of the paste, even under either high-temperature heating or low-temperature heating temperature-conditions. (Requirement 1) The liquid constituent has a viscosity of 20,000 mPa∙s or less at 25°C. (Requirement 2) The liquid constituent is a silane-based compound.

Description

Technical Field

[0001] The present invention relates to an adhesive paste that enables a semiconductor element to be satisfactorily mounted even after being left for a long time after being applied to an object to be coated, and the cured product obtained under any temperature conditions of high-temperature heating and low-temperature heating has excellent adhesiveness, a method of using this adhesive paste as an adhesive for a semiconductor element fixing material, and a method of manufacturing a semiconductor device using this adhesive paste as an adhesive for a semiconductor element fixing material.

Background Art

[0002] <关于本发明的背景技术>Conventionally, adhesive pastes have been variously improved according to their uses and have been widely used industrially as raw materials for optical components and molded bodies, adhesives, coating agents, and the like. In addition, adhesive pastes have also attracted attention as pastes for semiconductor element fixing materials such as adhesives for semiconductor element fixing materials.

[0003] Semiconductor elements include light semiconductor elements such as light-emitting elements such as lasers and light-emitting diodes (LEDs) and light-receiving elements such as solar cells, sensors such as transistors, temperature sensors, and pressure sensors, and integrated circuits. 96> An adhesive paste for semiconductor elements for fixing semiconductor elements is usually applied to an object to be coated, such as a substrate such as a lead frame, using a coating device having a discharge tube (needle) as described in Patent Document 1. In such a coating device having a discharge tube, for example, the discharge tube descends vertically and approaches the object to be coated, discharges a predetermined amount of adhesive paste from its tip, then the discharge tube rises and moves away from the object to be coated, and the object to be coated moves horizontally. By repeating this operation, the adhesive paste for semiconductor elements is continuously applied to the object to be coated. Then, a semiconductor element is mounted (placed) on the applied adhesive paste and adhered to the object to be coated.

[0005] Typically, after the adhesive paste is applied to the object to be coated, the semiconductor element is quickly mounted onto the applied adhesive paste and bonded to the object. However, in production lines and other similar environments, for various reasons, the applied adhesive paste may be left untouched for extended periods without the semiconductor elements being mounted. In such cases, if the applied adhesive paste is left for a long time, the viscosity of the adhesive paste changes, and the semiconductor element may not be mounted in a desirable state.

[0006] Furthermore, in recent years, optical semiconductor devices that emit blue light and white light, which have shorter peak wavelengths, have been developed and are being widely used. The brightness of these optical semiconductor devices with shorter peak wavelengths has increased dramatically, and consequently, the amount of heat generated by these optical semiconductor devices tends to increase even further. However, with the increasing brightness of optical semiconductor devices in recent years, the adhesives used to fix these devices have been exposed to higher energy light and higher temperatures generated by the semiconductor devices for extended periods, sometimes leading to a decrease in adhesive strength or degradation and subsequent delamination.

[0007] Therefore, there is a need for an adhesive paste that can reliably mount semiconductor elements onto the adhesive paste even after being left for a long time after being applied to the object to be coated, and whose cured product obtained by heating at high temperatures exhibits excellent adhesion.

[0008] On the other hand, optical components and sensor chips used in semiconductor devices are susceptible to heat. Therefore, when employing a heat curing method for adhesives, it is sometimes preferable to cure the adhesive at the lowest possible temperature to avoid the effects of heat on optical components and sensor chips.

[0009] Therefore, in order to precisely control the temperature range in which the adhesive paste is heated to obtain a cured product, it is desired that not only is the cured product obtained by heating at high temperatures highly adhesive, but that the cured product obtained by heating at low temperatures also exhibits excellent adhesive properties. [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] Japanese Patent Publication No. 2002-009232 [Overview of the Initiative] [Problems that the invention aims to solve]

[0011] This invention was made in view of the above circumstances, (i) To provide an adhesive paste that allows semiconductor elements to be mounted well even after a long time has elapsed since application to the object to be coated (excellent chip mountability), and in which the cured product obtained by heating at high temperature exhibits excellent adhesion. (ii) To provide an adhesive paste that offers an excellent balance between chip mountability and the adhesive properties of the resulting cured product under both high-temperature and low-temperature heating conditions, and (iii) The objective is to provide a method for using these adhesive pastes as adhesives for fixing semiconductor devices, and a method for manufacturing a semiconductor device using these adhesive pastes as adhesives for fixing semiconductor devices. In this invention, "high-temperature heating" (hereinafter sometimes referred to as "heating at high temperatures") means "heating at 150°C to 190°C," and "low-temperature heating" (hereinafter sometimes referred to as "heating at low temperatures") means "heating at 80°C to 120°C." Furthermore, "excellent adhesive properties" means "high adhesive strength." [Means for solving the problem]

[0012] The inventors diligently conducted research to solve the above problems. As a result, they discovered that an adhesive paste containing a specific amount of a liquid component which is a thermosetting organopolysiloxane compound and a silane compound having a specific viscosity can mount semiconductor elements well even after 20 minutes or more have elapsed since application to the object to be coated, and that the resulting cured product exhibits excellent adhesion under both high-temperature and low-temperature heating conditions, thus completing the present invention.

[0013] Thus, the present invention provides the adhesive pastes described in [1] to

[12] below, a method for using the adhesive paste described in

[13] , and a method for manufacturing a semiconductor device using the adhesive paste described in

[14] .

[0014] [1] An adhesive paste containing a thermosetting organopolysiloxane 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 of 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.

[0015] [2] The adhesive paste according to [1], wherein the thermosetting organopolysiloxane compound (A) is a polysilsesquioxane compound. [3] The adhesive paste according to [1] or [2], wherein the liquid component (L) is at least one selected from the group consisting of a bifunctional silane compound, a trifunctional silane compound, and a silicone oil. [4] The adhesive paste according to any one of [1] to [3], further comprising a solvent (S), wherein the solvent (S) contains an organic solvent (SL) having a boiling point of 100°C or higher and less than 254°C. [5] The adhesive paste according to [4], wherein the organic solvent (SL) has a boiling point of 100°C or higher and less than 200°C. [6] The adhesive paste according to [4] or [5], wherein the content of the organic solvent (SL) is 10% by mass or more and 50% by mass or less with respect to the total mass of the adhesive paste.

[0016] [7] Furthermore, an adhesive paste according to any of [1] to [6], which contains the following component (B). (B) Component: Fine particles [8] An adhesive paste according to any of [1] to [7], wherein the solid content concentration is 50% by mass or more and 90% by mass or less. [9] Percentage of mass loss of the adhesive paste before and after heating the adhesive paste at 170°C for 2 hours. 170℃2h However, the adhesive paste described in any of [1] to [8] is less than 55%.

[10] After heating the adhesive paste at 170°C for 2 hours, the mass reduction rate of the adhesive paste before and after heating is the mass reduction rate. 170℃2h The mass reduction rate of the adhesive paste before and after heating the adhesive paste at 100°C for 2 hours is defined as the mass reduction rate. 100℃2h In that case, the mass reduction rate 170℃2h -mass reduction rate 100℃2h However, the adhesive paste described in any of [1] to [9] is less than 14%.

[11] An adhesive paste according to any of [1] to

[10] , which substantially does not contain a precious metal catalyst.

[12] An adhesive paste for semiconductor device fixing material, as described in any of [1] to

[11] .

[0017] A method for using the adhesive paste described in any of [1] to

[12] as an adhesive for semiconductor device fixing material. A method for manufacturing a semiconductor device, wherein the adhesive paste described in any of [1] to

[12] is used as an adhesive for fixing semiconductor devices, the method comprising the following steps (BI) and (BII). Process (BI): A process of applying the adhesive paste to one or both bonding surfaces of the semiconductor element and the support substrate, and then pressing them together. Process (BII): A process to heat-cur the adhesive paste of the compressed material obtained in process (BI) and fix the semiconductor element to the support substrate. [Effects of the Invention]

[0018] According to the present invention, an adhesive paste is provided that achieves both chip mountability, enabling good mounting of semiconductor elements even after a long period of time has elapsed since application to the object to be coated, and adhesive properties of the cured product obtained by heating at high temperatures. Furthermore, the present invention provides an adhesive paste that offers an excellent balance between chip mountability and the adhesive properties of the resulting cured product, regardless of whether the heating is high or low temperature. Furthermore, the present invention provides a method for using these adhesive pastes as adhesives for fixing semiconductor devices, and a method for manufacturing a semiconductor device using these adhesive pastes as adhesives for fixing semiconductor devices. [Modes for carrying out the invention]

[0019] The present invention will be described in detail below, divided into three sections: 1) adhesive paste, 2) method of using the adhesive paste, and method of manufacturing a semiconductor device using the adhesive paste.

[0020] 1) Adhesive paste The adhesive paste of the present invention is an adhesive paste containing a thermosetting organopolysiloxane 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 of 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.

[0021] In this invention, "adhesive paste" refers to "a viscous liquid that is fluid at room temperature (23°C)." Because the adhesive paste of the present invention possesses the properties described above, it offers excellent workability in the application process. Here, "excellent workability in the coating process" means "in the coating process, when the adhesive paste is dispensed from the discharge pipe and then the discharge pipe is pulled up, the amount of stringing is small or breaks immediately, preventing resin from splashing or droplets from spreading after coating, thus preventing contamination of the surrounding area."

[0022] The adhesive paste of the present invention has a tack-free time of 20 minutes or more, preferably 30 minutes or more, more preferably 50 minutes or more, and particularly preferably 70 minutes or more. A tack-free time of 20 minutes or more results in an adhesive paste with excellent chip-mounting properties. The tack-free time can be measured by the method described in the examples.

[0023] [Thermosetting organopolysiloxane compound (A)] The adhesive paste of the present invention contains a thermosetting organopolysiloxane compound (A) (hereinafter sometimes referred to as "component (A)"). The adhesive paste of the present invention, by containing component (A), makes it easier to obtain a cured product with excellent adhesion under both high-temperature and low-temperature heating conditions.

