Adhesive paste, method of using adhesive paste, and method of manufacturing semiconductor device

Abstract

To provide: an adhesive paste, a hardened material of which obtained by heating at low temperatures has an excellent adhesive property and which can favorably mount a semiconductor element even after a lapse of long time after application to a material to be applied; a method for using the adhesive paste as an adhesive for a fixing material of the semiconductor element; and a production method of a semiconductor device.SOLUTION: Disclosed is an adhesive paste including a thermosetting organopolysiloxane compound (A) and an organic solvent (SL) having a boiling point of 100°C or more but less than 254°C. The mass reduction rate of the adhesive paste before and after heating at 100°C for 2 hrs, mass reduction rate 100°C2h, is 10% or more and, when the rate of the paste before and after heating at 170°C for 2 hrs is denoted as mass reduction rate170°C2h, (mass reduction rate170°C2h)-(mass reduction100°C2h) is less than 14%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an adhesive paste that provides excellent adhesiveness when cured by heating at a low temperature and that can mount semiconductor elements well even after being left for a long time after being applied to an object to be coated; a method for using this adhesive paste as an adhesive for semiconductor element fixing material; and a method for manufacturing a semiconductor device that uses this adhesive paste as an adhesive for semiconductor element fixing material. [Background technology]

[0002] Conventionally, adhesive pastes have been improved in various ways depending on the application, and have been widely used in industry as raw materials for optical components and molded bodies, adhesives, coating agents, and the like. The adhesive paste has also been attracting attention as a paste for semiconductor element fixing materials, such as an adhesive for semiconductor element fixing materials.

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

[0004] An adhesive paste for semiconductor elements that fixes semiconductor elements is usually applied to an object to be coated, such as a substrate such as a lead frame, using an application device having a discharge pipe (needle). In a coating device having such a discharge pipe, for example, the discharge pipe descends vertically to approach the object to be coated, and after discharging a predetermined amount of adhesive paste from its tip, the discharge pipe rises and moves away from the object to be coated, and the object to be coated moves sideways. By repeating this operation, the adhesive paste for semiconductor elements is continuously applied to the object to be coated. Then, the semiconductor element is mounted on the applied adhesive paste and adhered to the object to be coated.

[0005] Usually, after the adhesive paste is applied to the object, a semiconductor element is quickly mounted on the applied adhesive paste and adhered to the object. However, in a production line or the like, for some reason, the applied adhesive paste may be left as is for a long period of time without a semiconductor element being mounted. In such cases, if the applied adhesive paste is left for a long period of time, the viscosity of the adhesive paste changes, and the semiconductor element may not be mounted in a desirable state. To solve this problem, Patent Document 1 proposes an adhesive obtained by dissolving a specific polysilsesquioxane compound in a solvent containing a high-boiling organic solvent having a boiling point of 254°C or more and 300°C or less. The document describes that the adhesive is capable of mounting optical elements as well as immediately after application, even 20 minutes or more after application on a substrate, and also has excellent adhesive properties.

[0006] However, optical components and sensor chips are easily affected by heat, so when a heat curing method is used to harden the adhesive, it is preferable to harden the adhesive at as low a temperature as possible to avoid the effects of heat on the optical components and sensor chip. However, the adhesive described in Patent Document 1 requires a long, high-temperature heat treatment at 170°C for two hours, and there was concern that a large amount of solvent would remain if the adhesive were heated at a lower temperature (for example, 100°C for two hours), making it difficult to obtain sufficient adhesive strength.In addition, when heated at a low temperature, the rate at which the concentration of the components (active ingredients) in the adhesive excluding the solvent increases is slow, making it difficult to sufficiently heat-cure the adhesive, and there was concern that a cured product with sufficient adhesive strength would not be obtained. Furthermore, if acetone or the like, which has a very low boiling point, is used as the solvent, the adhesive may dry out quickly after being discharged, which may result in failure to mount the semiconductor element properly.

[0007] Therefore, there is a demand for an adhesive paste that has excellent adhesive properties when cured by heating at a low temperature, and that allows semiconductor elements to be mounted on the adhesive paste as well as immediately after application, even when left for a long time after application to the substrate. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2018-168286 Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention has been made in view of the above circumstances, and aims to provide an adhesive paste which, when heated at a low temperature, produces a cured product with excellent adhesiveness and which is capable of satisfactorily mounting a semiconductor element even long after application to an object to be coated; a method for using this adhesive paste as an adhesive for a semiconductor element fixing material; and a method for manufacturing a semiconductor device which uses this adhesive paste as an adhesive for a semiconductor element fixing material. In the present invention, low temperature refers to a temperature of 80°C to 120°C. Moreover, "excellent adhesiveness" means "high adhesive strength." [Means for solving the problem]

[0010] The present inventors conducted extensive research to solve the above problems, and as a result, they discovered that an adhesive paste having a controlled mass loss rate, obtained by dissolving a thermosetting organopolysiloxane compound in a solvent containing an organic solvent having a boiling point of 100°C or higher but lower than 254°C, efficiently volatilizes the solvent when heated at a low temperature, resulting in a cured product with excellent adhesiveness and capable of successfully mounting a semiconductor element even long after application to an object to be coated.

[0011] Thus, according to the present invention, there are provided adhesive pastes (1) to (10) below, a method for using the adhesive paste (11), and a method for manufacturing a semiconductor device using the adhesive paste (12).

[0012] [1] An adhesive paste comprising a thermosetting organopolysiloxane compound (A) and a solvent (S), wherein the thermosetting organopolysiloxane compound (A) is dissolved in the solvent (S), and the solvent (S) contains an organic solvent (SL) having a boiling point of 100°C or higher but lower than 254°C, and the adhesive paste is heated at 100°C for 2 hours, and the mass loss rate of the adhesive paste before and after heating is 100℃2h is 10% or more, and the mass loss rate of the adhesive paste before and after heating at 170 ° C for 2 hours is 170℃2h When the mass reduction rate is 170℃2h -mass reduction rate 100℃2h but less than 14% adhesive paste.

[0013] [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 organic solvent (SL) has a boiling point of 100°C or higher and lower than 200°C. [4] The adhesive paste according to any one of [1] to [3], wherein the content of the organic solvent (SL) is 10% by mass or more and 50% by mass or less, based on the total mass of the adhesive paste. [5] The adhesive paste according to any one of [1] to [4], wherein the solvent (S) contains an organic solvent (SH) having a boiling point of 254°C or higher and 300°C or lower.

[0014] [6] The adhesive paste according to any one of [1] to [5], further comprising the following component (B): Component (B): Silane coupling agent [7] The adhesive paste according to any one of [1] to [6], further comprising the following component (C): (C) Component: Fine particles [8] The adhesive paste according to any one of [1] to [7], having a solid content concentration of 50% by mass or more and 90% by mass or less. [9] The adhesive paste according to any one of [1] to [8], which is substantially free of a noble metal catalyst.

[10] The adhesive paste according to any one of [1] to [9], which is an adhesive for a semiconductor element fixing material.

[0015]

[11] A method of using the adhesive paste according to any one of [1] to

[10] as an adhesive for a semiconductor element fixing material.

[12] A method for manufacturing a semiconductor device using the adhesive paste according to any one of [1] to

[10] as an adhesive for a semiconductor element fixing material, the method comprising the following steps (BI) and (BII): Step (BI): A step of applying the adhesive paste to the adhesive surface of one or both of the semiconductor element and the supporting substrate, and pressing them together. Step (BII): A step of heating and hardening the adhesive paste of the pressure-bonded product obtained in Step (BI) to fix the semiconductor element to the support substrate. [Effects of the Invention]

[0016] According to the present invention, an adhesive paste is provided which has both adhesive properties of a cured product obtained by heating at a low temperature and chip mountability that enables semiconductor elements to be mounted satisfactorily even long periods of time after application to an object to be coated. The present invention also provides a method for using this adhesive paste as an adhesive for a semiconductor element fixing material, and a method for manufacturing a semiconductor device using this adhesive paste as an adhesive for a semiconductor element fixing material. DETAILED DESCRIPTION OF THE INVENTION

[0017] The present invention will be described in detail below, divided into the following sections: 1) adhesive paste, 2) method of using the adhesive paste, and method of manufacturing a semiconductor device using the adhesive paste.

[0018] 1) Adhesive paste The adhesive paste of the present invention contains a thermosetting organopolysiloxane compound (A) and a solvent (S), and the thermosetting organopolysiloxane compound (A) is dissolved in the solvent (S), and the solvent (S) contains an organic solvent (SL) having a boiling point of 100°C or higher but lower than 254°C. After heating the adhesive paste at 100°C for 2 hours, the mass loss rate of the adhesive paste before and after heating is 100℃2h is 10% or more, and the mass loss rate of the adhesive paste before and after heating at 170 ° C for 2 hours is 170℃2h When the mass reduction rate is 170℃2h -mass reduction rate 100℃2h However, it is less than 14%.

