TW202244235A - Adhesive paste, method for using adhesive paste, and method for manufacturing semiconductor device - Google Patents

Abstract

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

Description

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

The present invention relates to a semiconductor element that can be mounted well even after it is coated on an object to be coated and left for a long time, and the obtained cured product has excellent properties under either high-temperature heating or low-temperature heating conditions. Adhesive adhesive paste; a method of using the adhesive paste as an adhesive for semiconductor element fixing materials; and a method of manufacturing a semiconductor device using the adhesive paste as an adhesive for semiconductor element fixing materials.

Conventionally, adhesive pastes have been variously improved according to their uses, and are widely used industrially as raw materials for optical components, molded articles, etc., adhesives, coating agents, and the like. Furthermore, such adhesive pastes continue to attract attention as pastes for semiconductor element fixing materials such as adhesives for semiconductor element fixing materials.

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

Adhesive paste for semiconductor elements used for fixing semiconductor elements is usually applied to substrates such as lead frames using a coating device having a discharge pipe (needle) as described in Patent Document 1. 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 a predetermined amount of bonding paste is discharged from its front end, the discharge pipe rises to leave the object to be coated and is simultaneously coated. The coating moves laterally. Then, by repeating this operation, the adhesive paste for semiconductor elements is continuously coated on the object to be coated. Thereafter, the semiconductor element is mounted (mounted) on the applied adhesive paste and adhered to the object to be applied.

Usually, after the adhesive paste is applied to the object to be coated, the semiconductor element is quickly mounted on the applied adhesive paste and adhered to the object to be applied. However, in a production line or the like, the applied adhesive paste may be left as it is for a long time without mounting a semiconductor element for some reason. In this case, if the applied adhesive paste is left for a long time, the viscosity of the adhesive paste may change, and the semiconductor element may not be mounted in a good state.

In addition, in recent years, optical semiconductor elements such as blue light and white light having shorter peak wavelengths of light emission have been developed and widely used. Such an optical semiconductor element having a relatively short peak wavelength of light emission has been rapidly increased in brightness, and the amount of heat generated by the optical semiconductor element tends to further increase along with this. However, with the high brightness of optical semiconductor elements in recent years, the adhesive paste used for fixing optical elements is exposed to higher energy light and higher temperature heat energy generated from semiconductor elements for a long time, which may cause Problems such as reduction of adhesive force, deterioration and peeling.

Therefore, there is a need for an adhesive paste that can satisfactorily mount a semiconductor element on an adhesive paste even after it has been applied to an object to be coated and left to stand for a long time, and that the cured product obtained by heating at a high temperature has excellent adhesiveness.

On the other hand, optical components used for semiconductor elements, sensor wafers, and the like are easily affected by heat. Therefore, when the heat curing method is used as a method of curing the adhesive, it is preferable to cure the adhesive at as low a temperature as possible from the viewpoint of avoiding the influence of heating on the optical components and the sensor wafer.

Therefore, in order to be able to precisely adjust the temperature range of the cured product obtained by heating the adhesive paste, not only the cured product obtained by heating at a high temperature is required to be excellent in adhesiveness, but also the cured product obtained by heating at a low temperature is required to be excellent in adhesiveness. . [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2002-009232

[Problem to be solved by the invention]

The present invention is accomplished in view of this situation, and its purpose is to: (i) To provide an adhesive paste that can mount semiconductor elements well (excellent wafer mountability) even after it is applied on the object to be coated and left for a long time, and the cured product obtained by heating at a high temperature has excellent adhesiveness ; and (iii) To provide a method of using the adhesive paste as an adhesive for a semiconductor element fixing material, and a method of manufacturing a semiconductor device using the adhesive paste as an adhesive for a semiconductor element fixing material. Also, in the present invention, "heating at high temperature (hereinafter sometimes referred to as "heating at high temperature")" means "heating at 150°C to 190°C", and "heating at low temperature (hereinafter sometimes referred to as "heating at high temperature")" means "heating at 150°C to 190°C". Heating at low temperature ")" means "heating at 80°C to 120°C". Furthermore, "excellent adhesiveness" means "high adhesive strength". [means used to solve a problem]

In order to solve the above problems, the inventors of this case have carried out intensive research. As a result, it was found that an adhesive paste containing a specific amount of a liquid component having a thermosetting organopolysiloxane compound and a silane-based compound with a specific viscosity, even after 20 minutes or more after applying it to the object to be coated, , the semiconductor element can still be mounted well, and the adhesiveness of the cured product obtained under any of the temperature conditions of high-temperature heating and low-temperature heating is excellent, and the present invention has been completed.