[0024] The thermosetting organopolysiloxane compound (A) of the present invention is a compound having a carbon-silicon bond and a siloxane bond (-Si-O-Si-) within its molecule. From the viewpoint of easily obtaining an adhesive paste that exhibits excellent adhesive properties, it is preferable that component (A) is solid at 25°C. Furthermore, since component (A) is a thermosetting compound, it is preferable that it has at least one functional group selected from the group consisting of functional groups that can undergo a condensation reaction upon heating and functional groups that can undergo a condensation reaction via hydrolysis. Such functional groups are preferably at least one selected from the group consisting of hydroxyl groups and alkoxy groups, with hydroxyl groups and alkoxy groups having 1 to 10 carbon atoms being more preferred. There are no restrictions on the main chain structure of the thermosetting organopolysiloxane compound (A), and it may be linear, ladder-like, or cage-like. For example, a linear main chain structure can be represented by the structure shown in equation (a-1) below, a ladder-like main chain structure can be represented by the structure shown in equation (a-2) below, and a cage-like main chain structure can be represented by the structure shown in equation (a-3) below.

[0025] [ka]

[0026] [ka]

[0027] [ka]

[0028] In formulas (a-1) to (a-3), Rx, Ry, and Rz each independently represent a hydrogen atom or an organic group. Preferred organic groups are unsubstituted or substituted alkyl groups, unsubstituted or substituted cycloalkyl groups, unsubstituted or substituted alkenyl groups, unsubstituted or substituted aryl groups, or alkylsilyl groups. The multiple Rx in formula (a-1), the multiple Ry in formula (a-2), and the multiple Rz in formula (a-3) may be the same or different. However, it is not possible for both Rx in formula (a-1) to be hydrogen atoms.

[0029] Examples of the unsubstituted or substituted alkyl groups include C1 to C10 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, and n-octyl group.

[0030] Examples of unsubstituted or substituted cycloalkyl groups include cycloalkyl groups having 3 to 10 carbon atoms, such as cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl groups.

[0031] Examples of unsubstituted or substituted alkenyl groups include C2 to C10 alkenyl groups such as vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, and 3-butenyl group.

[0032] Examples of substituents on the alkyl, cycloalkyl, and alkenyl groups include halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; hydroxyl groups; thiol groups; epoxy groups; glycidoxy groups; (meth)acryloyloxy groups; and unsubstituted or substituted aryl groups such as phenyl groups, 4-methylphenyl groups, and 4-chlorophenyl groups.

[0033] Examples of unsubstituted or substituted aryl groups include aryl groups having 6 to 10 carbon atoms, such as phenyl, 1-naphthyl, and 2-naphthyl groups.

[0034] Examples of substituents on the aryl group include halogen atoms such as fluorine, chlorine, bromine, and iodine; C1-C6 alkyl groups such as methyl and ethyl groups; C1-C6 alkoxy groups such as methoxy and ethoxy groups; nitro groups; cyano groups; hydroxyl groups; thiol groups; epoxy groups; glycidoxy groups; (meth)acryloyloxy groups; and unsubstituted or substituted aryl groups such as phenyl, 4-methylphenyl, and 4-chlorophenyl groups.

[0035] Examples of alkylsilyl groups include trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, tri-t-butylsilyl group, methyldiethylsilyl group, dimethylsilyl group, diethylsilyl group, methylsilyl group, and ethylsilyl group.

[0036] Among these, Rx, Ry, and Rz are preferably hydrogen atoms, unsubstituted or substituted C1-C6 alkyl groups, or phenyl groups, with unsubstituted or substituted C1-C6 alkyl groups being particularly preferred.

[0037] Thermosetting organopolysiloxane compounds (A) can be obtained, for example, by known production methods involving polycondensation of silane compounds having hydrolyzable functional groups (alkoxy groups, halogen atoms, etc.).

[0038] The silane compound used should be appropriately selected depending on the structure of the target thermosetting organopolysiloxane compound (A). Preferred specific examples include difunctional silane compounds such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, and diethyldiethoxysilane; Trifunctional silane compounds such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and phenyldiethoxymethoxysilane; Examples include tetrafunctional silane compounds such as tetramethoxysilane, tetraethoxysilane, tetran-propoxysilane, tetraisopropoxysilane, tetran-butoxysilane, tetrat-butoxysilane, tetras-butoxysilane, methoxytriethoxysilane, dimethoxydiethoxysilane, and trimethoxyethoxysilane.

[0039] The mass-average molecular weight (Mw) of the thermosetting organopolysiloxane compound (A) is typically 800 to 30,000, preferably 1,000 to 20,000, more preferably 1,200 to 15,000, and particularly preferably 3,000 to 10,000. By using a thermosetting organopolysiloxane compound (A) with a mass-average molecular weight (Mw) within the above range, it becomes easier to obtain an adhesive paste that provides a cured product with superior heat resistance and adhesion.

[0040] The molecular weight distribution (Mw / Mn) of the thermosetting organopolysiloxane compound (A) is not particularly limited, but is usually between 1.0 and 10.0, preferably between 1.1 and 6.0. By using a thermosetting organopolysiloxane compound (A) with a molecular weight distribution (Mw / Mn) within the above range, it becomes easier to obtain an adhesive paste 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 determined, for example, as standard polystyrene equivalent values ​​obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as the solvent.

[0041] The thermosetting organopolysiloxane compound (A) of the present invention is preferably a polysilsesquioxane compound obtained by polycondensation of a trifunctional organosilane compound. The adhesive paste of the present invention contains a polysilsesquioxane compound as component (A), which makes it easier to obtain a cured product with superior adhesive properties under both high-temperature and low-temperature heating conditions.

[0042] The polysilsesquioxane compound of the present invention is a compound having a repeating unit represented by the following formula (a-4). By containing, as the component (A), a polysilsesquioxane compound having a repeating unit represented by the following formula (a-4), the adhesive paste of the present invention can easily obtain a cured product having excellent adhesiveness under any temperature conditions of high-temperature heating and low-temperature heating.

[0043]

Chemical formula

[0044] In the formula (a-4), R 1 represents an organic group. As the organic group, a group selected from the group consisting of an unsubstituted alkyl group, an alkyl group having a substituent, an unsubstituted cycloalkyl group, a cycloalkyl group having a substituent, an unsubstituted alkenyl group, an alkenyl group having a substituent, an unsubstituted aryl group, an aryl group having a substituent, and an alkylsilyl group is preferable, and a group selected from the group consisting of an unsubstituted alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms having a substituent, an unsubstituted aryl group having 6 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms having a substituent is more preferable.

[0045] Examples of the "unsubstituted alkyl group having 1 to 10 carbon atoms" include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, an n-nonyl group, an n-decyl group, and the like. R 1 The carbon number of the "unsubstituted alkyl group having 1 to 10 carbon atoms" represented by is preferably 1 to 6, and more preferably 1 to 3.

[0046] R 1 The carbon number of the "alkyl group having 1 to 10 carbon atoms having a substituent" represented by is preferably 1 to 6, and more preferably 1 to 3. Note that this carbon number means the carbon number of the part excluding the substituent (the alkyl group part). Therefore, R 1If R is a "carbon 1 to carbon 10 alkyl group having substituents", 1 The number of carbon atoms can sometimes exceed 10. Examples of alkyl groups in "alkyl groups having 1 to 10 carbon atoms with substituents" are the same as those listed as "unsubstituted alkyl groups having 1 to 10 carbon atoms."

[0047] Examples of substituents in "alkyl groups having 1 to 10 carbon atoms with substituents" include halogen atoms such as fluorine, chlorine, and bromine atoms; cyano groups; and groups represented by the formula OG. The number of substituent atoms (excluding hydrogen atoms) in a "substituted alkyl group having 1 to 10 carbon atoms" is usually 1 to 30, preferably 1 to 20. Here, G represents a hydroxyl protecting group. There are no particular restrictions on the hydroxyl protecting group, and known protecting groups that are known to protect hydroxyl groups can be used. For example, acyl groups; silyl groups such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, and t-butyldiphenylsilyl group; acetal groups such as methoxymethyl group, methoxyethoxymethyl group, 1-ethoxyethyl group, tetrahydropyran-2-yl group, and tetrahydrofuran-2-yl group; alkoxycarbonyl groups such as t-butoxycarbonyl group; ether groups such as methyl group, ethyl group, t-butyl group, octyl group, allyl group, triphenylmethyl group, benzyl group, p-methoxybenzyl group, fluorenyl group, trityl group, and benzhydryl group; and so on.

[0048] Examples of "unsubstituted aryl groups having 6 to 12 carbon atoms" include the phenyl group, 1-naphthyl group, and 2-naphthyl group. R 1 The "unsubstituted aryl group with 6 to 12 carbon atoms" represented by preferably has 6 carbon atoms.

[0049] R 1 The "substituted aryl group having 6 to 12 carbon atoms" represented by is preferably 6 carbon atoms. Note that this carbon number refers to the carbon number of the part excluding the substituent (the aryl group part). Therefore, R 1If R is a "substituted aryl group having 6 to 12 carbon atoms", 1 The number of carbon atoms can sometimes exceed 12. Examples of aryl groups referred to as "substituted aryl groups having 6 to 12 carbon atoms" include those similar to those listed as "unsubstituted aryl groups having 6 to 12 carbon atoms."

[0050] Examples of substituents for "aryl groups having 6 to 12 carbon atoms with substituents" include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and isooctyl groups; halogen atoms such as fluorine, chlorine, and bromine atoms; and alkoxy groups such as methoxy and ethoxy groups. The number of substituent atoms (excluding hydrogen atoms) in a "substituted aryl group having 6 to 12 carbon atoms" is usually 1 to 30, preferably 1 to 20.

[0051] Among these, R 1 From the viewpoint of easily obtaining a structurally stable polysilsesquioxane compound and achieving more stable performance as an adhesive paste, it is preferable that the compound be at least one selected from the group consisting of an unsubstituted C1-C10 alkyl group, a C1-C10 alkyl group having a fluorine atom, and an unsubstituted C6-C12 aryl group. R 1 However, by using polysilsesquioxane compounds, which are unsubstituted alkyl groups having 1 to 10 carbon atoms, it becomes easier to obtain adhesive pastes that provide cured products with superior heat resistance and adhesion. R 1 However, by using a polysilsesquioxane compound, which is an alkyl group having 1 to 10 carbon atoms and containing a fluorine atom, it becomes easier to obtain adhesive pastes and cured products with a long tack-free time and a low refractive index, making them suitable for use in optical semiconductor devices where a low refractive index is desired. A C1-C10 alkyl group containing a fluorine atom is defined by the chemical formula: C m H (2m-n+1) F nExamples of groups represented by (where m is an integer from 1 to 10, and n is an integer from 1 to (2m+1)) include the 3,3,3-trifluoropropyl group. R 1 By using a polysilsesquioxane compound in which the aryl group has 6 to 12 carbon atoms and is unsubstituted, it becomes easier to obtain adhesive pastes and cured products with a high refractive index, making them suitable for use in optical semiconductor devices where a high refractive index is desired.