[0019] In the present invention, the adhesive paste refers to a viscous liquid that has fluidity. The adhesive paste of the present invention has the properties in the above-described state, and therefore has excellent workability in the application step. Here, excellent workability in the application process means that in the application process, when the adhesive paste is discharged from the discharge pipe and then the discharge pipe is pulled up, the amount of stringiness is small or the pipe breaks immediately, preventing resin from flying or droplets from spreading after application and contaminating the surrounding area.

[0020] The adhesive paste of the present invention is a paste having a mass loss rate of the adhesive paste before and after heating at 100°C for 2 hours. 100℃2h is 10% or more, preferably 12% or more and less than 50%, and more preferably 13% or more and less than 45%. Mass reduction rate 100℃2h When the cured product obtained by heating at a low temperature has a viscosity of at least the above lower limit, the cured product has excellent adhesiveness. Also, mass reduction rate 100℃2h If the content of the cured product obtained by heating at a low temperature is equal to or greater than the upper limit, the amount of the active ingredient that exhibits the adhesive function will be reduced, and there is a risk that high adhesive strength will not be exhibited. However, by keeping the content of the cured product below the upper limit, this risk can be reduced. Here, the term "active ingredient" refers to the ingredients contained in the adhesive paste excluding the solvent (S).

[0021] In addition, the adhesive paste of the present invention is heated at 170°C for 2 hours, and the mass loss rate of the adhesive paste before and after heating is measured as a mass loss rate. 170℃2h When the mass reduction rate is 170℃2h -mass reduction rate 100℃2h is less than 14%, preferably less than 12%, and more preferably 1% or more and less than 10%. Mass reduction rate 170℃2h -mass reduction rate 100℃2h When the viscosity is less than the upper limit, the solvent volatilizes efficiently when heated at a low temperature in the same manner as when heated at a high temperature, and the cured product obtained by heating at a low temperature has superior adhesiveness. Mass reduction rate 100℃2h and mass reduction rate 170℃2h can be measured by the method described in the Examples.

[0022] [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, containing component (A), makes it easier to obtain a cured product with excellent adhesiveness by heating at a low temperature.

[0023] The thermosetting organopolysiloxane compound (A) of the present invention is a compound having a carbon-silicon bond and a siloxane bond (-Si-O-Si-) in the molecule. Furthermore, since component (A) is a thermosetting compound, it preferably has at least one functional group selected from the group consisting of functional groups capable of undergoing a condensation reaction upon heating and functional groups capable of undergoing a condensation reaction via hydrolysis. Such a functional group is preferably at least one selected from the group consisting of a hydroxyl group and an alkoxy group, and more preferably a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms. There are no limitations on the main chain structure of the thermosetting organopolysiloxane compound (A), and it may be linear, ladder-like, or cage-like. For example, an example of a linear main chain structure is a structure represented by the following formula (a-1), an example of a ladder-like main chain structure is a structure represented by the following formula (a-2), and an example of a cage-like main chain structure is a structure represented by the following formula (a-3).

[0024] [ka]

[0025] [ka]

[0026] [ka]

[0027] In formulas (a-1) to (a-3), Rx, Ry, and Rz each independently represent a hydrogen atom or an organic group, and the organic group is preferably an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or an alkylsilyl group. 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, two Rx in formula (a-1) cannot both be hydrogen atoms.

[0028] Examples of the alkyl group of the unsubstituted or substituted alkyl group include alkyl groups having 1 to 10 carbon atoms, such as a 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.

[0029] Examples of the cycloalkyl group of the unsubstituted or substituted cycloalkyl group include cycloalkyl groups having 3 to 10 carbon atoms, such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.

[0030] Examples of the alkenyl group of the unsubstituted or substituted alkenyl group include alkenyl groups having 2 to 10 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, and 3-butenyl.

[0031] Examples of the substituent on the alkyl group, cycloalkyl group, and alkenyl group include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group; a thiol group; an epoxy group; a glycidoxy group; a (meth)acryloyloxy group; and unsubstituted or substituted aryl groups such as a phenyl group, a 4-methylphenyl group, and a 4-chlorophenyl group.

[0032] Examples of the aryl group of the unsubstituted or substituted aryl group include aryl groups having 6 to 10 carbon atoms, such as a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

[0033] Examples of the substituent on the aryl group include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkyl groups having 1 to 6 carbon atoms such as methyl group and ethyl group; alkoxy groups having 1 to 6 carbon atoms such as methoxy group and ethoxy group; nitro group; cyano group; hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth)acryloyloxy group; and unsubstituted or substituted aryl groups such as phenyl group, 4-methylphenyl group, and 4-chlorophenyl group.

[0034] Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tri-t-butylsilyl group, a methyldiethylsilyl group, a dimethylsilyl group, a diethylsilyl group, a methylsilyl group, and an ethylsilyl group.

[0035] Among these, Rx, Ry, and Rz are preferably a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms, or a phenyl group, and particularly preferably an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms.

[0036] The thermosetting organopolysiloxane compound (A) can be obtained by a known production method, for example, by polycondensing a silane compound having a hydrolyzable functional group (alkoxy group, halogen atom, etc.).

[0037] The silane compound to be used may be appropriately selected depending on the structure of the desired thermosetting organopolysiloxane compound (A). Preferred specific examples include bifunctional 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 thereof include tetrafunctional silane compounds such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-t-butoxysilane, tetra-s-butoxysilane, methoxytriethoxysilane, dimethoxydiethoxysilane, and trimethoxyethoxysilane.

[0038] The weight average molecular weight (Mw) of the thermosetting organopolysiloxane compound (A) is usually from 800 to 30,000, preferably from 1,000 to 20,000, more preferably from 1,200 to 15,000, and particularly preferably from 3,000 to 10,000. By using a thermosetting organopolysiloxane compound (A) having a weight average molecular weight (Mw) within the above range, it becomes easier to obtain an adhesive paste that gives a cured product with excellent heat resistance and adhesiveness.

[0039] The molecular weight distribution (Mw / Mn) of the thermosetting organopolysiloxane compound (A) is not particularly limited, but is usually from 1.0 to 10.0, preferably from 1.1 to 6.0. By using a thermosetting organopolysiloxane compound (A) having a molecular weight distribution (Mw / Mn) within the above range, it becomes easier to obtain an adhesive paste that gives a cured product with excellent heat resistance and adhesiveness. The mass average molecular weight (Mw) and number average molecular weight (Mn) can be determined, for example, as a standard polystyrene equivalent value by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

[0040] 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 excellent adhesiveness when heated at a low temperature.

[0041] The polysilsesquioxane compound of the present invention is a compound having a repeating unit represented by the following formula (a-4). The adhesive paste of the present invention contains, as component (A), a polysilsesquioxane compound having a repeating unit represented by the following formula (a-4), which makes it easier to obtain a cured product with excellent adhesiveness by heating at a low temperature.

[0042] [ka]

[0043] In formula (a-4), R 1represents an organic group. The organic group is preferably 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, and more preferably 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.

[0044] 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, and an n-decyl group. R 1 The "unsubstituted alkyl group having 1 to 10 carbon atoms" represented by the following formula (I) preferably has 1 to 6 carbon atoms, and more preferably has 1 to 3 carbon atoms.

[0045] R 1 The number of carbon atoms in the "substituted alkyl group having 1 to 10 carbon atoms" represented by the formula (I) is preferably 1 to 6, and more preferably 1 to 3. Note that this number of carbon atoms refers to the number of carbon atoms in the portion excluding the substituent (the alkyl group portion). Therefore, R 1 is a "substituted alkyl group having 1 to 10 carbon atoms", R 1 The number of carbon atoms may exceed 10. Examples of the alkyl group in the "substituted alkyl group having 1 to 10 carbon atoms" include the same groups as those given as the "unsubstituted alkyl group having 1 to 10 carbon atoms".

[0046] Examples of the substituent in the "substituted alkyl group having 1 to 10 carbon atoms" include a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; a cyano group; and a group represented by the formula: OG. The number of atoms of the substituent in the "substituted alkyl group having 1 to 10 carbon atoms" (excluding the number of hydrogen atoms) is usually 1 to 30, and preferably 1 to 20. Here, G represents a protecting group for a hydroxyl group. The protecting group for a hydroxyl group is not particularly limited, and examples thereof include known protecting groups known as protecting groups for a hydroxyl group. Examples thereof include acyl-based protecting groups; silyl-based protecting groups such as trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, and t-butyldiphenylsilyl; acetal-based protecting groups such as methoxymethyl, methoxyethoxymethyl, 1-ethoxyethyl, tetrahydropyran-2-yl, and tetrahydrofuran-2-yl; alkoxycarbonyl-based protecting groups such as t-butoxycarbonyl; and ether-based protecting groups such as methyl, ethyl, t-butyl, octyl, allyl, triphenylmethyl, benzyl, p-methoxybenzyl, fluorenyl, trityl, and benzhydryl.

[0047] Examples of the "unsubstituted aryl group having 6 to 12 carbon atoms" include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. R 1 The number of carbon atoms in the "unsubstituted aryl group having 6 to 12 carbon atoms" represented by the following formula is preferably 6.