Therefore, according to the present invention, the following adhesive pastes of [1] to [12], the method of using the adhesive paste of [13], and the method of manufacturing a semiconductor device using the adhesive paste of [14] are provided.

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

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

[7] The adhesive paste as described in [1] or [2], further comprising the following (B) component: (B) component: fine particles. [8] The adhesive paste according to [1] or [2], wherein the solid content concentration is 50% by mass or more and 90% by mass or less. [9] The adhesive paste according to [1] or [2], wherein after heating the adhesive paste at 170°C for 2 hours, the mass loss rate of the adhesive paste before and after heating is less than 55% at _170°C for 2 hours. [10] The bonding paste as described in [1] or [2], wherein, when the bonding paste is heated at 170°C for 2 hours, the mass loss rate of the above-mentioned bonding paste before and after heating is set at a mass loss rate of _{170°C for 2 hours} , and after heating the above-mentioned adhesive paste at 100°C for 2 hours, when the mass loss rate of the above-mentioned adhesive paste before and after heating is set as the mass loss rate of _{100°C for 2h} , the mass loss rate of _{170°C for 2h} - the mass loss rate of _{100°C for 2h} is less than 14%. [11] The adhesive paste according to [1] or [2], which substantially does not contain a noble metal catalyst. [12] The adhesive paste according to [1] or [2], which is an adhesive for semiconductor element fixing materials.

[13] A method of using the adhesive paste according to any one of [1] to [12] as an adhesive for a semiconductor element fixing material. [14] A method of manufacturing a semiconductor device, which is a method of manufacturing a semiconductor device using the adhesive paste described in any one of [1] to [12] as an adhesive for fixing a semiconductor element, comprising the following steps (B1 ) and steps (BII): Step (BI): a step of applying the above-mentioned bonding paste on the bonding surface of one or both of the semiconductor element and the supporting substrate and bonding under pressure; Step (BII): a step of heating and curing the above-mentioned adhesive paste of the pressure bonding body obtained in the step (BI), and fixing the above-mentioned semiconductor element on the above-mentioned support substrate. [Efficacy of the invention]

According to the present invention, it is possible to provide an adhesive paste that achieves both wafer mountability, which enables semiconductor elements to be satisfactorily mounted even after being applied to an object to be coated and left for a long time, and adhesiveness of a cured product obtained by heating at a high temperature. Furthermore, according to the present invention, it is possible to provide an adhesive paste having an excellent balance between wafer mountability and adhesiveness of a cured product obtained under either temperature conditions of high-temperature heating or low-temperature heating. Furthermore, according to the present invention, there can be provided a method of using the adhesive paste as an adhesive for a semiconductor element fixing material; and a method of manufacturing a semiconductor device using the adhesive paste as an adhesive for a semiconductor element fixing material.

[Mode for Carrying Out the Invention]

Hereinafter, the present invention will be described in detail by dividing the present invention into 1) an adhesive paste, 2) a method of using the adhesive paste, and a method of manufacturing a semiconductor device using the adhesive paste.

1) Paste The adhesive paste of the present invention is an adhesive paste containing a thermosetting organopolysiloxane compound (A) and a liquid component (L) satisfying the following requirements 1 and 2, wherein the content of the liquid component (L) is relatively When the total mass of the adhesive paste is more than 15% by mass, and the tack free time of the adhesive paste is more than 20 minutes: [requirement 1] The viscosity at 25°C is below 20,000 mPa·s; [Requirement 2] It is a silane compound.