[0052] The content of the repeating units represented by formula (a-4) in the polysilsesquioxane compound (i.e., the T-sites described later) is usually 50 to 100 mol%, more preferably 70 to 100 mol%, even more preferably 90 to 100 mol%, and particularly preferably 100 mol%, relative to the total number of repeating units. By using a polysilsesquioxane compound having the above-mentioned proportion of repeating units (T-sites) represented by formula (a-4), an adhesive paste that readily exhibits heat resistance, adhesion, and refractive index properties can be obtained. The proportion of repeating units (T sites) represented by formula (a-4) in a polysilsesquioxane compound is, for example, when NMR peak assignment and area integration are possible, 29 Si-NMR and 1 This can be determined by measuring H-NMR.

[0053] 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 mixed solvents consisting of two or more of these. Therefore, using these solvents, polysilsesquioxane compounds can be prepared in solution. 29 Si-NMR can be measured.

[0054] The repeating unit represented by formula (a-4) above is preferably represented by the following formula (a-5).

[0055] [ka]

[0056] As shown in formula (a-5), polysilsesquioxane compounds generally have a T site, which is a silicon atom bonded to three oxygen atoms, and other groups (R 1 It has a substructure formed by the combination of one of the following.

[0057] In formula (a-5), R 1 R in the above formula (a-4) is 1 This has the same meaning as *. * represents a Si atom, a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, and at least one of the three *s is a Si atom. Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, isobutyl, and t-butyl groups. Multiple *s may all be the same or different.

[0058] Furthermore, polysilsesquioxane compounds are thermosetting compounds that can undergo condensation reactions and / or hydrolysis reactions upon heating. Therefore, it is preferable that at least one of the * in formula (a-5) of the multiple repeating units (T sites) of the polysilsesquioxane compound be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom. Furthermore, if the polysilsesquioxane compound is soluble in the solvent used for measurement, 29 By measuring Si-NMR, it is possible to confirm the presence of a hydrogen atom or an alkyl group having 1 to 10 carbon atoms in the * in formula (a-5), and whether the three * in formula (a-5) are all Si atoms in a repeating unit. moreover, 29If Si-NMR peak assignment and area integration are possible, the total number of repeating units in formula (a-5) where all three * are Si atoms can be estimated relative to the total number of repeating units (T sites) represented by formula (a-4) in the polysilsesquioxane compound. The total number of repeating units in the polysilsesquioxane compound where all three * atoms in formula (a-5) are Si atoms is preferably 30 to 95 mol%, and more preferably 40 to 90 mol%, from the viewpoint of obtaining an adhesive paste that gives a cured product with superior heat resistance.

[0059] Polysilsesquioxane compounds are a type of R 1 It may also be a homopolymer having two or more R 1 It may also be a copolymer having [a specific characteristic].

[0060] When the polysilsesquioxane compound is a copolymer, it may be a random copolymer, block copolymer, graft copolymer, alternating copolymer, etc., but a random copolymer is preferred from the viewpoint of ease of manufacture, etc. Furthermore, the structure of the polysilsesquioxane compound may be any of the following: ladder structure, double-decker structure, cage structure, partially cleaved cage structure, cyclic structure, or random structure.

[0061] In the present invention, polysilsesquioxane compounds can be used individually or in combination of two or more.

[0062] The method for producing polysilsesquioxane compounds is not particularly limited. For example, the following formula (a-6)

[0063] [ka]

[0064] (In the formula, R1 R in the above formula (a-4) is 1 It expresses the same meaning as R. 2 X represents an alkyl group with 1 to 10 carbon atoms. 1 R represents a halogen atom, and p represents an integer from 0 to 3. Multiple R 2 , and multiple X 1 These elements may be identical or different from one another. A polysilsesquioxane compound can be produced by polycondensing at least one of the silane compounds (1) shown in the diagram. R 2 Examples of C1-C10 alkyl groups include those similar to those shown as the C1-C10 alkyl group * in formula (a-5) above. X 1 Examples of halogen atoms include chlorine atoms and bromine atoms.

[0065] Specific examples of silane compounds (1) include alkyltrialkoxysilane compounds such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and ethyltripropoxysilane; Alkylhalogenolalkoxysilane compounds such as methylchlorodimethoxysilane, methylchlorodiethoxysilane, methyldichloromethoxysilane, methylbromodimethoxysilane, ethylchlorodimethoxysilane, ethylchlorodiethoxysilane, ethyldichloromethoxysilane, and ethylbromodimethoxysilane; Alkyl trihalogenosilane compounds such as methyltrichlorosilane, methyltribromosilane, ethyltrichlorosilane, and ethyltribromosilane;

[0066] Substituted alkyltrialkoxysilane compounds such as 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 2-cyanoethyltrimethoxysilane, and 2-cyanoethyltriethoxysilane; Substituted alkylhalogenalkoxysilane compounds such as 3,3,3-trifluoropropylchlorodimethoxysilane, 3,3,3-trifluoropropylchlorodiethoxysilane, 3,3,3-trifluoropropyldichloromethoxysilane, 3,3,3-trifluoropropyldichloroethoxysilane, 2-cyanoethylchlorodimethoxysilane, 2-cyanoethylchlorodiethoxysilane, 2-cyanoethyldichloromethoxysilane, and 2-cyanoethyldichloroethoxysilane; Substituted alkyltrihalogenosilane compounds such as 3,3,3-trifluoropropyltrichlorosilane and 2-cyanoethyltrichlorosilane;

[0067] Phenyltrialkoxysilane compounds with or without substituents, such as phenyltrimethoxysilane and 4-methoxyphenyltrimethoxysilane; Phenylhalogenoalkoxysilane compounds with or without substituents, such as phenylchlorodimethoxysilane, phenyldichloromethoxysilane, 4-methoxyphenylchlorodimethoxysilane, and 4-methoxyphenyldichloromethoxysilane; Examples include phenyltrihalogenosilane compounds with or without substituents, such as phenyltrichlorosilane and 4-methoxyphenyltrichlorosilane; and so on. These silane compounds (1) can be used individually or in combination of two or more.

[0068] The method for polycondensing the silane compound (1) is not particularly limited. For example, one method is to add a predetermined amount of polycondensation catalyst to the silane compound (1) in a solvent or without a solvent and stir at a predetermined temperature. More specifically, (a) a method in which a predetermined amount of acid catalyst is added to the silane compound (1) and stirred at a predetermined temperature, (b) a method in which a predetermined amount of base catalyst is added to the silane compound (1) and stirred at a predetermined temperature, (c) a method in which a predetermined amount of acid catalyst is added to the silane compound (1), stirred at a predetermined temperature, and then an excess amount of base catalyst is added to make the reaction system basic, and then stirred at a predetermined temperature. Among these, method (a) or (c) is preferred because it allows for efficient acquisition of the desired polysilsesquioxane compound.

[0069] The polycondensation catalyst used may be either an acid catalyst or a base catalyst. Furthermore, two or more polycondensation catalysts may be used in combination, but it is preferable to use at least one acid catalyst. Examples of acid catalysts include inorganic acids such as phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, and nitric acid; and organic acids such as citric acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid. Among these, at least one selected from phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, citric acid, acetic acid, and methanesulfonic acid is preferred.

[0070] Examples of base catalysts include aqueous 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; metal alkoxides such as sodium methoxide, sodium ethoxide, sodium t-butoxide, and potassium t-butoxide; metal hydrides such as sodium hydride and calcium hydride; metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide; metal carbonates such as sodium carbonate, potassium carbonate, and magnesium carbonate; and metal bicarbonates such as sodium bicarbonate and potassium bicarbonate.

[0071] The amount of polycondensation catalyst used is typically in the range of 0.05 to 10 mol%, preferably 0.1 to 5 mol%, relative to the total molar amount of silane compound (1).

[0072] When a solvent is used during polycondensation, the solvent can be appropriately selected depending on the type of silane compound (1), etc. Examples include 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 methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, s-butyl alcohol, and t-butyl alcohol. These solvents can be used individually or in combination of two or more. Furthermore, when employing the method described in (c) above, the polycondensation reaction may be carried out in an aqueous system in the presence of an acid catalyst, and then an organic solvent and a base catalyst (such as aqueous ammonia) may be added to the reaction solution, and the polycondensation reaction may be carried out again under neutral or basic conditions.

[0073] The amount of solvent used is usually 0.001 liters to 10 liters, preferably 0.01 liters to 0.9 liters, per mole of the total amount of silane compound (1).

[0074] The temperature used for polycondensation of the silane compound (1) is typically within the range from 0°C to the boiling point of the solvent used, preferably between 20°C and 100°C, and more preferably between 30°C and 95°C. If the reaction temperature is too low, the polycondensation reaction may not proceed sufficiently. On the other hand, if the reaction temperature is too high, it becomes difficult to suppress gelation. The reaction is usually completed in 30 minutes to 30 hours.

[0075] Furthermore, depending on the type of monomer used, it may be difficult to increase the molecular weight. For example, R 1 A monomer in which is an alkyl group having a fluorine atom is R 1 These monomers tend to be less reactive than monomers with typical alkyl groups. In such cases, reducing the amount of catalyst and carrying out the reaction for a long time under mild conditions makes it easier to obtain the polysilsesquioxane compound with the desired molecular weight.

[0076] After the reaction is complete, if an acid catalyst is used, the reaction solution is neutralized by adding an alkaline aqueous solution such as sodium bicarbonate. If a base catalyst is used, the reaction solution is neutralized by adding an acid such as hydrochloric acid. The salt produced at this time is then removed by filtration or washing with water to obtain the desired polysilsesquioxane compound.

[0077] When producing a polysilsesquioxane compound by the above method, the OR of silane compound (1) 2 or X 1 Of these, the portion that did not undergo hydrolysis and subsequent condensation reactions remains in the polysilsesquioxane compound.

[0078] If component (A) is, for example, a polysilsesquioxane compound obtained by a polycondensation reaction of silane compound (1), the curing proceeds by a condensation reaction. Therefore, the adhesive paste of the present invention is different from general heat-curing silicone adhesives that cure by an addition reaction in the presence of a precious metal catalyst such as a platinum catalyst. Therefore, the adhesive paste containing the polysilsesquioxane compound of the present invention substantially does not contain a noble metal catalyst, or contains a small amount of a noble metal catalyst. Here, "substantially free of precious metal catalysts, or containing a small amount of precious metal catalysts" means "that, in addition to the fact that components that could be interpreted as precious metal catalysts are not intentionally added, the content of precious metal catalysts relative to the amount of active ingredients in the adhesive paste is, for example, less than 1 ppm by mass in terms of the mass of the catalyst metal element." Here, "active ingredient" refers to "the components of the adhesive paste excluding the solvent (S) (described later) contained within it." Adhesive pastes are preferably substantially free of or contain very little precious metal catalysts, considering factors such as stable manufacturing due to variations in formulation, storage stability, and the high cost of precious metal catalysts.