[0048] R 1 The number of carbon atoms in the "substituted aryl group having 6 to 12 carbon atoms" represented by the formula (I) is preferably 6. Note that this number of carbon atoms refers to the number of carbon atoms in the portion excluding the substituent (the aryl group portion). Therefore, R 1 is a "substituted aryl group having 6 to 12 carbon atoms", R 1 The number of carbon atoms may exceed 12. Examples of the aryl group in the "substituted aryl group having 6 to 12 carbon atoms" include the same groups as those exemplified as the "unsubstituted aryl group having 6 to 12 carbon atoms".

[0049] Examples of the substituent in the "substituted aryl group having 6 to 12 carbon atoms" 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; halogen atoms such as fluorine, chlorine, and bromine; and alkoxy groups such as methoxy and ethoxy. The number of atoms of the substituent in the "substituted aryl group having 6 to 12 carbon atoms" is usually 1 to 30, and preferably 1 to 20 (excluding the number of hydrogen atoms).

[0050] Among these, R 1 From the viewpoint of facilitating the production of a polysilsesquioxane compound with a stable structure and achieving more stable performance as an adhesive paste, the alkyl group is preferably at least one 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 and a fluorine atom, and an unsubstituted aryl group having 6 to 12 carbon atoms. R 1 However, by using a polysilsesquioxane compound that is an unsubstituted alkyl group having 1 to 10 carbon atoms, it becomes easier to obtain an adhesive paste that gives a cured product that is more excellent in heat resistance and adhesiveness. R 1 However, by using a polysilsesquioxane compound which is an alkyl group having 1 to 10 carbon atoms and a fluorine atom, it becomes easier to obtain an adhesive paste or cured product with a low refractive index, and it becomes easier to use it suitably for optical semiconductor elements which require a low refractive index. The alkyl group having 1 to 10 carbon atoms and a fluorine atom includes the alkyl group having the composition formula: C m H (2m-n+1) F n (m is an integer of 1 to 10, and n is an integer of 1 or more and (2m+1) or less.) Of these, a 3,3,3-trifluoropropyl group is preferred. R 1By using a polysilsesquioxane compound in which R is an unsubstituted aryl group having 6 to 12 carbon atoms, it becomes easier to obtain an adhesive paste or cured product with a high refractive index, and the compound can be easily used in optical semiconductor elements that require a high refractive index.

[0051] The content of the repeating unit represented by the formula (a-4) (i.e., the T site described below) in the polysilsesquioxane compound is typically 50 to 100 mol %, more preferably 70 to 100 mol %, even more preferably 90 to 100 mol %, and particularly preferably 100 mol %, based on all repeating units. By using a polysilsesquioxane compound in which the content ratio of the repeating unit (T site) represented by the formula (a-4) is in the above-mentioned ratio, an adhesive paste that is likely to exhibit heat resistance, adhesiveness, and refractive index performance can be obtained. The content of the repeating unit (T site) represented by the formula (a-4) in the polysilsesquioxane compound can be calculated, for example, by the following formula, when NMR peak assignment and area integration are possible: 29 Si-NMR and 1 It can be determined by measuring H-NMR.

[0052] Polysilsesquioxane compounds are soluble in various organic solvents, such as 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, the polysilsesquioxane compounds in a solution state can be prepared using these solvents. 29 Si-NMR can be measured.

[0053] The repeating unit represented by the formula (a-4) is preferably represented by the following formula (a-5).

[0054] [ka]

[0055] As shown in formula (a-5), polysilsesquioxane compounds have a structure generally called a T site, in which three oxygen atoms are bonded to a silicon atom and other groups (R 1 ) is bonded to the partial structure.

[0056] In formula (a-5), R 1 is R in the formula (a-4). 1 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 * is a Si atom. Examples of the alkyl group having 1 to 10 carbon atoms represented by * include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, and t-butyl group. Multiple *s may be the same or different.

[0057] Furthermore, the polysilsesquioxane compound is a thermosetting compound that can undergo a condensation reaction via a condensation reaction and / or hydrolysis upon heating. Therefore, at least one of the *'s in the formula (a-5) of the multiple repeating units (T sites) contained in the polysilsesquioxane compound is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom. In addition, when 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 at * in the formula (a-5) and whether all three * in the formula (a-5) are repeating units each consisting of a Si atom. moreover, 29 When the assignment of Si-NMR peaks and integration of the areas are possible, it is possible to roughly calculate the total number of repeating units in which all three *s in formula (a-5) are Si atoms 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 which all three *'s in formula (a-5) are Si atoms relative to the total number of repeating units (T sites) represented by formula (a-4) in this polysilsesquioxane compound is preferably 30 to 95 mol %, and more preferably 40 to 90 mol %, from the viewpoint of making it easier to obtain an adhesive paste that gives a cured product with superior heat resistance.

[0058] Polysilsesquioxane compounds are a type of R 1 It may be a polymer having two or more R 1 The compound may be a copolymer having the following formula:

[0059] When the polysilsesquioxane compound is a copolymer, the polysilsesquioxane compound may be any of a random copolymer, a block copolymer, a graft copolymer, an alternating copolymer, etc., but from the viewpoint of ease of production, etc., a random copolymer is preferred. The structure of the polysilsesquioxane compound may be any of a ladder structure, a double-decker structure, a cage structure, a partially cleaved cage structure, a cyclic structure, and a random structure.

[0060] In the present invention, the polysilsesquioxane compounds can be used singly or in combination of two or more.

[0061] The method for producing the polysilsesquioxane compound is not particularly limited. For example, a method for producing the polysilsesquioxane compound represented by the following formula (a-6)

[0062] [ka]

[0063] (In the formula, R 1 is R in the formula (a-4). 1 It has the same meaning as R 2 represents an alkyl group having 1 to 10 carbon atoms, and X 1 represents a halogen atom, and p represents an integer of 0 to 3. 2 , and multiple X1 may be the same as or different from each other.) A polysilsesquioxane compound can be produced by polycondensing at least one silane compound (1) represented by the following formula: R 2 Examples of the alkyl group having 1 to 10 carbon atoms include the same as those shown as the alkyl group having 1 to 10 carbon atoms represented by * in the formula (a-5). X 1 Examples of the halogen atom include a chlorine atom and a bromine atom.

[0064] Specific examples of the silane compound (1) include alkyltrialkoxysilane compounds such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and ethyltripoxysilane; alkylhalogenoalkoxysilane compounds such as methylchlorodimethoxysilane, methylchlorodiethoxysilane, methyldichloromethoxysilane, methylbromodimethoxysilane, ethylchlorodimethoxysilane, ethylchlorodiethoxysilane, ethyldichloromethoxysilane, and ethylbromodimethoxysilane; Alkyltrihalogenosilane compounds such as methyltrichlorosilane, methyltribromosilane, ethyltrichlorosilane, and ethyltribromosilane;

[0065] substituted alkyltrialkoxysilane compounds such as 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 2-cyanoethyltrimethoxysilane, and 2-cyanoethyltriethoxysilane; substituted alkylhalogenoalkoxysilane 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;

[0066] phenyltrialkoxysilane compounds, such as phenyltrimethoxysilane and 4-methoxyphenyltrimethoxysilane, which may or may not have a substituent; phenylhalogenoalkoxysilane compounds, which may or may not have a substituent, such as phenylchlorodimethoxysilane, phenyldichloromethoxysilane, 4-methoxyphenylchlorodimethoxysilane, and 4-methoxyphenyldichloromethoxysilane; phenyltrihalogenosilane compounds, such as phenyltrichlorosilane and 4-methoxyphenyltrichlorosilane, which may or may not have a substituent; and the like. These silane compounds (1) can be used singly or in combination of two or more.

[0067] The method for polycondensing the silane compound (1) is not particularly limited. For example, a method can be used in which a predetermined amount of a polycondensation catalyst is added to the silane compound (1) in a solvent or without a solvent, followed by stirring at a predetermined temperature. More specifically, examples include (a) a method in which a predetermined amount of an acid catalyst is added to the silane compound (1) and the mixture is stirred at a predetermined temperature, (b) a method in which a predetermined amount of a base catalyst is added to the silane compound (1) and the mixture is stirred at a predetermined temperature, and (c) a method in which a predetermined amount of an acid catalyst is added to the silane compound (1) and the mixture is stirred at a predetermined temperature, and then an excess amount of a base catalyst is added to make the reaction system basic, followed by stirring at a predetermined temperature. Among these, methods (a) and (c) are preferred because they allow the desired polysilsesquioxane compound to be obtained efficiently.

[0068] The polycondensation catalyst used may be either an acid catalyst or a base catalyst. Two or more polycondensation catalysts may be used in combination, but it is preferred to use at least an acid catalyst. Examples of the acid catalyst 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.

[0069] Examples of the base catalyst 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 hydrogencarbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate.

[0070] The amount of the polycondensation catalyst used is usually in the range of 0.05 to 10 mol %, preferably 0.1 to 5 mol %, based on the total molar amount of the silane compound (1).

[0071] When a solvent is used during polycondensation, the solvent can be appropriately selected depending on the type of silane compound (1). Examples of suitable solvents 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 alone or in combination. Furthermore, when using the above method (c), after polycondensation reaction in an aqueous system in the presence of an acid catalyst, an organic solvent and an excess amount of a basic catalyst (such as aqueous ammonia) can be added to the reaction solution, and further polycondensation reaction can be carried out under basic conditions.