In addition, in the present invention, the term "adhesive paste" means "a viscous liquid at room temperature (23° C.) and a fluid state". Since the adhesive paste of this invention has the characteristic of the said state, it is excellent in processability in a coating process. Here, "excellent processability in the coating step" means "in the coating step, when the adhesive paste is discharged from the discharge pipe, and then the discharge pipe is pulled up, the amount of threading is small or interrupted immediately without occurrence of Splashing of resin or contaminating the surrounding area due to spread of liquid droplets after coating.”

The tack-free time of the adhesive paste of the present invention is at least 20 minutes, preferably at least 30 minutes, more preferably at least 50 minutes, and most preferably at least 70 minutes. Since the tack-free time is 20 minutes or more, the adhesive paste is excellent in die mountability. The tack-free time can be measured by the method described in the examples.

[Thermosetting organopolysiloxane compound (A)] The adhesive paste of the present invention contains a thermosetting organopolysiloxane compound (A) (hereinafter sometimes referred to as "component (A)"). Since the adhesive paste of the present invention contains the component (A), a cured product excellent in adhesiveness can be easily obtained even under any temperature conditions of high-temperature heating or low-temperature heating.

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. It is preferable that (A) component is solid at 25 degreeC from a viewpoint of easily obtaining the adhesive paste which can exhibit the performance excellent in adhesiveness easily. Furthermore, since component (A) is a thermosetting compound, it preferably has at least one selected from the group consisting of a functional group capable of condensation reaction by heating and a functional group capable of condensation reaction by hydrolysis. functional group. Such a functional group is preferably at least one selected from the group consisting of a hydroxyl group and an alkoxy group, more preferably a hydroxyl group and an alkoxy group having 1 to 10 carbon atoms. The main chain structure of the thermosetting organopolysiloxane compound (A) is not limited, and may be any of linear, ladder, and cage. For example, the structure represented by the following formula (a-1) can be cited as the linear main chain structure; the structure represented by the following formula (a-2) can be mentioned as the ladder-like main chain structure; Examples of the cage-like main chain structure include structures represented by the following formula (a-3).

[chemical formula 1]

[chemical formula 2]

[chemical formula 3]

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, unsubstituted A substituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group or an alkylsilyl group. A plurality of Rx in the formula (a-1), a plurality of Ry in the formula (a-2), and a plurality of Rz in the formula (a-3) may be the same as or different from each other. However, there is no case where both Rx of the above formula (a-1) are hydrogen atoms.

As the alkyl group of the above-mentioned unsubstituted or substituted alkyl group, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl Alkyl groups having 1 to 10 carbon atoms such as n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl and n-octyl.

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

Examples of the alkenyl group of unsubstituted or substituted alkenyl include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, etc. Alkenyl groups having 2 to 10 carbon atoms.

Examples of substituents for the above-mentioned alkyl, cycloalkyl, and alkenyl groups include halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms; hydroxyl groups; thiol groups; epoxy groups; (glycidoxy); (meth)acryloxy ((meth)acryloyloxy); unsubstituted or substituted aromatic groups such as phenyl, 4-methylphenyl, 4-chlorophenyl, and the like.

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

Examples of substituents for the aryl group include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkyl groups having 1 to 6 carbon atoms such as methyl and ethyl; methoxy, ethoxy Alkoxy groups with carbon atoms of 1 to 6; nitro; cyano; hydroxyl; thiol; epoxy, glycidyloxy; (meth)acryloxy; phenyl, 4- Unsubstituted or substituted aromatic groups such as methylphenyl and 4-chlorophenyl, etc.

Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tritertiary butylsilyl group, a methyldiethylsilyl group, a dimethylsilyl group, Ethyl silyl, methyl silyl, ethyl silyl, etc.

Among them, 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, particularly preferably an unsubstituted or substituted carbon atom group. It is an alkyl group of 1-6.