[0079] [Liquid component (L)] The liquid component (L) constituting the adhesive paste of the present invention (hereinafter sometimes referred to as "component (L)") satisfies the following requirements 1 and 2. [Requirement 1] The 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) mixes well with component (A), making it easy to obtain an adhesive paste with stable performance. Examples of liquid components (L) that satisfy requirements 1 and 2 above include bifunctional silane compounds, trifunctional silane compounds, polyfunctional silane compounds, and silicone oils.

[0080] 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 particularly preferably 5,000 mPa·s or less. Adhesive pastes containing a liquid component (L) with a viscosity at 25°C below the above upper limit become less volatile at room temperature (20°C ± 15°C), making it easier to obtain adhesive pastes with a long tack-free time. On the other hand, adhesive pastes containing a high-viscosity liquid component (L) whose viscosity at 25°C exceeds the above upper limit may have a shorter tack-free time due to their high viscosity; however, this risk can be reduced by keeping the viscosity below the above upper limit. Furthermore, by including a liquid component (L) with a viscosity at 25°C below the above upper limit, it becomes easier to obtain an adhesive paste that offers excellent workability in the coating process and provides a cured product with superior adhesion, heat resistance, and crack suppression of the cured product under both high-temperature and low-temperature heating conditions. Here, "superior crack suppression of the cured product" means "when heating the adhesive paste to obtain a cured product, no cracking occurs in the cured product due to temperature changes."

[0081] Examples of bifunctional silane compounds include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldimethoxysilane.

[0082] Commercially available bifunctional silane compounds 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, KBM-202SS is preferred because it mixes well with other active ingredients and easily yields an adhesive paste with stable performance.

[0083] Examples of trifunctional silane compounds include 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-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane Examples include lan, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, 2-trimethoxysilylethyl succinic anhydride, 2-triethoxysilylethyl succinic anhydride, 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, and 3-mercaptopropyltrimethoxysilane.

[0084] Commercially available trifunctional silane compounds can also be used. Examples of commercially available products include 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 Co., Ltd.). Among these, X-12-967C, KBM-103, KBM-503, KBM-5103, and KBE-9007N can be preferably used, and X-12-967C, KBM-5103, and KBE-9007N can be particularly preferably used, as they mix well with other active ingredients and make it easier to obtain an adhesive paste with stable performance.

[0085] Examples of polyfunctional silane compounds include compounds having a nitrogen atom in the molecule and four or more alkoxy groups bonded to silicon atoms, and compounds having an organic main chain and four or more alkoxy groups bonded to organic functional groups and silicon atoms. Having four or more alkoxy groups bonded to silicon atoms means that the total number of alkoxy groups bonded to the same silicon atom and alkoxy groups bonded to different silicon atoms is four or more.

[0086] Examples of polyfunctional silane compounds having a nitrogen atom in the molecule and four or more alkoxy groups bonded to a silicon atom in the molecule include isocyanurate compounds and urea compounds.

[0087] Examples of isocyanurate compounds include those represented by the following formula (l-1), and examples of urea compounds include those represented by the following formula (l-2).

[0088] [ka]

[0089] In the formula, R aR represents alkoxy groups with 1 to 6 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and t-butoxy groups. a The elements may be identical or different. Each of t1 to t5 independently represents an integer from 1 to 10, preferably from 1 to 6, and particularly preferably 3.

[0090] Specific examples of compounds represented by formula (l-1) include 1,3,5-N-tris(3-trimethoxysilylpropyl)isocyanurate, 1,3,5-N-tris(3-triethoxysilylpropyl)isocyanurate, 1,3,5-N-tris(3-tri-i-propoxysilylpropyl)isocyanurate, 1,3,5-N-tris(3-tributoxysilylpropyl)isocyanurate, and other 1,3,5-N-tris[(tri(carbon 1-6)alkoxy)silyl(carbon 1-10)alkyl]isocyanurate compounds; 1,3,5-N-Tris(3-dimethoxymethylsilylpropyl) isocyanurate, 1,3,5-N-Tris(3-dimethoxyethylsilylpropyl) isocyanurate, 1,3,5-N-Tris(3-dimethoxyi-propylsilylpropyl) 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 Methylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-diethoxyethylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-diethoxyi-propylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-diethoxyn-propylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-diethoxyphenylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-di-i-propoxymethylsilylpropyl) isocyanurate 1,3,5-N-tris(3-di-i-propoxyethylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-di-i-propoxy-i-propylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-di-i-propoxy-n-propylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-di-i-propoxyphenylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-dibutoxymethylsilylpropyl) isocyanurate, 1,3, Examples include 1,3,5-N-tris[(di(C1-C6)alkoxy)silyl(C1-C10)alkyl]isocyanurates such as 5-N-tris(3-dibutoxyethylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dibutoxyi-propylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dibutoxyphenylsilylpropyl)isocyanurate, etc.

[0091] Specific examples of compounds represented by formula (l-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 other N,N'-bis[(tri(carbon 1-6)alkoxysilyl)(carbon 1-10)alkyl]urea; N,N'-bis(3-dimethoxymethylsilylpropyl)urea, N,N'-bis(3-dimethoxyethylsilylpropyl)urea, N,N'-bis(3-diethoxymethylsilylpropyl)urea, etc. N,N'-bis[(di(carbon 1-6)alkoxy(carbon 1-6)alkylsilyl(carbon 1-10)alkyl)urea; Examples include N,N'-bis(3-dimethoxyphenylsilylpropyl)urea, N,N'-bis(3-diethoxyphenylsilylpropyl)urea, and other N,N'-bis[(di(carbon 1-6)alkoxy(carbon 6-20)arylsilyl(carbon 1-10)alkyl)ureas;

[0092] As a compound having a nitrogen atom in its molecule and four or more alkoxy groups bonded to silicon atoms in its molecule, commercially available products can also be used. An example of a commercially available product is KBM-9659 (manufactured by Shin-Etsu Chemical Co., Ltd.). Among these, KBM-9659 is preferred because it mixes well with other active ingredients and easily yields an adhesive paste with stable performance.

[0093] As a compound having an organic main chain and four or more alkoxy groups bonded to organic functional groups and silicon atoms, commercially available products can be used. Examples of commercially available products include X-12-1048, X-12-981S, X-12-1159L, etc. (all manufactured by Shin-Etsu Chemical Co., Ltd.). Among these, X-12-1159L is preferred because it mixes well with other active ingredients and easily yields an adhesive paste with stable performance.

[0094] Silicone oils include straight silicone oil and modified silicone oil. Straight silicone oils are linear polymer compounds consisting of siloxane bonds, and examples include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil.

[0095] Modified silicone oils are polysiloxanes to which organic groups have been introduced into the side chains or terminals. Modified silicone oils are classified into side-chain type, double-ended type, single-ended type, and side-chain double-ended type depending on the bonding position of the introduced organic groups. Furthermore, they are classified into reactive silicone oils and non-reactive silicones depending on the properties of the introduced organic groups. Examples of organic groups include amino groups, epoxy groups, methacrylic groups, acrylic groups, silanol groups, and carboxyl groups.

[0096] Commercially available silicone oils can also be used. Examples of commercially available straight silicone oils include the KF-96L series, KF-50 series, and KF-99 series (all manufactured by Shin-Etsu Chemical Co., Ltd.). Furthermore, commercially available modified silicone oils include, for example, the KF series such as KF-868, in which monoamines are introduced into the side chain; the X-22-173 series such as X-22-173BX, in which acrylic groups are introduced into both ends, and X-22-173BX, in which an epoxy group is introduced into one end (all manufactured by Shin-Etsu Chemical Co., Ltd.); and XF42-334 (manufactured by Momentive Performance Materials Japan). Among these, modified silicone oils are preferable because they mix well with other active ingredients and provide a stable adhesive paste. X-22-2445 and XF42-334 are particularly preferable.

[0097] Among these liquid components (L), from the viewpoint of easily obtaining an adhesive paste with a longer tack-free time, bifunctional silane compounds, trifunctional silane compounds, and silicone oil are more preferred, with bifunctional silane compounds and silicone oil being particularly preferred. Furthermore, from the viewpoint of easily obtaining an adhesive paste with excellent adhesive strength in the cured product obtained by heating at low temperatures, trifunctional silane compounds and silicone oil are particularly preferred. The liquid component (L) may be used alone or in combination of two or more types.

[0098] The liquid component (L) content 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 particularly preferably 21% by mass or more and less than 35% by mass, relative to the total mass of the adhesive paste. By setting the content of the liquid component (L) relative to the total mass of the adhesive paste within the above range, the effect of using the liquid component (L) can be further enhanced.

[0099] [Other ingredients] The adhesive paste of the present invention contains a thermosetting organopolysiloxane compound (A) and a liquid component (L), but may also contain the following components. (1) Solvent (S) The solvent (S) contained in the adhesive paste of the present invention is not particularly limited as long as it can dissolve or disperse the components of the adhesive paste of the present invention. The solvent (S) preferably includes an organic solvent (SL) with a boiling point of 100°C or higher and less than 254°C. Here, "boiling point" refers to "the 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 less than 254°C, preferably 100°C or higher and less than 200°C, more preferably 105°C or higher and less than 185°C, and particularly preferably 110°C or higher and less than 170°C.

[0100] Such organic solvents (SL) volatilize more efficiently when heated at low temperatures compared to high-boiling point organic solvents with a boiling point between 254°C and 300°C. Therefore, by including an organic solvent (SL) as the solvent (S), the mass loss rate can be improved. 170℃2h -mass reduction rate 100℃2h (As described later) it is easier to obtain an adhesive paste with less than 14% of this substance. In addition, such organic solvents (SL) have a relatively slow volatilization rate compared to low-boiling point organic solvents with a boiling point of less than 100°C. Therefore, adhesive pastes containing organic solvents (SL) readily achieve sufficient adhesive strength when heated at low temperatures because the solvent evaporates efficiently without leaving a large amount of residue. In addition, the concentration of the active ingredients in the adhesive paste increases rapidly even when heated at low temperatures, making it easy to cure. As a result, semiconductor elements can be mounted well even long after application to the substrate, and the resulting cured product exhibits excellent adhesion.