[0072] The amount of the solvent used is usually 0.001 liters or more and 10 liters or less, and preferably 0.01 liters or more and 0.9 liters or less, per mole of the total amount of the silane compound (1).

[0073] The temperature at which the silane compound (1) is polycondensed is usually in the range of 0°C to the boiling point of the solvent used, preferably in the range of 20°C to 100°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 within 30 minutes to 30 hours.

[0074] Depending on the type of monomer used, it may be difficult to increase the molecular weight. For example, R 1 is an alkyl group having a fluorine atom, R 1 In such cases, a polysilsesquioxane compound having the desired molecular weight can be more easily obtained by reducing the amount of catalyst and carrying out the reaction under mild conditions for a long period of time.

[0075] After completion of the reaction, neutralization is carried out by adding an aqueous alkali solution such as sodium bicarbonate to the reaction solution when an acid catalyst was used, or by adding an acid such as hydrochloric acid to the reaction solution when a base catalyst was used, and the salt generated during this process is removed by filtration, washing with water, or the like, to obtain the target polysilsesquioxane compound.

[0076] When producing a polysilsesquioxane compound by the above method, the OR of the silane compound (1) 2 or X 1 The portion of the polysilsesquioxane that has not undergone hydrolysis and subsequent condensation reaction remains in the polysilsesquioxane compound.

[0077] When component (A) is, for example, a polysilsesquioxane compound obtained by a polycondensation reaction of silane compound (1), curing proceeds through a condensation reaction, including the reaction with a silane coupling agent described below. Therefore, the adhesive paste of the present invention is different from general heat-curing silicone adhesives that cure through an addition reaction in the presence of a noble metal catalyst such as a platinum catalyst. Therefore, the adhesive paste containing the polysilsesquioxane compound of the present invention contains substantially no precious metal catalyst or contains a small amount of precious metal catalyst. Here, "substantially not containing a precious metal catalyst or containing a small amount of precious metal catalyst" means "not intentionally adding any component that can be interpreted as a precious metal catalyst, and the content of precious metal catalyst relative to the amount of active ingredient in the adhesive paste, converted into the mass of catalytic metal element, is, for example, less than 1 mass ppm." From the viewpoints of stable production taking into account formulation variations, storage stability, and the fact that precious metal catalysts are expensive, it is preferable that the adhesive paste contains substantially no precious metal catalyst or has a low content of precious metal catalyst.

[0078] [Solvent (S)] The adhesive paste of the present invention is prepared by dissolving the thermosetting organopolysiloxane compound (A) in a solvent (S) containing an organic solvent (SL) having a boiling point of 100°C or higher and lower than 254°C. Here, the boiling point refers to the boiling point at 1013 hPa (the same applies throughout this specification). The organic solvent (SL) is not particularly limited as long as it has a boiling point of 100° C. or higher and lower than 254° C. and is capable of dissolving or dispersing the components of the adhesive paste of the present invention. The boiling point of the organic solvent (SL) is 100°C or higher and lower than 254°C, preferably 100°C or higher and lower than 200°C, more preferably 105°C or higher and lower than 185°C, and particularly preferably 110°C or higher and lower than 170°C.

[0079] Such organic solvents (SL) volatilize more efficiently when heated at low temperatures than organic solvents with high boiling points of 254°C or higher and 300°C or lower. Therefore, by including the organic solvent (SL), the mass loss rate 100℃2h is 10% or more, and the mass reduction rate 170℃2h -mass reduction rate 100℃2h In addition, such an organic solvent (SL) has a relatively slow evaporation rate compared to a low-boiling organic solvent having a boiling point of less than 100°C. Therefore, when an adhesive paste containing an organic solvent (SL) is heated at a low temperature, it volatilizes efficiently without leaving a large amount of solvent behind, making it easy to obtain sufficient adhesive strength, and in addition, even when heated at a low temperature, the concentration of the active ingredient in the adhesive paste increases quickly, making it easy to harden. Therefore, the resulting cured product has excellent adhesion and is capable of mounting semiconductor elements well even long after application to the substrate.

[0080] Specific examples of the organic solvent (SL) include diethylene glycol monobutyl ether acetate (boiling point 247 ° C), dipropylene glycol-n-butyl ether (boiling point 229 ° C), dipropylene glycol methyl ether acetate (boiling point 209 ° C), diethylene glycol butyl methyl ether (boiling point 212 ° C), dipropylene glycol-n-propyl ether (boiling point 212 ° C), tripropylene glycol dimethyl ether (boiling point 215 ° C), triethylene glycol dimethyl ether (boiling point 216 ° C), diethylene glycol monoethyl ether acetate (boiling point 218 ° C), diethylene glycol-n-butyl ether (boiling point 230 ° C), ethylene glycol monophenyl ether (boiling point 245 ° C), Examples of the methyl ether 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 to 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 to 197 ° C), cyclohexanol (boiling point 161 ° C), and cyclohexadienone (boiling point 104 to 104.5 ° C). Among these, as the organic solvent (SL), from the viewpoint of being able to more effectively exhibit the effect of using the organic solvent (SL) and from the viewpoint of being able to easily mix the active ingredient well, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, and cyclohexanone are preferred, and ethylene glycol monobutyl ether acetate and cyclohexanone are more preferred. The organic solvent (SL) may be used alone or in combination of two or more kinds.

[0081] In the adhesive paste of the present invention, the content of the organic solvent (SL) is preferably 10% by mass or more and 50% by mass or less, more preferably 18% by mass or more and 45% by mass or less, and particularly preferably 20% by mass or more and 40% by mass or less, relative to the total mass of the adhesive paste. By setting the content of the organic solvent (SL) relative to the total mass of the adhesive paste within the above range, the workability in the process of filling the adhesive paste into a syringe and the application process can be improved, and the effects of using the organic solvent (SL) can be more effectively achieved. Here, excellent workability in the step of filling a syringe with adhesive paste means that an appropriate amount can be filled into the syringe without air bubbles.

[0082] The adhesive paste of the present invention may contain a solvent other than the organic solvent (SL). As the solvent other than the organic solvent (SL), an organic solvent having a boiling point of 254° C. or higher and 300° C. or lower (hereinafter, sometimes referred to as "organic solvent (SH)") is 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) in combination with solvents other than organic solvents (SL), the temperature range in which the adhesive paste is heated to obtain a hardened product can be more precisely adjusted, thereby reducing the impact of heating on optical components and sensor chips that are easily affected by heat.

[0083] Specific examples of the organic solvent (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 to 294°C), tetraethylene glycol dimethyl ether (boiling point 275°C), and polyethylene glycol monomethyl ether (boiling point 290 to 310°C). Among these, tripropylene glycol-n-butyl ether and 1,6-hexanediol diacrylate are preferred as the organic solvent (SH) from the viewpoint that the effect of using the organic solvent (SL) and the organic solvent (SH) in combination can be more easily obtained.

[0084] When an organic solvent (SL) and an organic solvent (SH) are used in combination, specifically, a combination of diethylene glycol monoethyl ether acetate (organic solvent (SL)) and tripropylene glycol-n-butyl ether (organic solvent (SH)), a combination of ethylene glycol monobutyl ether acetate (organic solvent (SL)) and tripropylene glycol-n-butyl ether (organic solvent (SH)), a combination of cyclohexanone (organic solvent (SL)) and tripropylene glycol-n-butyl ether (organic solvent (SH)), a combination of diethylene glycol monoethyl ether acetate (organic solvent (SL)) and 1,6-hexanediol diacrylate (organic solvent (SH)), a combination of ethylene glycol monobutyl ether acetate (organic solvent (SL)) and 1,6-hexanediol diacrylate (organic solvent (SH)), and a combination of cyclohexanone (organic solvent (SL)) and 1,6-hexanediol diacrylate (organic solvent (SH)) are preferred.

[0085] The organic solvent (SL) preferably accounts for 60% by mass or more of the entire solvent (S), more preferably 65% ​​by mass or more, and particularly preferably 70% by mass or more. By using the organic solvent (SL) of the entire solvent (S) within the above range, the effect of using the organic solvent (SL) can be more effectively exhibited.

[0086] The adhesive paste of the present invention preferably contains the solvent (S) in an amount 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. By having the solid content concentration within this range, the active ingredient can be easily mixed well, the workability is excellent in the process of filling the adhesive paste into a syringe and the application process, and the effect of using the organic solvent (SL) can be more effectively exhibited. Furthermore, when die bonding is performed, it is possible to prevent the occurrence of voids between the adhesive paste and the substrate or the like to which it is to be bonded, thereby increasing the reliability of the package.

[0087] [Other ingredients] The adhesive paste of the present invention contains a thermosetting organopolysiloxane compound (A) and a solvent (S), and may also contain the components shown below.