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

The silane compound to be used can be appropriately selected according to the structure of the target thermosetting organopolysiloxane compound (A). Preferable specific examples include bifunctional silane compounds such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, and diethyldiethoxysilane. ; Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-butyltriethoxysilane, phenyltrimethoxysilane Trifunctional silane compounds such as oxysilane, phenyltriethoxysilane, phenyldiethoxymethoxysilane, etc.; Tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-tertiary butoxysilane, tetra-secondary butoxysilane, methyl Quadrifunctional silane compounds such as oxytriethoxysilane, dimethoxydiethoxysilane, trimethoxyethoxysilane, etc.

The mass average molecular weight (Mw) of the thermosetting organopolysiloxane compound (A) is usually 800 to 30,000; preferably 1,000 to 20,000; more preferably 1,200 to 15,000; most preferably 3,000 Above, below 10,000. By using the thermosetting organopolysiloxane compound (A) whose mass average molecular weight (Mw) is in the said range, it becomes easy to obtain the adhesive paste which can provide the hardened|cured material more excellent in heat resistance and adhesiveness.

The molecular weight distribution (Mw/Mn) of the thermosetting organopolysiloxane compound (A) is not particularly limited, but is usually 1.0 or more and 10.0 or less; preferably 1.1 or more and 6.0 or less. By using the thermosetting organopolysiloxane compound (A) whose molecular weight distribution (Mw/Mn) is in the said range, the adhesive paste which can provide the hardened|cured material more excellent in heat resistance and adhesiveness can be obtained easily. The mass average molecular weight (Mw) and number average molecular weight (Mn) of the thermosetting organopolysiloxane compound (A) can be determined by, for example, Gel Permeation Chromatography (Gel Permeation Chromatography) using tetrahydrofuran (THF) as a solvent. , GPC) and converted into standard polystyrene conversion value to obtain.

The thermosetting organopolysiloxane compound (A) of the present invention is preferably a polysilsesquioxane compound formed by polycondensation of a trifunctional organosilane compound. Since the adhesive paste of the present invention contains a polysilsesquioxane compound as the component (A), a cured product with better adhesiveness can be easily obtained even under any temperature conditions of high-temperature heating or low-temperature heating.

The polysilsesquioxane compound of the present invention is a compound having a repeating unit represented by the following formula (a-4). Since the adhesive paste of the present invention contains a polysilsesquioxane compound having a repeating unit represented by the following formula (a-4) as component (A), even under any temperature conditions of high-temperature heating and low-temperature heating Both can easily obtain a cured product with better adhesion.

[chemical formula 4]

In formula (a-4), R ¹ represents an organic group. The organic group is selected from unsubstituted alkyl, substituted alkyl, unsubstituted cycloalkyl, substituted cycloalkyl, unsubstituted alkenyl, substituted alkenyl, unsubstituted Substituted aryl groups, aryl groups with substituents, and alkylsilyl groups are preferred; groups selected from unsubstituted alkyl groups with 1 to 10 carbon atoms, carbon with substituents A group consisting of an alkyl group with 1 to 10 atoms, an unsubstituted aryl group with 6 to 12 carbon atoms, and an aryl group with a substituent with 6 to 12 carbon atoms is more preferred .

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

The number of carbon atoms in the "alkyl group having 1 to 10 carbon atoms having a substituent" represented by R1 is preferably ¹ to 6, more preferably 1 to 3. In addition, this number of carbon atoms refers to the number of carbon atoms of the part (part of the alkyl group) except the substituent. Therefore, when R ¹ is "an alkyl group having 1 to 10 carbon atoms having a substituent", the number of carbon atoms in R ¹ may exceed 10. Examples of the "alkyl group having a substituent having 1 to 10 carbon atoms" include the same ones as those exemplified for the "unsubstituted alkyl group having 1 to 10 carbon atoms".