[0101] 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), and ethylene glycol monophenyl ether (boiling point 245°C). Examples include tripropylene glycol methyl ether (boiling point 242°C), propylene glycol phenyl ether (boiling point 243°C), triethylene glycol monomethyl ether (boiling point 249°C), benzyl alcohol (boiling point 204.9°C), phenethyl alcohol (boiling point 219-221°C), ethylene glycol monobutyl ether acetate (boiling point 192°C), ethylene glycol monoethyl ether (boiling point 134.8°C), ethylene glycol monomethyl ether (boiling point 124.5°C), propylene glycol monomethyl ether acetate (boiling point 146°C), cyclopentanone (boiling point 130°C), cyclohexanone (boiling point 157°C), cycloheptanone (boiling point 180°C), cyclooctanone (boiling point 195-197°C), cyclohexanol (boiling point 161°C), and cyclohexadienone (boiling point 104-104.5°C). Among these, diethylene glycol monoethyl ether acetate and cyclohexanone are preferred as organic solvents (SL) from the viewpoint of being able to better express the effects of using organic solvents (SL) and from the viewpoint of being able to easily mix the active ingredients well, and cyclohexanone is more preferred. Organic solvents (SL) may be used individually or in combination of two or more.

[0102] The adhesive paste of the present invention preferably contains an organic solvent (SL) of 10% to 50% by mass, more preferably 13% to 40% by mass, and particularly preferably 15% to 30% by mass, based on the total mass of the adhesive paste. By setting the content of organic solvent (SL) relative to the total mass of the adhesive paste within the above range, the workability in the process of filling the syringe with the adhesive paste and the application process can be improved, and the effects of using organic solvent (SL) can be further realized. Here, "excellent workability in the process of filling the syringe with adhesive paste" means "the ability to fill the syringe with the appropriate amount without air bubbles."

[0103] The adhesive paste of the present invention may contain solvents other than organic solvents (SL). As a solvent other than organic solvents (SL), organic solvents with a boiling point between 254°C and 300°C (hereinafter sometimes referred to as "organic solvents (SH)") are preferred. The organic solvent (SH) is not particularly limited as long as it has a boiling point of 254°C or higher and 300°C or lower, and is capable of dissolving or dispersing the components of the adhesive paste of the present invention. By using organic solvents (SL) and other solvents in combination, the temperature range for heating the adhesive paste to obtain a cured product can be controlled more precisely, thereby reducing the effects of heating on optical components and sensor chips that are susceptible to heat.

[0104] 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, tripropylene glycol-n-butyl ether and 1,6-hexanediol diacrylate are preferred as organic solvents (SH) from the viewpoint of obtaining the effect of using both organic solvents (SL) and organic solvents (SH) in combination.

[0105] When using an organic solvent (SL) and an organic solvent (SH) 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)); and cyclohexanone (organic solvent (SL)) and 1,6-hexanediol diacrylate (organic solvent (SH)).

[0106] The organic solvent (SL) preferably accounts for 60% by mass or more of the total solvent (S), more preferably 65% ​​by mass or more, and particularly preferably 70% by mass or more. By using the organic solvent (SL) within the above range for the entire solvent (S), the effects of using the organic solvent (SL) can be more effectively realized.

[0107] The adhesive paste of the present invention preferably contains an amount of solvent (S) such that the solid content concentration is preferably 50% by mass or more and 90% by mass or less, more preferably 70% by mass or more and 90% by mass or less. Having a solid content concentration within this range allows for good mixing of the active ingredients, resulting in excellent workability in the process of filling the adhesive paste into syringes and in the application process, while also allowing the effects of using organic solvents (SL) to be more fully realized. Furthermore, when performing die bonding, the generation of voids between the adhesive paste and the substrate or other object to be bonded can be suppressed, thereby improving the reliability of the package.

[0108] (2) Fine particles (B) The adhesive paste of the present invention may contain fine particles as component (B). Examples of fine particles include fine particles with an average primary particle diameter of 5 nm or more and 40 nm or less (B1) (hereinafter sometimes referred to as "component (B1)") and fine particles with an average primary particle diameter of more than 0.04 μm and 8 μm or less (B2) (hereinafter sometimes referred to as "component (B2)").

[0109] By incorporating fine particles (B1), it becomes easier to obtain an adhesive paste that offers excellent workability in the coating process and provides a cured product with superior adhesion and heat resistance under both high-temperature and low-temperature heating conditions. To make this effect easier to obtain, the average primary particle diameter of the fine particles (B1) is preferably 5 nm to 30 nm, more preferably 5 nm to 20 nm. The average primary particle size of the fine particles (B1) can be determined by observing the shape of the fine particles using a transmission electron microscope.

[0110] The specific surface area of ​​the fine particles (B1) is preferably 10 m². 2 / g or more 500m 2 / g or less, more preferably 20m 2 / g or more 300m 2 It is less than / g. Having a specific surface area within the above range makes it easier to obtain an adhesive paste with superior workability during the coating process. The specific surface area can be determined using the BET multipoint method.

[0111] The shape of the fine particles (B1) may be spherical, chain-like, needle-like, plate-like, flake-like, rod-like, fibrous, etc., but it is preferable that they be spherical. Here, "spherical" means "approximately spherical, including not only a perfect sphere but also polyhedral shapes that can approximate a sphere, such as a spheroid, oval, konpeito-like, or cocoon-like shape."

[0112] There are no particular restrictions on the constituent components of the fine particles (B1), and examples include metals, metal oxides, minerals, metal carbonates, metal sulfates, metal hydroxides, metal silicates, inorganic components, organic components, silicones, etc. Furthermore, the fine particles (B1) used may have a modified surface.

[0113] Metals are elements belonging to Group 1 (excluding H), Groups 2-11, Group 12 (excluding Hg), Group 13 (excluding B), Group 14 (excluding C and Si), Group 15 (excluding N, P, As and Sb), or Group 16 (excluding O, S, Se, Te and Po) of the periodic table.

[0114] Examples of metal oxides include titanium oxide, alumina, boehmite, chromium oxide, nickel oxide, copper oxide, zirconium oxide, indium oxide, zinc oxide, and composite oxides thereof. Fine particles of metal oxides also include sol particles composed of these metal oxides.

[0115] Examples of minerals include smectite and bentonite. Examples of smectites include montmorillonite, beiderite, hectorite, saponite, stivunsite, nontronite, and soakonite.

[0116] 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. In addition, examples of inorganic components include silica. Examples of silica include dry silica, wet silica, and surface-modified silica (silica with a modified surface). Examples of organic components include acrylic polymers.

[0117] Silicone refers to artificial polymer compounds that have a main skeleton composed of siloxane bonds. Examples include dimethylpolysiloxane, diphenylpolysiloxane, and methylphenylpolysiloxane.

[0118] The fine particles (B1) can be used individually or in combination of two or more types. Among these, silica, metal oxides, and minerals are preferred in the present invention because they easily yield an adhesive paste with excellent transparency, and silica is more preferred.

[0119] Among silicas, surface-modified silica is preferred because it is relatively easy to mix as an adhesive paste and because it is easier to obtain an adhesive paste with superior workability in the coating process, and hydrophobic surface-modified silica is more preferred. Examples of hydrophobic surface-modified silica include silica on which trialkylsilyl groups having 1 to 20 carbon atoms, such as trimethylsilyl groups; dialkylsilyl groups having 1 to 20 carbon atoms, such as dimethylsilyl groups; alkylsilyl groups having 1 to 20 carbon atoms, such as octylsilyl groups; silica on which the surface has been treated with silicone oil; and so on. Hydrophobic surface-modified silica can be obtained, for example, by surface-modifying silica particles with a silane coupling agent having trialkylsilyl groups with 1 to 20 carbon atoms, alkylsilyl groups with 1 to 20 dicarbon atoms, or alkylsilyl groups with 1 to 20 carbon atoms, or by treating silica particles with silicone oil.

[0120] When the adhesive paste of the present invention contains fine particles (B1) [component (B1)], the amount of component (B1) is not particularly limited, but the amount is preferably such that the mass ratio of component (A) to component (B1) [component (A):component (B1)] is 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, and more preferably 100:0.8 to 100:30. By using component (B1) within the above range, the effect of adding component (B1) can be more effectively expressed.

[0121] By incorporating fine particles (B2), it becomes easier to obtain an adhesive paste that offers excellent workability in the coating process and provides a cured product with superior adhesion and heat resistance under both high-temperature and low-temperature heating conditions. To make this effect easier to obtain, the average primary particle diameter of the fine particles (B2) is preferably greater than 0.06 μm and 7 μm or less, more preferably greater than 0.3 μm and 6 μm or less, and even more preferably greater than 1 μm and 4 μm or less.

[0122] The average primary particle diameter of fine particles (B2) can be determined by measuring the particle size distribution using the laser scattering method with a laser diffraction / scattering particle size distribution analyzer (for example, LA-920, manufactured by Horiba, Ltd.).

[0123] The shape of the fine particles (B2) may be the same as that exemplified for the shape of the fine particles (B1), but it is preferable that they be spherical. Furthermore, the constituent components of the fine particles (B2) are the same as those exemplified for the constituent components of the fine particles (B1). The fine particles (B2) can be used individually or in combination of two or more types.

[0124] Among these, as for the fine particles (B2), at least one fine particle selected from the group consisting of metal oxides coated with silicone, silica, and silicone is preferred, from the viewpoint of being relatively easy to mix as an adhesive paste, and from the viewpoint of easily obtaining a cured product with excellent adhesiveness and heat resistance. Silica and silicone are more preferred.

[0125] When the adhesive paste of the present invention contains fine particles (B2) [component (B2)], the amount of component (B2) is not particularly limited, but the amount is preferably such that the mass ratio of component (A) to component (B2) [component (A):component (B2)] is 100:0.1 to 100:40, more preferably 100:0.2 to 100:30, more preferably 100:0.3 to 100:20, even more preferably 100:0.5 to 100:15, and particularly preferably 100:0.8 to 100:12. By using component (B2) within the above range, the effect of adding component (B2) can be more effectively expressed.

[0126] (3) Other additives The adhesive paste of the present invention may contain other components [component (C)] other than components (A), (L), and (B) above, to the extent that they do not impede the purpose of the present invention. (C) Examples of components include antioxidants, UV absorbers, and light stabilizers.

[0127] Antioxidants are added to prevent oxidative degradation during heating. Examples of antioxidants include phosphorus-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants.

[0128] 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 distearyl-3,3'-thiodipropionate.