[0088] (1) Silane coupling agent (B) The adhesive paste of the present invention may contain a silane coupling agent as component (B). Examples of the silane coupling agent include a silane coupling agent (B1) having a nitrogen atom in the molecule (hereinafter, sometimes referred to as "component (B1)") and a silane coupling agent (B2) having an acid anhydride structure in the molecule (hereinafter, sometimes referred to as "component (B2)").

[0089] The adhesive paste containing the silane coupling agent (B1) has excellent workability in the application step, and also has excellent curing properties due to the condensation reaction with the component (A) when heated, giving a cured product that is excellent in adhesion, heat resistance, and crack suppression properties when heated at low temperatures. Here, having superior crack suppression properties in the cured product means that when the adhesive paste is heated to obtain a cured product, cracks do not occur in the cured product due to temperature changes.

[0090] The silane coupling agent (B1) is not particularly limited as long as it is a silane coupling agent having a nitrogen atom in the molecule. Examples thereof include trialkoxysilane compounds represented by the following formula (b-1), dialkoxyalkylsilane compounds or dialkoxyarylsilane compounds represented by the following formula (b-2), etc.

[0091] [ka]

[0092] In the above formula, R a represents an alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, or a t-butoxy group. a They may be the same or different. R b represents an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or a t-butyl group; or an aryl group having or having no substituent, such as a phenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, or a 1-naphthyl group.

[0093] R c represents an organic group having a nitrogen atom and having 1 to 10 carbon atoms. c may further be bonded to another group containing a silicon atom. R c Specific examples of the organic group having 1 to 10 carbon atoms include an N-2-(aminoethyl)-3-aminopropyl group, a 3-aminopropyl group, an N-(1,3-dimethyl-butylidene)aminopropyl group, a 3-ureidopropyl group, and an N-phenyl-aminopropyl group.

[0094] Among the compounds represented by the above formula (b-1) or (b-2), R c In the case where the group (I) is an organic group bonded to another group containing a silicon atom, examples of the compound include those that bond to another silicon atom via an isocyanurate skeleton to form an isocyanurate-based silane coupling agent, and those that bond to another silicon atom via a urea skeleton to form a urea-based silane coupling agent.

[0095] Among these, as the silane coupling agent (B1), isocyanurate-based silane coupling agents and urea-based silane coupling agents are preferred because they tend to give cured products with higher adhesive strength, and moreover, those having four or more alkoxy groups bonded to silicon atoms in the molecule are preferred. "Having four or more alkoxy groups bonded to a silicon atom" 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.

[0096] An example of an isocyanurate-based silane coupling agent having four or more alkoxy groups bonded to a silicon atom is a compound represented by the following formula (b-3), and an example of a urea-based silane coupling agent having four or more alkoxy groups bonded to a silicon atom is a compound represented by the following formula (b-4).

[0097] [ka]

[0098] In the formula, R a represents R in the formulas (b-1) and (b-2). a Each of t1 to t5 independently represents an integer of 1 to 10, preferably an integer of 1 to 6, and particularly preferably 3.

[0099] Specific examples of the compound represented by formula (b-3) include 1,3,5-N-tris[(tri(C1-6)alkoxy)silyl(C1-10)alkyl]isocyanurates such as 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, and 1,3,5-N-tris(3-tributoxysilylpropyl)isocyanurate; 1,3,5-N-tris(3-dimethoxymethylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dimethoxyethylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dimethoxy-i-propylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dimethoxy-n-propylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dimethoxyphenylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-diethoxy 1,3,5-N-tris(3-diethoxyethylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-diethoxy-i-propylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-diethoxy-n-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-propoxyi-propylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-di-i-propoxyn-propylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-di-i-propoxyphenylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dibutoxymethylsilylpropyl)isocyanurate, 1,3, Examples of 1,3,5-N-tris[(di(C1-C6)alkoxy)silyl(C1-C10)alkyl]isocyanurates include 5-N-tris(3-dibutoxyethylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dibutoxyi-propylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dibutoxyn-propylsilylpropyl)isocyanurate, and 1,3,5-N-tris(3-dibutoxyphenylsilylpropyl)isocyanurate.

[0100] Specific examples of the compound represented by formula (b-4) include N,N'-bis[(tri(C1-C6)alkoxysilyl)(C1-C10)alkyl]ureas such as N,N'-bis(3-trimethoxysilylpropyl)urea, N,N'-bis(3-triethoxysilylpropyl)urea, N,N'-bis(3-tripropoxysilylpropyl)urea, N,N'-bis(3-tributoxysilylpropyl)urea, and N,N'-bis(2-trimethoxysilylethyl)urea; N,N'-bis[(di(C1-6)alkoxy(C1-6)alkylsilyl(C1-10)alkyl)ureas such as N,N'-bis(3-dimethoxymethylsilylpropyl)urea, N,N'-bis(3-dimethoxyethylsilylpropyl)urea, and N,N'-bis(3-diethoxymethylsilylpropyl)urea; N,N'-bis[(di(C1-6)alkoxy(C6-20)arylsilyl(C1-10)alkyl)ureas such as N,N'-bis(3-dimethoxyphenylsilylpropyl)urea and N,N'-bis(3-diethoxyphenylsilylpropyl)urea; and the like. The silane coupling agent (B1) can be used alone or in combination of two or more.

[0101] Among these, it is preferable to use, as the silane coupling agent (B1), 1,3,5-N-tris(3-trimethoxysilylpropyl)isocyanurate, 1,3,5-N-tris(3-triethoxysilylpropyl)isocyanurate (hereinafter, the two are referred to as "isocyanurate compounds"), N,N'-bis(3-trimethoxysilylpropyl)urea, N,N'-bis(3-triethoxysilylpropyl)urea (hereinafter, the two are referred to as "urea compounds"), and combinations of the above isocyanurate compounds and urea compounds.

[0102] When the isocyanurate compound and the urea compound are used in combination, the mass ratio of the isocyanurate compound to the urea compound is preferably 100:1 to 100:200, more preferably 100:10 to 100:110. By using the isocyanurate compound and the urea compound in combination in such a ratio, an adhesive paste can be obtained that gives a cured product with higher adhesive strength and more excellent heat resistance.

[0103] When the adhesive paste of the present invention contains a silane coupling agent (B1) [component (B1)], the content of component (B1) is not particularly limited, but the amount is such that the mass ratio of component (A) to component (B1) [component (A) : component (B1)] is preferably 100:0.1 to 100:90, more preferably 100:0.5 to 100:70, more preferably 100:1 to 100:55, more preferably 100:3 to 100:45, and even more preferably 100:5 to 100:35. By using the component (B1) in the above range, the effect of adding the component (B1) can be more effectively achieved.

[0104] The adhesive paste containing the silane coupling agent (B2) has excellent workability in the application step and gives a cured product that is superior in adhesiveness and heat resistance when heated at low temperatures.

[0105] Examples of the silane coupling agent (B2) include tri(C1-C6)alkoxysilyl(C2-C8)alkyl succinic anhydrides, such as 2-(trimethoxysilyl)ethyl succinic anhydride, 2-(triethoxysilyl)ethyl succinic anhydride, 3-(trimethoxysilyl)propyl succinic anhydride, and 3-(triethoxysilyl)propyl succinic anhydride; Di(C1-C6)alkoxymethylsilyl(C2-C8)alkyl succinic anhydrides such as 2-(dimethoxymethylsilyl)ethyl succinic anhydride; (C1-C6)alkoxydimethylsilyl(C2-C8)alkyl succinic anhydrides such as 2-(methoxydimethylsilyl)ethyl succinic anhydride;

[0106] Trihalogenosilyl (C2-C8) alkyl succinic anhydrides such as 2-(trichlorosilyl)ethyl succinic anhydride and 2-(tribromosilyl)ethyl succinic anhydride; Dihalogenomethylsilyl (C2-C8) alkyl succinic anhydrides such as 2-(dichloromethylsilyl)ethyl succinic anhydride; halogenodimethylsilyl (having 2 to 8 carbon atoms) alkyl succinic anhydrides such as 2-(chlorodimethylsilyl)ethyl succinic anhydride; and the like. The silane coupling agent (B2) can be used alone or in combination of two or more kinds.

[0107] Among these, as the silane coupling agent (B2), tri(C1-6)alkoxysilyl(C2-8)alkyl succinic anhydride is preferred, and 3-(trimethoxysilyl)propyl succinic anhydride or 3-(triethoxysilyl)propyl succinic anhydride is particularly preferred.

[0108] When the adhesive paste of the present invention contains a silane coupling agent (B2) [component (B2)], the content of component (B2) is not particularly limited, but the mass ratio of component (A) to component (B2) [component (A) : component (B2)] is preferably 100:0.01 to 100:40, more preferably 100:0.01 to 100:30, and even more preferably 100:0.1 to 100:10. By using the component (B2) in the above range, the effect of adding the component (B2) can be more effectively achieved.

[0109] (2) Fine particles (C) The adhesive paste of the present invention may contain fine particles as component (C). Examples of the fine particles include fine particles (C1) having an average primary particle diameter of 5 nm or more and 40 nm or less (hereinafter, sometimes referred to as "component (C1)") and fine particles (C2) having an average primary particle diameter of more than 0.04 μm and 8 μm or less (hereinafter, sometimes referred to as "component (C2)").