Examples of the substituent of the "alkyl group having 1 to 10 carbon atoms having substituents" include halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms; cyano groups; groups represented by the formula: OG, and the like. The number of atoms (however, excluding the number of hydrogen atoms) of the substituent of the "alkyl group having 1-10 carbon atoms having a substituent" is usually 1-30, preferably 1-20. Here, G represents a protecting group for a hydroxyl group. The protecting group for the hydroxy group is not particularly limited, and known protecting groups for the hydroxy group are exemplified. For example, acyl series; silane series such as trimethylsilyl, triethylsilyl, tertiary butyldimethylsilyl, tertiary butyldiphenylsilyl, etc.; methoxy Methyl, methoxyethoxymethyl, 1-ethoxyethyl, tetrahydropyran-2-yl, tetrahydrofuran-2-yl, etc. Acetal series; alkoxycarbonyl series such as tertiary butoxycarbonyl; methyl, ethyl, tertiary butyl, octyl, allyl, triphenylmethyl, benzyl, p-methoxy Ether systems such as benzyl, fluorenyl, trityl, benzhydryl, etc.

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

The number of carbon atoms in the "aromatic group having a substituent and having 6 to 12 carbon atoms" represented by R1 is preferably ⁶ . In addition, this number of carbon atoms refers to the number of carbon atoms of the part (part of the aromatic group) except the substituent. Therefore, when R ¹ is "an aromatic group having 6 to 12 carbon atoms having a substituent", the number of carbon atoms in R ¹ may exceed 12. Examples of the "aryl group having a substituent having 6 to 12 carbon atoms" include the same ones as those exemplified as "unsubstituted aryl group having 6 to 12 carbon atoms".

As the substituent of "an aromatic group having 6 to 12 carbon atoms having a substituent", methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, Alkyl groups such as tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, etc.; halogen atoms such as fluorine atom, chlorine atom, bromine atom, etc.; methoxyl group, ethoxyl group, etc. alkoxyl; etc. The number of atoms (however, excluding the number of hydrogen atoms) of the substituent of the "aryl group having 6 to 12 carbon atoms having a substituent" is usually 1-30, preferably 1-20.

Among them, R ¹ is preferably selected from unsubstituted polysilsesquioxane compounds having 1 to 10 carbon atoms from the viewpoint of easily obtaining a polysilsesquioxane compound with a stable structure and more stable performance as an adhesive paste. At least one selected from the group consisting of an alkyl group, an alkyl group having 1 to 10 carbon atoms having a fluorine atom, and an unsubstituted aromatic group having 6 to 12 carbon atoms. By using a polysilsesquioxane compound in which R ¹ is an unsubstituted alkyl group having 1 to 10 carbon atoms, it is easy to obtain an adhesive paste that can provide a cured product that is more excellent in heat resistance and adhesiveness. By using a polysilsesquioxane compound in which R1 is an alkyl group having a fluorine atom and a carbon number of ¹ to 10, it is easy to obtain an adhesive paste, a cured product, etc. with a long time for tack removal and a low refractive index. Suitable for optical semiconductor elements that need to have a low refractive index. As an alkyl group having 1 to 10 carbon atoms having a fluorine atom, the composition formula: C _m H _(2m-n+1) F _n (m is an integer of 1 to 10; n is 1 or more, (2m A group represented by an integer below +1). Among them, 3,3,3-trifluoropropyl is preferred. By using a polysilsesquioxane compound with R1 being ^an unsubstituted aromatic group with 6 to 12 carbon atoms, it is easy to obtain adhesive pastes and cured products with high refractive index, so it is easy to apply to applications requiring high refractive index. High-efficiency optical semiconductor components.

The content ratio of the repeating unit represented by the above formula (a-4) in the polysilsesquioxane compound (that is, the T site (site) described later) is usually 50 to 100 with respect to all the repeating units. mol%, 70-100 mol% is more preferable, 90-100 mol% is still more preferable, and 100 mol% is especially preferable. By using a polysilsesquioxane compound having the repeating unit (T site) represented by the above formula (a-4) in the above-mentioned ratio, it is possible to obtain properties that can easily exhibit heat resistance, adhesiveness, and refractive index The follow-up ointment. If, for example, assignment of NMR peaks and integration of areas are possible, the content ratio of the repeating unit (T site) represented by the above formula (a-4) in the polysilsesquioxane compound can be determined by Obtained by measuring ²⁹ Si-NMR and ¹ H-NMR.