[0129] These antioxidants can be used individually or in combination of two or more. The amount of antioxidant used is usually 10% by mass or less relative to component (A).

[0130] UV absorbers are added to improve the light resistance of the resulting adhesive paste. Examples of UV absorbers include salicylic acids, benzophenones, benzotriazoles, and hindered amines. These ultraviolet absorbers can be used individually or in combination of two or more. The amount of UV absorber used is typically 10% by mass or less relative to component (A).

[0131] Light stabilizers are added to improve the light resistance of the resulting adhesive paste. Examples of light stabilizers include hindered amines such as poly[{6-(1,1,3,3,-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidine)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidine)imino}]. These light stabilizers can be used individually or in combination of two or more. The total amount of component (C) used is usually 20% by mass or less relative to component (A).

[0132] The adhesive paste of the present invention can be manufactured, for example, by a manufacturing method having the following steps (AI) and (AII). Step (AI): A step in which at least one of the compounds represented by the above formula (a-6) is polycondensed in the presence of a polycondensation catalyst to obtain a polysilsesquioxane compound. Step (AII): Dissolve the polysilsesquioxane compound obtained in step (AI) in solvent (S), and add the liquid component (L) to the resulting solution containing the polysilsesquioxane compound in an amount of 15% by mass or more relative to the total mass of the adhesive paste.

[0133] As a method for obtaining a polysilsesquioxane compound by polycondensing at least one of the compounds represented by the above formula (a-6) in step (AI) in the presence of a polycondensation catalyst, the same method as exemplified in section 1) Adhesive Paste can be mentioned. Furthermore, the solvent (S) and liquid component (L) used in step (AII) can be the same as those exemplified as solvent (S) and liquid component (L) in section 1) Adhesive Paste.

[0134] In step (AII), a method for dissolving the polysilsesquioxane compound in the solvent (S) includes, for example, mixing the polysilsesquioxane compound with the liquid component (L) and, optionally, the components (B) and (C) with the solvent (S), degassing, and dissolving them. The mixing method and degassing method are not particularly limited, and known methods can be used. There are no particular restrictions on the order in which the ingredients are mixed. According to the manufacturing method comprising the above steps (AI) and (AII), the adhesive paste of the present invention can be manufactured efficiently and simply.

[0135] The present invention relates to the adhesive paste, and the mass loss rate of the adhesive paste before and after heating the adhesive paste at 170°C for 2 hours. 170℃2h Preferably, it is less than 55%, more preferably 10% or more and less than 45%, and particularly preferably 15% or more and less than 30%. As the mass of the adhesive paste decreases, the volume also decreases, therefore the mass reduction rate 170℃2h If the value exceeds the above upper limit, there is a risk that the horizontally mounted chip may tilt after the adhesive paste has hardened, but if it is below the above upper limit, this risk can be reduced.

[0136] Furthermore, the adhesive paste of the present invention is the mass reduction rate of the adhesive paste before and after heating the adhesive paste at 100°C for 2 hours. 100℃2h Preferably, it is 10% or more, more preferably 12% or more but less than 50%, and particularly preferably 13% or more but less than 45%. Mass reduction rate 100℃2h When this value is above the lower limit mentioned above, the cured product obtained by heating at a low temperature exhibits superior adhesive properties. On the other hand, mass reduction rate 100℃2h If the value exceeds the above upper limit, the amount of active ingredients that exhibit adhesive function in the cured product obtained by heating at a low temperature will decrease, which may result in a lack of high adhesive strength. However, if the value is below the above upper limit, this risk can be reduced.

[0137] Furthermore, the adhesive paste of the present invention has a mass loss rate. 170℃2h -mass reduction rate 100℃2h Preferably, it is less than 14%, more preferably less than 12%, and particularly preferably 1% or more and less than 10%. Mass reduction rate 170℃2h -mass reduction rate 100℃2hBecause the above upper limit is below this value, when heated at a low temperature, the solvent evaporates efficiently, just as when heated at a high temperature. As a result, the cured product obtained by heating at a low temperature has superior adhesive properties, allowing the temperature range for heating and curing the adhesive paste to be adjusted, and reducing the impact of heating on optical components and sensor chips. Mass reduction rate 170℃2h and mass reduction rate 100℃2h This can be measured by the method described in the examples.

[0138] A cured product can be obtained by heating the adhesive paste to volatilize the solvent (S) and harden it. The heating temperature for curing is usually 80 to 190°C, preferably 80 to 120°C or 150 to 190°C. 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.

[0139] The cured product obtained by curing the adhesive paste of the present invention exhibits excellent adhesive properties. The excellent adhesive properties of the cured product obtained by curing the adhesive paste of the present invention can be confirmed, for example, as follows: a square with sides of 1 mm (area of ​​1 mm²) 2 The adhesive paste of the present invention is applied to the mirror surface of a silicon chip, the applied surface is placed on a silver-plated copper plate and pressed down (thickness of adhesive paste after pressing: approximately 2 μm), and then cured by heat treatment (for example, 100°C for 2 hours, 170°C for 2 hours). This is then left for 60 seconds on the measurement stage of a bond tester that has been pre-adjusted to a predetermined temperature (for example, 23°C, 100°C), and stress is applied to the adhesive surface horizontally (shear direction) at a speed of 200 μm / s from a position 100 μm above the adherend, and the adhesive strength (N / mm□) between the test piece and the adherend is measured.

[0140] The adhesive strength of the cured product obtained by curing the adhesive paste of the present invention is preferably 7 N / mm² or more, more preferably 10 N / mm² or more, even more preferably 13 N / mm² or more, and particularly preferably 15 N / mm² or more at 23°C. Furthermore, the adhesive strength of the cured product obtained by curing the adhesive paste of the present invention is preferably 7 N / mm² or more at 100°C, more preferably 10 N / mm² or more, even more preferably 13 N / mm² or more, and particularly preferably 15 N / mm² or more. In this specification, "1mm□" means "1mm square," that is, "1mm × 1mm (a square with sides of 1mm in length)."

[0141] Because of the above-described characteristics, the adhesive paste of the present invention can be suitably used as an adhesive for semiconductor device fixing materials.

[0142] 2) Method for using adhesive paste, and method for manufacturing a semiconductor device using adhesive paste A method for manufacturing a semiconductor device using the adhesive paste of the present invention as an adhesive for fixing optical elements comprises the following steps (BI) and (BII). Process (BI): A process of applying adhesive paste to one or both bonding surfaces of a semiconductor element and a support substrate, and then pressing them together. Process (BII): A process to heat-cur the adhesive paste of the compressed material obtained in process (BI) and fix the semiconductor element to the support substrate.

[0143] Examples of semiconductor devices include light-emitting elements such as lasers and light-emitting diodes (LEDs), light-receiving elements such as solar cells, optical semiconductor devices, transistors, sensors such as temperature sensors and pressure sensors, and integrated circuits. Among these, optical semiconductor devices are preferred from the viewpoint that the effects of using the adhesive paste of the present invention are more readily apparent.

[0144] Materials for support substrates used to bond semiconductor devices include: glass such as soda-lime glass and heat-resistant hard glass; ceramics; sapphire; metals such as iron, copper, aluminum, gold, silver, platinum, chromium, titanium and their alloys, stainless steel (SUS302, SUS304, SUS304L, SUS309, etc.); and synthetic resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, polyphenylene sulfide, polyetherimide, polyimide, polyamide, acrylic resin, norbornene-based resin, cycloolefin resin, and glass epoxy resin.

[0145] The adhesive paste of the present invention is preferably filled into a syringe. The adhesive paste is pre-filled in a syringe, resulting in superior workability during the application process. The syringe material may be synthetic resin, metal, or glass, but synthetic resin is preferred. There are no particular restrictions on the syringe capacity; it should be determined appropriately according to the amount of adhesive paste to be filled or applied. Commercially available syringes can also be used. Examples of commercially available syringes include the SS-01T series (manufactured by TERUMO Corporation) and the PSY series (manufactured by Musashi Engineering Co., Ltd.).

[0146] In the semiconductor device manufacturing method of the present invention, a syringe filled with adhesive paste descends vertically and approaches a support substrate. After a predetermined amount of adhesive paste is dispensed from the tip of the syringe, the syringe rises and moves away from the support substrate, while the support substrate moves laterally. By repeating this operation, adhesive paste is continuously applied to the support substrate. Subsequently, a semiconductor element is mounted on the applied adhesive paste and pressed against the support substrate.

[0147] The amount of adhesive paste applied is not particularly limited; any amount that, upon curing, can firmly bond the semiconductor element to be bonded and the support substrate is acceptable. Typically, the amount of adhesive paste applied results in a film thickness of 0.5 μm to 5 μm, preferably 1 μm to 3 μm.

[0148] Next, the semiconductor element is fixed to the support substrate by heating and curing the adhesive paste of the resulting compressed material. The heating temperature and heating time are as described in section 1) Adhesive Paste.

[0149] The semiconductor device obtained by the semiconductor device manufacturing method of the present invention has semiconductor elements that are well mounted on an adhesive paste, and the semiconductor elements are fixed with high adhesive strength. [Examples]

[0150] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited in any way to the following examples. In each example, parts and percentages are based on mass unless otherwise specified.

[0151] [Average molecular weight measurement] The mass-average molecular weight (Mw) and number-average molecular weight (Mn) of the thermosetting organopolysiloxane compound (A) obtained in the production example were measured using the following apparatus and conditions, converted to standard polystyrene equivalents. Device name: HLC-8220GPC, manufactured by Tosoh Corporation Column: A sequential concatenation of TSKgelGMHXL, TSKgelGMHXL, and TSKgel2000HXL. Solvent: tetrahydrofuran Injection volume: 20μl Measurement temperature: 40℃ Flow rate: 1ml / min Detector: Differential refractometer

[0152] [Measurement of IR spectrum] The IR spectrum of the thermosetting organopolysiloxane compound (A) obtained in the manufacturing example was measured using a Fourier transform infrared spectrophotometer (PerkinElmer Spectrum100).

[0153] [Viscosity evaluation] Using a rheometer (Anton Paar, product name "MCR301"), with a cone plate of radius 50 mm and cone angle 0.5°, at 25°C, the shear rate was 1 s. -1 The viscosity was measured.