[0110] The adhesive paste containing the fine particles (C1) has excellent workability in the application step and gives a cured product that is superior in adhesiveness and heat resistance when heated at low temperatures. Since this effect can be more easily obtained, the average primary particle size of the fine particles (C1) is preferably 5 nm or more and 30 nm or less, more preferably 5 nm or more and 20 nm or less. The average primary particle size of the fine particles (C1) can be determined by observing the shape of the fine particles using a transmission electron microscope.

[0111] The specific surface area of ​​the fine particles (C1) is preferably 10 m 2 / g or more 500m 2 / g or less, more preferably 20m 2 / g or more 300m 2 When the specific surface area is within the above range, an adhesive paste having excellent workability in the application step can be easily obtained. The specific surface area can be determined by the BET multipoint method.

[0112] The shape of the fine particles (C1) may be any of spherical, chain-like, needle-like, plate-like, flake-like, rod-like, fibrous, etc., but is preferably spherical. Here, spherical means a nearly spherical shape including a true sphere, as well as a polyhedral shape that can approximate a sphere, such as a spheroid, oval, confetti-like, or cocoon-like shape.

[0113] The constituent components of the fine particles (C1) are not particularly limited, and examples thereof include metals, metal oxides, minerals, metal carbonates, metal sulfates, metal hydroxides, metal silicates, inorganic components, organic components, and silicones. The fine particles (C1) used may be surface-modified.

[0114] Metal refers to an element belonging to Group 1 (excluding H), Groups 2 to 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) in the periodic table.

[0115] 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. The metal oxide fine particles also include sol particles made of these metal oxides.

[0116] Examples of minerals include smectite and bentonite. Examples of smectite include montmorillonite, beidellite, hectorite, saponite, stevensite, nontronite, and sauconite.

[0117] Examples of metal carbonates include calcium carbonate and magnesium carbonate, examples of metal sulfates include calcium sulfate and barium sulfate, examples of metal hydroxides include aluminum hydroxide, and examples of metal silicates include aluminum silicate, calcium silicate, and magnesium silicate. Furthermore, examples of inorganic components include silica, etc. Examples of silica include dry silica, wet silica, and surface-modified silica (surface-modified silica). The organic component may be an acrylic polymer or the like.

[0118] Silicone refers to an artificial polymer compound having a main skeleton formed by siloxane bonds, such as dimethylpolysiloxane, diphenylpolysiloxane, and methylphenylpolysiloxane.

[0119] The fine particles (C1) can be used singly or in combination of two or more kinds. Among these, in the present invention, silica, metal oxides, and minerals are preferred, and silica is more preferred, since an adhesive paste with excellent transparency can be easily obtained.

[0120] Among silicas, surface-modified silica is preferred, and hydrophobic surface-modified silica is more preferred, from the viewpoint that it is relatively easy to mix into an adhesive paste and that an adhesive paste having excellent workability in the application step is easily obtained. Examples of hydrophobic surface-modified silica include silica having, on its surface, a trialkylsilyl group having 1 to 20 tricarbon atoms, such as a trimethylsilyl group; an alkylsilyl group having 1 to 20 dicarbon atoms, such as a dimethylsilyl group; or an alkylsilyl group having 1 to 20 carbon atoms, such as an octylsilyl group; and silica whose surface has been treated with silicone oil. Hydrophobic surface-modified silica can be obtained, for example, by surface-modifying silica particles with a silane coupling agent having a trialkylsilyl group having 1 to 20 tricarbon atoms, an alkylsilyl group having 1 to 20 dicarbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or the like, or by treating silica particles with silicone oil.

[0121] When the adhesive paste of the present invention contains fine particles (C1) [component (C1)], the content of component (C1) is not particularly limited, but the amount is such that the mass ratio of component (A) to component (C1) [component (A) : component (C1)] is preferably 100:0.1 to 100:90, more preferably 100:0.2 to 100:60, more preferably 100:0.3 to 100:50, more preferably 100:0.5 to 100:40, and more preferably 100:0.8 to 100:30. By using the component (C1) in the above range, the effect of adding the component (C1) can be more effectively achieved.

[0122] An adhesive paste containing the fine particles (C2) gives a cured product that is superior in adhesiveness and heat resistance when heated at a low temperature. To more easily obtain this effect, the average primary particle size of the fine particles (C2) is preferably more than 0.06 μm and not more than 7 μm, more preferably more than 0.3 μm and not more than 6 μm, and even more preferably more than 1 μm and not more than 4 μm.

[0123] The average primary particle diameter of the fine particles (C2) can be determined by measuring the particle size distribution by a laser scattering method using a laser diffraction / scattering particle size distribution analyzer (for example, Horiba, Ltd., product name "LA-920") or the like.

[0124] The shape of the fine particles (C2) may be the same as those exemplified as the shape of the fine particles (C1), but is preferably spherical. In addition, examples of the constituent components of the fine particles (C2) include the same as those exemplified as the constituent components of the fine particles (C1). The fine particles (C2) can be used singly or in combination of two or more kinds. Among these, at least one type of fine particle selected from the group consisting of metal oxide, silica, and silicone whose surface is coated with silicone is preferred, and silica and silicone are more preferred, from the viewpoint that mixing into an adhesive paste is relatively easy and that a cured product having excellent adhesive properties and heat resistance is easily obtained.

[0125] When the adhesive paste of the present invention contains fine particles (C2) [component (C2)], the content of component (C2) is not particularly limited, but the amount is such that the mass ratio of component (A) to component (C2) [component (A) : component (C2)] is preferably 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 the component (C2) in the above range, the effect of adding the component (C2) can be more effectively achieved.

[0126] (3) Other additives The adhesive paste of the present invention may contain a component (D) other than the above components (A) to (C) as long as it does not impair the object of the present invention. Examples of the component (D) include antioxidants, ultraviolet absorbers, and light stabilizers.

[0127] The antioxidant is added to prevent oxidative deterioration during heating. Examples of the antioxidant include phosphorus-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants.

[0128] Examples of phosphorus-based antioxidants include phosphites and oxaphosphaphenanthrene oxides. Examples of the phenol-based antioxidant include monophenols, bisphenols, and polymeric 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 either individually or in combination of two or more. The amount of antioxidant used is usually 10% by mass or less based on the component (A).

[0130] The ultraviolet absorber is added for the purpose of improving the light resistance of the resulting adhesive paste. Examples of ultraviolet absorbers include salicylic acids, benzophenones, benzotriazoles, and hindered amines. These ultraviolet absorbents may be used alone or in combination of two or more. The amount of the ultraviolet absorber used is usually 10% by mass or less based on the component (A).

[0131] The light stabilizer is added for the purpose of improving 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 may be used either individually or in combination of two or more. The total amount of component (D) used is usually 20 mass % or less relative to component (A).

[0132] The adhesive paste of the present invention can be produced, for example, by a production method including the following steps (AI) and (AII). Step (AI): A step of polycondensing at least one compound represented by the above formula (a-6) in the presence of a polycondensation catalyst to obtain a polysilsesquioxane compound. Step (AII): A step of dissolving the polysilsesquioxane compound obtained in Step (AI) in a solvent (S) containing an organic solvent (SL) having a boiling point of 100°C or higher but lower than 254°C to obtain a solution containing the polysilsesquioxane compound.

[0133] In step (AI), at least one compound represented by formula (a-6) is polycondensed in the presence of a polycondensation catalyst to obtain a polysilsesquioxane compound, and examples thereof include the methods exemplified in the section 1) Adhesive Paste. Examples of the organic solvent (SL) and solvent (S) used in step (AII) include the same organic solvent (SL) and solvent (S) exemplified in the section 1) Adhesive Paste.

[0134] In step (AII), examples of a method for dissolving the polysilsesquioxane compound in the solvent (S) containing the organic solvent (SL) include a method in which the polysilsesquioxane compound, and optionally the components (B) to (D), are mixed with the solvent (S), degassed, and then dissolved. The mixing method and degassing method are not particularly limited, and known methods can be used. The order of mixing is not particularly limited. According to the production method including the above steps (AI) and (AII), the adhesive paste of the present invention can be produced efficiently and simply.

[0135] In the present invention, the adhesive paste is heated to volatilize the solvent (S) and harden, thereby obtaining a hardened product. The heating temperature during curing is usually 80° C. to 180° C., and preferably 80° C. to 120° C. The heating time during curing is usually 30 minutes to 10 hours, preferably 30 minutes to 5 hours, and more preferably 30 minutes to 3 hours.

[0136] The cured product obtained by curing the adhesive paste of the present invention has excellent adhesiveness. The excellent adhesiveness of the cured product obtained by curing the adhesive paste of the present invention can be confirmed, for example, as follows. 2 The adhesive paste of the present invention is applied to the mirror surface of a silicon chip (100 mm square), and the applied surface is placed on a silver-plated copper plate and pressed (thickness of adhesive paste after pressing: approximately 2 μm), and then heat-treated at 100°C for 2 hours to harden. This is then left on the measurement stage of a bond tester at 23°C for 30 seconds, and stress is applied to the adhesive surface in the horizontal direction (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.