Polysilsesquioxane compounds can be dissolved in ketone-based solvents such as acetone; aromatic hydrocarbon-based solvents such as benzene; sulfur-containing solvents such as dimethylsulfone; ether-based solvents such as tetrahydrofuran; Various organic solvents such as ester solvents; halogen-containing solvents such as chloroform; and mixed solvents of two or more of the above solvents. Therefore, using these solvents, it is possible to measure ²⁹ Si-NMR in a solution state of the polysilsesquioxane compound.

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

[chemical formula 5]

As shown in the formula (a-5), the polysilsesquioxane compound has three oxygen atoms bonded to a silicon atom generally collectively referred to as a T site, and one other bonded to this silicon atom Partial structure of group (R ¹ ).

In the formula (a-5), R ¹ represents the same meaning as R ¹ in the above formula (a-4). * 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 in * include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, secondary butyl group, isobutyl group, tertiary butyl group and the like. Plural * may mutually be same, and may mutually differ.

Furthermore, the polysilsesquioxane compound is a thermosetting compound, and is a compound capable of undergoing a condensation reaction by heating and/or a condensation reaction by hydrolysis. Therefore, at least one of the * in the above-mentioned formula (a-5) of the multiple repeating units (T sites) of the polysilsesquioxane compound has a hydrogen atom or a carbon atom number of 1 to 10 An alkyl group is preferred, and a hydrogen atom is more preferred. Also, when the polysilsesquioxane compound is soluble in the solvent for measurement, the presence or absence of a hydrogen atom or an alkyl group having 1 to 10 carbon atoms in * in the above formula (a-5), Whether all three * in the above formula (a-5) are repeating units of Si atoms can be confirmed by measuring ²⁹ Si-NMR. In addition, if the assignment of the peak of ²⁹ Si-NMR and the integral of the area are possible, it can be estimated that the repeating unit represented by the above formula (a-4) in the polysilsesquioxane compound (T site ), all of the three * in the above formula (a-5) are the total number of repeating units of Si atoms. In the above formula (a-5), the total number of repeating units in which 3 * are all Si atoms is relative to the repeating unit represented by the above formula (a-4) in this polysilsesquioxane compound (T position The total number of dots) is more preferably 30 to 95 mol%, more preferably 40 to 90 mol%, from the viewpoint of easily obtaining an adhesive paste that can provide a cured product with better heat resistance.

The polysilsesquioxane compound may have one type of R ¹ (homopolymer) or may have two or more types of R ¹ (copolymer).

When the polysilsesquioxane compound is a copolymer, the polysilsesquioxane compound may be any of random copolymers, block copolymers, graft copolymers, alternating copolymers, etc., but in terms of ease of manufacture, etc. Considering the point of view, the random copolymer is preferable. Furthermore, the structure of the polysilsesquioxane compound may be any one of ladder structure, double decker structure, cage structure, partially split cage structure, ring structure, and random structure.

In the present invention, the polysilsesquioxane compound may be used alone or in combination of two or more.

The method for producing the polysilsesquioxane compound is not particularly limited. For example, polysilsesquioxane compounds can be produced by polycondensing at least one of silane compounds (1) represented by the following formula (a-6).

[chemical formula 6]

(In the formula, R ¹ represents the same meaning as R ¹ in the above formula (a-4). R ² represents an alkyl group with 1 to 10 carbon atoms, X ¹ represents a halogen atom, and p represents an integer of 0 to 3 A plurality of R ² may be the same as or different from each other, and a plurality of X ¹ may be the same as or different from each other.) The alkyl group having 1 to 10 carbon atoms as R ² may be listed as the above-mentioned formula In (a-5), the same as those exemplified for the alkyl group having 1 to 10 carbon atoms of *. Examples of the halogen atom for X1 include ^a chlorine atom, a bromine atom, and the like.