[0154] (Manufacturing Example 1) 71.37 g (400 mmol) of methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was placed in a 300 ml eggplant-shaped flask. Then, an aqueous solution prepared by dissolving 0.10 g of 35% hydrochloric acid (0.25 mol% relative to the total amount of silane compounds) in 21.6 ml of distilled water was added while stirring. The entire mixture was stirred at 30°C for 2 hours, then the temperature was raised to 70°C and stirred for 5 hours. After the reaction mixture was returned to room temperature (23°C), 140 g of propyl acetate was added. To this, 0.12 g of 28% aqueous ammonia (0.5 mol% relative to the total amount of silane compounds) was added while stirring the entire mixture, and the temperature was raised to 70°C and stirred for 3 hours. Purified water was added to the reaction mixture, and the liquid-liquid mixture was separated. This procedure 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 thermosetting organopolysiloxane compound (A1). The thermosetting organopolysiloxane compound (A1) had a mass-average molecular weight (Mw) of 7,800 and a molecular weight distribution (Mw / Mn) of 4.52. Furthermore, the IR spectral data for the thermosetting organopolysiloxane compound (A1) is shown below. Si-CH3: 1272cm -1 ,1409cm -1 Si-O: 1132cm -1

[0155] (Manufacturing example 2) In a 300 mL round-bottom flask, 17.0 g (77.7 mmol) of 3,3,3-trifluoropropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 32.33 g (181.3 mmol) of methyltriethoxysilane were charged. Then, an aqueous solution prepared by dissolving 0.0675 g of 35% hydrochloric acid (0.65 mmol of HCl, 0.25 mol% of the total amount of silane compounds) in 14.0 ml of distilled water was added while stirring. The entire mixture was then stirred at 30°C for 2 hours, and then the temperature was raised to 70°C for 20 hours. While continuing to stir the contents, a mixed solution of 0.0394 g of 28% aqueous ammonia (containing 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 mixture was then stirred at 70°C for 40 minutes. After the reaction mixture cooled to room temperature (23°C), 50 g of propyl acetate and 100 g of water were added and liquid-liquid treatment was performed to obtain an organic layer containing the reaction product. Magnesium sulfate was added to this organic layer and it was dried. After removing magnesium sulfate by filtration, the organic layer was concentrated using an evaporator, and the concentrate was vacuum-dried to obtain 22.3 g of thermosetting organopolysiloxane compound (A2). The thermosetting organopolysiloxane compound (A2) had a mass-average molecular weight (Mw) of 5,500 and a molecular weight distribution (Mw / Mn) of 3.40. Furthermore, the IR spectral data for the thermosetting organopolysiloxane compound (A2) is shown below. Si-CH3: 1272cm -1 ,1409cm -1 Si-O: 1132cm -1 CF:1213cm -1

[0156] (Manufacturing Example 3) 28.91 g (145.8 mmol) of phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was charged into a 300 ml round-bottom flask. Then, an aqueous solution prepared by dissolving 0.0376 g of 35% hydrochloric acid (0.25 mol% relative to the total amount of silane compounds) in 7.874 ml of distilled water was added while stirring. The entire mixture was stirred at 30°C for 2 hours, then the temperature was raised to 70°C and stirred for 5 hours. After the reaction mixture was returned to room temperature (23°C), 50 g of propyl acetate and 100 g of water were added and liquid-liquid treatment was performed to obtain an organic layer containing the reaction product. Magnesium sulfate was added to this organic layer and it was dried. After removing magnesium sulfate by filtration, the organic layer was concentrated using an evaporator, and the concentrate was vacuum-dried to obtain 17.0 g of thermosetting organopolysiloxane compound (A3). The thermosetting organopolysiloxane compound (A3) had a mass-average molecular weight (Mw) of 1,100 and a molecular weight distribution (Mw / Mn) of 1.2. Furthermore, the IR spectral data for the thermosetting organopolysiloxane compound (A3) is shown below. Si-C6H5: 698cm -1 Si-O: 1132cm -1

[0157] (Manufacturing example 4) 72.275 g (364.5 mmol) of phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was charged into a 300 ml eggplant-shaped flask. Then, an aqueous solution prepared by dissolving 0.0938 g of 35% hydrochloric acid (0.25 mol% relative to the total amount of silane compounds) in 19.683 ml of distilled water was added while stirring. The entire mixture was stirred at room temperature (25°C) for 12 minutes, and then 0.0548 g of 28% by mass aqueous ammonia solution (0.25 mol% ammonia relative to the amount of phenyltrimethoxysilane) was added, and the mixture was stirred at room temperature for 2 hours. To this, 200 g of propyl acetate and 400 g of water were added and liquid-liquid treatment was performed to obtain an organic layer containing the reaction product. Magnesium sulfate was added to this organic layer and it was dried. After removing magnesium sulfate by filtration, the organic layer was concentrated using an evaporator, and the concentrate was vacuum-dried to obtain 64.94 g of viscous liquid polysilsesquioxane (L5). The mass-average molecular weight (Mw) of liquid polysilsesquioxane (L5) was 740, and the molecular weight distribution (Mw / Mn) was 1.48.

[0158] The compounds used in the examples and comparative examples are shown below. [Component (A)] Thermosetting organopolysiloxane compound (A1): Organopolysiloxane compound obtained in Preparation Example 1 (solid at 25°C) Thermosetting organopolysiloxane compound (A2): Organopolysiloxane compound obtained in Preparation Example 2 (solid at 25°C) Thermosetting organopolysiloxane compound (A3): Organopolysiloxane compound obtained in Preparation Example 3 (solid at 25°C)

[0159] [Liquid component (L)] (L1) Bifunctional silane compounds Dimethoxydiphenylsilane: Manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-202SS" (viscosity 8 mPa·s) (L2) Trifunctional silane compounds (L2-1)3-(trimethoxysilyl)propyl succinic anhydride: Manufactured by Shin-Etsu Chemical Co., Ltd., product name "X-12-967C" (viscosity 30 mPa·s) (L2-2)3-Methacryloxypropyltrimethoxysilane: Manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-503" (viscosity 8 mPa·s) (L2-3)3-Acryloxypropyltrimethoxysilane: Manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-5103" (viscosity 15 mPa·s) (L2-4)3-Isocyanate-propyltriethoxysilane: Manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBE-9007N" (viscosity 10 mPa·s) (L2-5) Phenyltrimethoxysilane: Manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-103" (viscosity 10 mPa·s) (L3) Polyfunctional silane compounds (L3-1) 1,3,5-N-tris[3-(trimethoxysilyl)propyl]isocyanurate: Manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-9659" (viscosity 800 mPa·s) (L3-2) Polyfunctional silane compounds with an organic main chain containing methoxy and isocyanate groups: Manufactured by Shin-Etsu Chemical Co., Ltd., product name "X-12-1159L" (viscosity 4,000 mPa·s) (L4) Silicone oil (L4-1) Acrylic-modified silicone oil at both ends: Manufactured by Shin-Etsu Chemical Co., Ltd., product name "X-22-2445" (viscosity 60 mPa·s) (L4-2) Alkyl Aralkyl Modified Silicone Oil: Manufactured by Momentive Performance Materials Japan, product name "XF42-334" (viscosity 1000 mPa·s) [Liquid components other than liquid component (L) (L5)] Liquid polysilsesquioxane: Polysilsesquioxane obtained in Production Example 4 (viscosity 197,000 mPa·s)

[0160] [Solvent (S)] (1) Organic solvent (SL) Diethylene glycol monoethyl ether acetate (EDGAC): Manufactured by Tokyo Chemical Industry Co., Ltd. (boiling point 218℃) Cyclohexanone: Manufactured by Tokyo Chemical Industry Co., Ltd. (Boiling point 157℃) (2) Organic solvent (SH) Tripropylene glycol-n-butyl ether (TPnB): Manufactured by Dow Chemical (boiling point 274°C) (3) Others Acetone: Manufactured by Tokyo Chemical Industry Co., Ltd. (boiling point 56℃)

[0161] [(B) component] Fine particles (B1): Silica fine particles (manufactured by Nippon Aerosil Co., Ltd., product name "AEROSIL RX300", average primary particle diameter: 7 nm, specific surface area: 210 m²) 2 / g) Microparticles (B2): Silicone microparticles (manufactured by Nikko Rica Co., Ltd., product name "MSP-SN08", average primary particle size: 0.8 μm, shape: spherical)

[0162] (Example 1) To 100 parts of a thermosetting organopolysiloxane compound (A1), 28 parts of EDGAC (SL), 10 parts of (L3-1), 3 parts of (L2-1), and 35 parts of (L1) were added, and the entire mixture was thoroughly mixed and degassed to obtain adhesive paste 1 with a solid content of 84%.

[0163] (Examples 2-24, Comparative Examples 1-3) Adhesive pastes 2-24 and 1r-3r were obtained in the same manner as in Example 1, except that the types and proportions of the compounds (each component) were changed to those shown in Table 1 below. In Examples 23 and 24, the fine particles (B1) and (B2) were added before the addition of EDGAC (SL) and each liquid component (L1 to L3).

[0164] The following tests were performed using adhesive pastes 1-24 and 1r-3r obtained in the examples and comparative examples. The results are shown in Table 2 below.

[0165] [Tack Free Time Evaluation] The adhesive pastes obtained in the examples and comparative examples were dispensed onto a stainless steel plate (SUS304, surface polished to 600 grit) to a diameter of 0.5 mm and left to stand under standard conditions (temperature: 23°C ± 1°C, relative humidity: 50 ± 5%). After a certain period of time, the applied adhesive paste was scratched in half with a needle, and it was observed whether the needle marks disappeared within 10 seconds. If the needle marks disappeared within 10 seconds, the sample was left undisturbed. The same observation was repeated every 2 minutes until 10 minutes had passed from the start of measurement, and then every 5 minutes thereafter, until the needle marks no longer disappeared within 10 seconds. Finally, the standing time N (minutes) until the needle marks no longer disappeared within 10 seconds was measured.

[0166] [Chip mountability evaluation] The adhesive pastes obtained in the examples and comparative examples were dispensed onto an electroless silver-plated copper plate (average surface roughness Ra: 0.025 μm) to a diameter of 0.5 mm and left to stand under standard conditions (temperature: 23°C ± 1°C, relative humidity: 50 ± 5%). After 30 minutes, a square with sides of 1 mm (area of ​​1 mm²) was formed. 2 A silicon chip was mounted, and the tilt of the chip was observed. If the chip could be mounted without tilting, it was evaluated as "good," and if problems such as tilting of the chip occurred, it was evaluated as "bad."