[0137] The adhesive strength of the cured product obtained by curing the adhesive paste of the present invention is preferably 7 N / mm□ or more at 23°C, more preferably 10 N / mm□ or more, even more preferably 14 N / mm□ or more, and particularly preferably 15 N / mm□ or more. In this specification, "1 mm square" means "1 mm square," that is, 1 mm x 1 mm (a square with one side measuring 1 mm).

[0138] Because of the above properties, the adhesive paste of the present invention can be suitably used as an adhesive for semiconductor element fixing materials.

[0139] 2) Method of using adhesive paste and method of manufacturing semiconductor device using adhesive paste A method for producing a semiconductor device using the adhesive paste of the present invention as an adhesive for an optical element fixing material is a method comprising the following steps (BI) and (BII). Step (BI): A step of applying adhesive paste to one or both of the adhesive surfaces of the semiconductor element and the supporting substrate and pressing them together. Step (BII): A step of heating and hardening the adhesive paste of the pressure-bonded product obtained in Step (BI) to fix the semiconductor element to the support substrate.

[0140] Examples of semiconductor elements include optical semiconductor elements such as light-emitting elements such as lasers and light-emitting diodes (LEDs), light-receiving elements such as solar cells, transistors, sensors such as temperature sensors and pressure sensors, integrated circuits, etc. Among these, optical semiconductor elements are preferred from the viewpoint that the effects of using the adhesive paste of the present invention can be more suitably exhibited.

[0141] Materials for the support substrate to which the semiconductor element is bonded include glasses such as soda lime glass and heat-resistant hard glass; ceramics; sapphire; metals such as iron, copper, aluminum, gold, silver, platinum, chromium, titanium and alloys of these metals, and 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, polyether ether ketone, polyethersulfone, polyphenylene sulfide, polyetherimide, polyimide, polyamide, acrylic resin, norbornene resin, cycloolefin resin, and glass epoxy resin.

[0142] The adhesive paste of the present invention is preferably filled in a syringe. The adhesive paste is filled in a syringe, which provides excellent workability in the application process. The syringe may be made of any of synthetic resin, metal, and glass, but is preferably made of synthetic resin. The capacity of the syringe is not particularly limited and may be determined appropriately according to the amount of adhesive paste to be filled or applied. Alternatively, commercially available syringes may be used, such as the SS-01T series (manufactured by TERUMO Corporation) and the PSY series (manufactured by Musashi Engineering Co., Ltd.).

[0143] In the method for manufacturing a semiconductor device of the present invention, a syringe filled with adhesive paste descends vertically to approach a support substrate, and 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, and the support substrate moves sideways. This operation is then repeated to continuously apply adhesive paste to the support substrate. After that, a semiconductor element is mounted on the applied adhesive paste and pressure-bonded to the support substrate.

[0144] The amount of adhesive paste to be applied is not particularly limited as long as it is an amount that can firmly bond the semiconductor element and the supporting substrate to be bonded by curing. Typically, the amount is such that the thickness of the adhesive paste coating is 0.5 μm to 5 μm, preferably 1 μm to 3 μm.

[0145] The adhesive paste in the resulting pressure-bonded product is then heated and hardened, thereby fixing the semiconductor element to the support substrate. The heating temperature and heating time are as explained in the section 1) Adhesive Paste.

[0146] The semiconductor device obtained by the method for manufacturing a semiconductor device of the present invention has a semiconductor element well mounted on the adhesive paste, and the semiconductor element is fixed with high adhesive strength. [Example]

[0147] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. In each example, parts and percentages are by weight unless otherwise specified.

[0148] [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 Examples were measured using the following apparatus under the following conditions, in terms of standard polystyrene. Device name: HLC-8220GPC, manufactured by Tosoh Corporation Column: TSKgel GMHXL, TSKgel GMHXL, and TSKgel 2000HXL connected in sequence Solvent: tetrahydrofuran Injection volume: 80μl Measurement temperature: 40℃ Flow rate: 1ml / min Detector: differential refractometer

[0149] [IR spectrum measurement] The IR spectrum of the thermosetting organopolysiloxane compound (A) obtained in the Production Examples was measured using a Fourier transform infrared spectrophotometer (Spectrum 100, manufactured by PerkinElmer).

[0150] (Production Example 1) A 300 ml eggplant-shaped flask was charged with 71.37 g (400 mmol) of methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), and 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 with stirring. The entire volume was stirred at 30°C for 2 hours, then heated to 70°C and stirred for 5 hours. After that, the reaction solution was returned to room temperature (23°C), and 140 g of propyl acetate was added. To this was added 0.12 g of 28% aqueous ammonia (0.5 mol % based on the total amount of the silane compounds) while stirring the entire volume, and the temperature was raised to 70° C., followed by further stirring for 3 hours. Purified water was added to the reaction mixture, and the layers were 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 dried in vacuo 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. The IR spectrum data of the thermosetting organopolysiloxane compound (A1) is shown below. Si-CH3: 1272 cm -1 ,1409cm -1 , Si-O: 1132 cm -1

[0151] (Production Example 2) A 300 mL eggplant-shaped flask was charged with 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, and then an aqueous solution prepared by dissolving 0.0675 g of 35% hydrochloric acid (HCl amount: 0.65 mmol, 0.25 mol% relative to the total amount of silane compounds) in 14.0 mL of distilled water was added with stirring, and the entire mixture was stirred at 30°C for 2 hours, then heated to 70°C and stirred for 20 hours. While continuing to stir the contents, a mixed solution of 0.0394 g of 28% aqueous ammonia (NH3 content: 0.65 mmol) and 46.1 g of propyl acetate was added thereto to adjust the pH of the reaction solution to 6.9, and the mixture was stirred at 70°C for 40 minutes. After the reaction mixture was cooled to room temperature, 50 g of propyl acetate and 100 g of water were added thereto for separation, and an organic layer containing the reaction product was obtained. Magnesium sulfate was added to this organic layer for drying. After removing the magnesium sulfate by filtration, the organic layer was concentrated using an evaporator, and the concentrate was dried in vacuo to obtain 22.3 g of a 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. The IR spectrum data of the thermosetting organopolysiloxane compound (A2) is shown below. Si-CH3: 1272 cm -1 ,1409cm -1 , Si-O: 1132 cm -1 ,CF:1213cm -1

[0152] (Production Example 3) A 300 ml eggplant-shaped flask was charged with 28.91 g (145.8 mmol) of phenyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.), and then an aqueous solution of 0.0376 g of 35% hydrochloric acid (0.25 mol% based on the total amount of silane compounds) dissolved in 7.874 ml of distilled water was added with stirring. The total volume was heated to 30 ° C for 2 hours, then heated to 70 ° C and stirred for 5 hours. After that, the reaction solution was returned to room temperature (23 ° C), and 50 g of propyl acetate and 100 g of water were added and the mixture was separated to obtain an organic layer containing the reaction product. Magnesium sulfate was added to this organic layer and the mixture was dried. After filtering off the magnesium sulfate, the organic layer was concentrated using an evaporator, and the concentrate was dried in vacuo to obtain 17.0 g of a 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. The IR spectrum data of the thermosetting organopolysiloxane compound (A3) is shown below. Si-C6H5:698cm -1 , Si-O: 1132 cm -1

[0153] The compounds used in the examples and comparative examples are shown below. [Component (A)] Thermosetting organopolysiloxane compound (A1): Organopolysiloxane compound obtained in Production Example 1 Thermosetting organopolysiloxane compound (A2): Organopolysiloxane compound obtained in Production Example 2 Thermosetting organopolysiloxane compound (A3): Organopolysiloxane compound obtained in Production Example 3

[0154] [Solvent (S)] (1) Organic solvent (SL) Diethylene glycol monoethyl ether acetate (EDGAC): manufactured by Tokyo Chemical Industry Co., Ltd. (boiling point 218°C) Ethylene glycol monobutyl ether acetate (BMGAC): manufactured by Tokyo Chemical Industry Co., Ltd. (boiling point 192°C) Cyclohexanone: manufactured by Tokyo Chemical Industry Co., Ltd. (boiling point 157°C) (2) Organic solvent (SH) Tripropylene glycol-n-butyl ether (TPnB): manufactured by The Dow Chemical Company (boiling point 274°C) (3) Other Acetone: Tokyo Chemical Industry Co., Ltd. (boiling point 56°C)

[0155] [(B) component] Silane coupling agent (B1): 1,3,5-N-tris[3-(trimethoxysilyl)propyl]isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-9659") Silane coupling agent (B2): 3-(trimethoxysilyl)propylsuccinic anhydride (manufactured by Shin-Etsu Chemical Co., Ltd., product name "X-12-967C") [(C) component] Fine particles (C1): Silica fine particles (manufactured by Nippon Aerosil Co., Ltd., product name "AEROSIL RX300", average primary particle diameter: 7 nm, specific surface area: 210 m 2 / g) Microparticles (C2): Silicone microparticles (manufactured by Nikko Rica Corporation, product name "MSP-SN08", average primary particle diameter: 0.8 μm, shape: spherical)

[0156] Example 1 28 parts of EDGAC (SL), 10 parts of silane coupling agent (B1), and 3 parts of silane coupling agent (B2) were added to 100 parts of thermosetting organopolysiloxane compound (A1), and the entire mixture was thoroughly mixed and degassed to obtain adhesive paste 1 with a solids concentration of 80%.