[0167] [Adhesive strength evaluation (1)] A square with sides of 1 mm (area of ​​1 mm) 2 The adhesive paste obtained in the examples and comparative examples was applied to the mirror surface of a silicon chip, and left to stand in a standard environment (temperature: 23°C ± 1°C, relative humidity: 50 ± 5%). After 30 minutes, the coated surface was placed on a substrate [electroless silver-plated copper plate (average roughness Ra of the silver-plated surface: 0.025 μm)], and pressed so that the thickness of the adhesive paste after pressing was approximately 2 μm. Then, it was cured by heat treatment at 170°C for 2 hours to obtain a substrate with a test piece attached. This substrate with a test piece attached was left on the measurement stage of a bond tester (Daisi, Series 4000) at 100°C for 60 seconds, and stress was applied to the adhesive surface horizontally (shear direction) at a speed of 200 μm / s from a height of 100 μm from the substrate, and the adhesive strength (N / mm□) between the test piece and the substrate at 100°C was measured.

[0168] [Adhesive strength evaluation (2)] In the adhesive strength evaluation (1), the adhesive strength (N / mm□) between the test piece and the adherend was measured in the same manner as in the adhesive strength evaluation (1), except that the temperature conditions for heat treatment and curing were changed to 100°C, and the heating temperature and measurement temperature of the bond tester were changed to 23°C.

[0169] [Measurement of mass loss rate] 15 mg of the adhesive paste obtained in the examples and comparative examples was put into a differential thermal-thermogravimetric simultaneous measurement device (manufactured by Shimadzu Corporation, product name "DTG-60"), heated at 100°C for 2 hours at a measurement start temperature of 40°C and a heating rate of 10°C / min, the mass of the adhesive paste before and after heating was measured, and the mass reduction rate 100℃2h (%) [{((mass of the adhesive paste before heating) - (mass of the adhesive paste after heating at 100°C for 2 hours)) / (mass of the adhesive paste before heating)} × 100] was calculated. Also, except that the heating conditions were changed to 170°C for 2 hours, the mass reduction rate 100℃2h (%) was measured in the same manner as the measurement method described above, and the mass reduction rate of the adhesive paste before and after heating 170℃2h (%) [{((mass of the adhesive paste before heating) - (mass of the adhesive paste after heating at 170°C for 2 hours)) / (mass of the adhesive paste before heating)} × 100] was calculated. Furthermore, from the measured mass reduction rates, the mass reduction rate 170℃2h - mass reduction rate 100℃2h (%) was calculated.

[0170]

Table 1

[0171]

Table 2

[0172] It can be seen from Tables 1 and 2 as follows. The adhesive pastes 1 to 24 of Examples 1 to 24 have a long tack-free time, excellent chip mounting properties, and excellent adhesive strength of the cured product obtained by heating the adhesive paste at a high temperature. As the liquid component (L), the adhesive paste containing a bifunctional silane-based compound, a trifunctional silane-based compound, and a silicone oil has a longer tack-free time and can be chip-mounted for a longer time compared to the adhesive paste containing a polyfunctional silane-based compound (Examples 2 to 4, 12 to 17). In addition, an adhesive paste containing a trifunctional silane compound and a silicone oil as the liquid component (L) is superior in the adhesive strength of the cured product obtained by heating the adhesive paste at a low temperature as compared with an adhesive paste containing a bifunctional silane compound (Examples 5 to 9). That is, by selecting the liquid component (L), taking into account the tack-free time (the standing time after application of the adhesive paste to the object to be coated) and the temperature range for heating the adhesive paste to obtain a cured product, an optimal adhesive paste can be obtained.

[0173] When an organic solvent (SL) having a lower boiling point is contained as the solvent (S), the tack-free time of the adhesive paste is shortened, but the cured product obtained by heating the adhesive paste at a low temperature is excellent in adhesive strength (Examples 5 and 10). In addition, an adhesive paste containing only the organic solvent (SL) as the solvent (S) has a shorter tack-free time as compared with an adhesive paste containing only the organic solvent (SH), but the cured product obtained by heating the adhesive paste at a low temperature is excellent in adhesive strength (Examples 18 and 19). Furthermore, when a mixed solvent of the organic solvent (SL) and the organic solvent (SH) is contained as the solvent (S), the adhesive paste having a higher content ratio of the organic solvent (SH) has a longer tack-free time. On the other hand, the adhesive paste having a higher content ratio of the organic solvent (SL) has a shorter tack-free time, but is excellent in the adhesive strength of the cured product obtained by heating the adhesive paste under any temperature conditions of high-temperature heating and low-temperature heating (Examples 20 and 21). That is, by selecting the organic solvent (SL) and the organic solvent (SH), taking into account the tack-free time (the standing time after application of the adhesive paste to the object to be coated) and the temperature range for heating the adhesive paste to obtain a cured product, an optimal adhesive paste can be obtained.

[0174] An adhesive paste having a high solid content concentration (and accordingly, a high content ratio of the component (L) with respect to the total mass of the adhesive paste) has a longer tack-free time and is excellent in the adhesive strength of the cured product obtained by heating the adhesive paste at a low temperature (Examples 1 and 22). Adhesive pastes containing fine particles (B) yield cured products with a longer tack-free time, excellent chip-mountability, and good adhesive strength under both high-temperature and low-temperature heating conditions, despite having a lower proportion of component (L) relative to the total mass of the adhesive paste compared to adhesive pastes without fine particles (B) (Examples 23 and 24). Even when the type of thermosetting organopolysiloxane compound (A) (type of polysilsesquioxane compound side chain) is changed, the tack-free time is long, the tip-mountability is excellent, and the adhesive strength of the resulting cured product is excellent regardless of whether the adhesive paste is heated at high or low temperatures (Examples 1, 5, 11, etc.).

[0175] On the other hand, in Comparative Example 1, adhesive paste 1r has a low liquid component (L) content of only 10% of the total mass of the adhesive paste, resulting in a short tack-free time and making it unsuitable for chip mounting in a short time. Furthermore, after mounting the silicon chip, a problem occurred where the chip tilted, resulting in poor chip mounting performance, and therefore it was not possible to measure the adhesive strength. The adhesive paste 2r in Comparative Example 2 contains a high-viscosity liquid component (L). This high viscosity results in a short tack-free time, which is unfavorable for chip mounting in a short time. Furthermore, after mounting the silicon chip, the chip tilted, resulting in poor chip mounting performance, making it impossible to measure the adhesive strength. The adhesive paste 3r in Comparative Example 3 contains only an organic solvent (SL) as the solvent (S). However, because the liquid component (L) content is low at 10% of the total mass of the adhesive paste, the tack-free time is short, which is unfavorable for chip mounting in a short time. Furthermore, after mounting the silicon chip, the chip tilts, resulting in poor chip mounting performance, and therefore the adhesive strength could not be measured.

Claims

1. An adhesive paste comprising a thermosetting organopolysiloxane compound (A), a liquid component (L) that satisfies the following requirements 1 and 2, and a solvent (S), The thermosetting organopolysiloxane compound (A) is a polysilsesquioxane compound, 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. The solvent (S) contains an organic solvent (SL) having a boiling point of 100°C or higher and less than 254°C. The content of the organic solvent (SL) is 10% by mass or more and 50% by mass or less, relative to the total mass of the adhesive paste. The mass reduction rate of the adhesive paste before and after heating at 100°C for 2 hours is 17% or more, and An adhesive paste having a tack-free time of 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. An adhesive paste comprising a thermosetting organopolysiloxane compound (A), a liquid component (L) that satisfies the following requirements 1 and 2, and a solvent (S), The thermosetting organopolysiloxane compound (A) is a polysilsesquioxane compound, 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. The solvent (S) contains an organic solvent (SL) having a boiling point of 100°C or higher and less than 254°C. The content of the organic solvent (SL) is 10% by mass or more and 50% by mass or less, relative to the total mass of the adhesive paste. When the mass loss rate of the adhesive paste before and after heating at 170°C for 2 hours is defined as mass loss rate 170°C2h, and when the adhesive paste before and after heating at 100°C for 2 hours is defined as mass loss rate 100°C2h, then the difference between mass loss rate 170°C2h and mass loss rate 100°C2h is less than 14%, and An adhesive paste having a tack-free time of 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.

3. An adhesive paste comprising a thermosetting organopolysiloxane compound (A), a liquid component (L) that satisfies the following requirements 1 and 2, and a solvent (S), The thermosetting organopolysiloxane compound (A) is a polysilsesquioxane compound, 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. The solvent (S) contains an organic solvent (SL) having a boiling point of 100°C or higher and less than 254°C. The content of the organic solvent (SL) is 10% by mass or more and 50% by mass or less, relative to the total mass of the adhesive paste. The adhesive strength of the cured product obtained by heating the adhesive paste at 100°C for 2 hours is 10 N / mm² or more at 100°C, and, An adhesive paste having a tack-free time of 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.

4. The adhesive paste according to any one of claims 1 to 3, wherein the liquid component (L) is at least one selected from the group consisting of a bifunctional silane compound, a trifunctional silane compound, and a silicone oil.

5. The adhesive paste according to any one of claims 1 to 4, wherein the organic solvent (SL) has a boiling point of 100°C or higher and less than 200°C.

6. Furthermore, the adhesive paste according to any one of claims 1 to 5, further containing the following component (B). (B) Component: Fine particles

7. The percentage of mass loss of the adhesive paste before and after heating it at 170°C for 2 hours. １７０℃２ｈ The adhesive paste according to any one of claims 1 to 6, wherein the amount is less than 55%.

8. The mass reduction rate of the adhesive paste before and after heating the adhesive paste at 170°C for 2 hours is defined as the mass reduction rate. １７０℃２ｈ The mass reduction rate of the adhesive paste before and after heating the adhesive paste at 100°C for 2 hours is defined as the mass reduction rate. １００℃２ｈ In that case, the mass reduction rate １７０℃２ｈ - Mass reduction rate １００℃２ｈ The adhesive paste according to claim 1 or 3, wherein the content is less than 14%.

9. The adhesive paste according to any one of claims 1 to 8, which substantially does not contain a precious metal catalyst.

10. An adhesive paste for semiconductor device fixing material, according to any one of claims 1 to 9.

11. A method for using the adhesive paste described in any one of claims 1 to 10 as an adhesive for semiconductor device fixing material.

12. A method for manufacturing a semiconductor device, using the adhesive paste described in any one of claims 1 to 10 as an adhesive for fixing semiconductor elements, comprising the following steps (BI) and (BII). Process (BI): A process of applying the adhesive paste to one or both bonding surfaces of the semiconductor element and the support substrate, and then pressing them together. Process (BII): A process of heating and curing the adhesive paste of the compressed material obtained in process (BI) to fix the semiconductor element to the support substrate.

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