[0157] (Examples 2 to 13, Comparative Examples 1 to 4) Adhesive pastes 2 to 13 and 1r to 4r were obtained in the same manner as in Example 1, except that the types and blending ratios of the compounds (each component) were changed to those shown in Table 1 below. In Examples 9 and 10, the fine particles (C1) and the fine particles (C2) were added before the addition of cyclohexanone (SL), the silane coupling agent (B1), and the silane coupling agent (B2).

[0158] The adhesive pastes 1 to 13 and 1r to 4r obtained in the examples and comparative examples were subjected to the following tests. The results are shown in Table 2.

[0159] [Measurement of mass loss rate] 15 mg of the adhesive paste obtained in the examples and comparative examples was placed in a differential thermal and thermogravimetric simultaneous analyzer (Shimadzu Corporation, product name "DTG-60"), and heated to 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 loss rate before and after heating was measured. 100℃2h The following formula was calculated: (%) [{[(mass of adhesive paste before heating)-(mass of adhesive paste after heating at 100°C for 2 hours)] / (mass of adhesive paste before heating)}×100]. In addition, except for changing the heating conditions to 170°C for 2 hours, the mass loss rate 100℃2h The mass loss rate of the adhesive paste before and after heating was measured in the same manner as in (%). 170℃2h The following formula was calculated: (%) [{[(mass of adhesive paste before heating)-(mass of adhesive paste after heating at 170°C for 2 hours)] / (mass of adhesive paste before heating)}×100]. Furthermore, from the measured mass loss rate, the mass loss rate 170℃2h -mass reduction rate 100℃2h (%) was calculated.

[0160] [Chip mounting evaluation] The adhesive pastes obtained in the examples and comparative examples were dispensed onto an electroless silver-plated copper plate (average roughness of the silver-plated surface Ra: 0.025 μm) so as to have a diameter of 0.5 mm, and were left to stand under a standard environment (temperature: 23°C ± 1°C, relative humidity: 50 ± 5%). After 5 minutes, a square with a side length of 1 mm (with an area of ​​1 mm) was formed. 2 ) was mounted on the substrate, and the tilt of the chip was observed. If the chip could be mounted without tilting, it was evaluated as "good", and if any defect such as tilting of the chip occurred, it was evaluated as "poor".

[0161] [Adhesion strength evaluation] A square with a side length of 1 mm (area 1 mm 2The adhesive pastes obtained in the Examples and Comparative Examples were applied to the mirror surface of a silicon chip (100 mm thick) and allowed to stand under standard conditions (temperature: 23°C ± 1°C, relative humidity: 50 ± 5%). After 5 minutes, the applied surface was placed on an adherend (electroless silver-plated copper plate (average roughness of the silver-plated surface, Ra: 0.025 μm)) and pressed so that the adhesive paste thickness after pressing was approximately 2 μm. The paste was then heat-treated at 100°C for 2 hours to harden the adhesive, yielding an adherend with a test piece attached. The adherend with the test piece attached was then placed on the measurement stage of a bond tester (Daisi, Series 4000) at 23°C for 30 seconds. A horizontal (shear) stress was applied to the adhesive surface from a height of 100 μm from the adherend at a speed of 200 μm / s, and the adhesive strength (N / mm□) between the test piece and the adherend at 23°C was measured.

[0162] [Table 1]

[0163] [Table 2]

[0164] The following can be seen from Tables 1 and 2: The adhesive pastes 1 to 13 of Examples 1 to 13 provide cured products that are excellent in adhesive strength and chip mounting properties. In particular, when a solvent with a lower boiling point is contained as the organic solvent (SL), the adhesive strength of the cured product obtained by curing the adhesive paste is superior (Examples 1 to 3). Even when a mixed solvent of organic solvent (SL) and organic solvent (SH) is used as the solvent (S), an adhesive paste having excellent adhesive strength of the cured product and excellent chip mounting properties can be obtained (Examples 4 to 6). Adhesive pastes with higher solid content concentrations have better adhesive strength in the cured products obtained by curing the adhesive pastes (Examples 4 and 7, Examples 3 and 8). The adhesive paste containing the microparticles (C) gives a cured product with good adhesive strength, despite the relatively low content of components (A) and (B) compared to the adhesive paste without the microparticles (C) (Examples 9 and 10). Even when the type of thermosetting organopolysiloxane compound (A) (type of polysilsesquioxane compound side chain) was changed, the adhesive strength of the cured product obtained by curing the adhesive paste was excellent (Examples 11 to 13).

[0165] On the other hand, the adhesive paste 1r of Comparative Example 1 contains only a high-boiling organic solvent (SH) as the solvent (S), and therefore the mass reduction rate 100℃2h The viscosity is small, a large amount of solvent remains, the adhesive paste cannot be cured sufficiently, and sufficient adhesive strength is not achieved. The adhesive paste 2r of Comparative Example 2 contains only an organic solvent with a very low boiling point as the solvent (S), so it dries immediately after application and has poor chip mounting properties. In the adhesive paste 3r of Comparative Example 3, the content of the organic solvent (SL) is small relative to the total mass of the adhesive paste and the entire solvent (S), so the mass reduction rate 100℃2h The adhesive paste cannot be cured sufficiently and does not exhibit sufficient adhesive strength. The adhesive paste 4r of Comparative Example 4 has a mass reduction rate 100℃2h Although the above requirement is satisfied, the solvent (S) contains a large proportion of organic solvent (SH), so when heated to 100°C, a relatively large amount of organic solvent (SH) remains in the cured product, preventing the adhesive paste from curing sufficiently and resulting in insufficient adhesive strength.

Claims

1. An adhesive paste that is an adhesive for a semiconductor element fixing material used for pressure-bonding a semiconductor element to a support substrate, the adhesive paste contains a thermosetting organopolysiloxane compound (A) and a solvent (S), and the thermosetting organopolysiloxane compound (A) is dissolved in the solvent (S); the solvent (S) contains an organic solvent (SL) having a boiling point of 100°C or higher and lower than 254°C, The solid content concentration of the adhesive paste is 50% by mass or more and 90% by mass or less, The mass loss rate of the adhesive paste before and after heating at 100°C for 2 hours １００℃２ｈ is 21% or more, and After heating the adhesive paste at 170°C for 2 hours, the mass loss rate of the adhesive paste before and after heating was measured. １７０℃２ｈ When the mass reduction rate is １７０℃２ｈ - Mass reduction rate １００℃２ｈ is less than 14%.

2. An adhesive paste that is an adhesive for a semiconductor element fixing material used for pressure-bonding a semiconductor element to a support substrate, the adhesive paste contains a thermosetting organopolysiloxane compound (A) and a solvent (S), and the thermosetting organopolysiloxane compound (A) is dissolved in the solvent (S); the solvent (S) contains an organic solvent having a boiling point of 100°C or higher and lower than 200°C, The solid content concentration of the adhesive paste is 50% by mass or more and 90% by mass or less, The mass loss rate of the adhesive paste before and after heating at 100°C for 2 hours １００℃２ｈ is 10% or more, and After heating the adhesive paste at 170°C for 2 hours, the mass loss rate of the adhesive paste before and after heating was measured. １７０℃２ｈ When the mass reduction rate is １７０℃２ｈ - Mass reduction rate １００℃２ｈ is less than 14%.

3. 2. The adhesive paste according to claim 1, wherein the content of the organic solvent (SL) is 10% by mass or more and 50% by mass or less, based on the total mass of the adhesive paste.

4. 3. The adhesive paste according to claim 2, wherein the content of the organic solvent having a boiling point of 100°C or more and less than 200°C is 10% by mass or more and 50% by mass or less, based on the total mass of the adhesive paste.

5. The adhesive paste according to any one of claims 1 to 4, wherein the solvent (S) contains an organic solvent (SH) having a boiling point of 254°C or higher and 300°C or lower.

6. The adhesive paste according to any one of claims 1 to 5, wherein the thermosetting organopolysiloxane compound (A) is a polysilsesquioxane compound.

7. The adhesive paste according to any one of claims 1 to 6, further comprising the following component (B): Component (B): Silane coupling agent

8. The adhesive paste according to any one of claims 1 to 7, further comprising the following component (C): (C) Component: Fine particles

9. 9. The adhesive paste according to claim 1, which is substantially free of a noble metal catalyst.

10. A method for manufacturing a semiconductor device using the adhesive paste according to any one of claims 1 to 9 as an adhesive for a semiconductor element fixing material, the method comprising the following steps (BI) and (BII): Step (BI): A step of applying the adhesive paste to the adhesive surface of one or both of the semiconductor element and the supporting substrate and pressing them together. Step (BII): A step of heating and hardening the adhesive paste of the pressure-bonded product obtained in step (BI) to fix the semiconductor element to the support substrate.

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