Specific examples of the silane compound (1) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, etc. Alkyltrialkoxysilane compounds; Methylchlorodimethoxysilane, Methylchlorodiethoxysilane, Methyldichloromethoxysilane, Methylbromodimethoxysilane, Ethylchlorodimethoxysilane, Ethylchlorodiethylsilane Alkyl halogenoalkoxysilane compounds such as oxysilane, ethyldichloromethoxysilane, ethylbromodimethoxysilane, etc.; Alkyl trihalogenosilane compounds such as methyl trichlorosilane, methyl tribromosilane, ethyl trichlorosilane, ethyl tribromosilane, etc.;

3,3,3-Trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 2-cyanoethyltrimethoxysilane, 2-cyanoethyltriethyl Substituted alkyltrialkoxysilane compounds such as oxysilane; 3,3,3-trifluoropropylchlorodimethoxysilane, 3,3,3-trifluoropropylchlorodiethoxysilane, 3,3,3-trifluoropropyldichloromethoxysilane , 3,3,3-trifluoropropyldichloroethoxysilane, 2-cyanoethylchlorodimethoxysilane, 2-cyanoethylchlorodiethoxysilane, 2-cyanoethyl Substituted alkylhalogenated alkoxysilane compounds such as dichloromethoxysilane and 2-cyanoethyldichloroethoxysilane; Substituted alkyl trihalide silane compounds such as 3,3,3-trifluoropropyltrichlorosilane and 2-cyanoethyltrichlorosilane;

Substituent or unsubstituted phenyltrialkoxysilane compounds such as phenyltrimethoxysilane and 4-methoxyphenyltrimethoxysilane; Substituents of phenylchlorodimethoxysilane, phenyldichloromethoxysilane, 4-methoxyphenylchlorodimethoxysilane, 4-methoxyphenyldichloromethoxysilane, etc. Phenylhaloalkoxysilane compounds with or without substituents; Substituent or unsubstituted phenyltrihalogenosilane compounds such as phenyltrichlorosilane and 4-methoxyphenyltrichlorosilane, etc. These silane compounds (1) may be used alone or in combination of two or more.

The method of polycondensing the above-mentioned silane compound (1) is not particularly limited. For example, there may be mentioned a method of adding a predetermined amount of a polycondensation catalyst to the silane compound (1) in a solvent or in a solvent-free state, and stirring at a predetermined temperature. More specifically, the following methods can be mentioned: (a) adding a predetermined amount of acid catalyst to the silane compound (1), and stirring at a predetermined temperature; (b) adding a predetermined amount of base catalyst to In the silane compound (1), the method of stirring at a predetermined temperature; (c) adding a predetermined amount of acid catalyst to the silane compound (1), and stirring at a predetermined temperature, adding an excessive amount of base catalyst, A method of making the reaction system alkaline and stirring at a predetermined temperature, etc. Among them, method (a) or method (c) is preferable because the target polysilsesquioxane compound can be obtained efficiently.

The polycondensation catalyst used may be either an acid catalyst or a base catalyst. In addition, although two or more types of polycondensation catalysts may be used in combination, it is preferable 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 nitrate; citric acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid. and other organic acids. Among them, at least one selected from phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, citric acid, acetic acid and methanesulfonic acid is preferred.

As the base catalyst, ammonia water; trimethylamine, triethylamine, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, pyridine, 1,8- Diazinebicyclo[5.4.0]undecene-7-ene (1,8-diazabicyclo[5.4.0]-7-undecene), aniline, picoline, 1,4-diazabicyclo[2.2.2 ] octane (1,4-diazabicyclo [2.2.2] octane), organic bases such as imidazole; organic salt hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; sodium methoxide, ethoxylate Metal alkoxides of sodium, tertiary butoxysodium, tertiary butoxypotassium, etc.; metal hydrides of sodium hydride, calcium hydride, etc.; sodium hydroxide, potassium hydroxide, calcium hydroxide, etc. Metal hydroxides; metal carbonates of sodium carbonate, potassium carbonate, magnesium carbonate, etc.; metal bicarbonates of sodium bicarbonate, potassium bicarbonate, etc.

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

When using a solvent at the time of polycondensation, the solvent to be used can be selected suitably according to the kind etc. of a silane compound (1). Examples include water; aromatic hydrocarbons such as benzene, toluene, and xylene; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; acetone, methyl ethyl Ketones such as ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, and tertiary butanol Wait. These solvents may be used alone or in combination of two or more. Furthermore, when adopting the method of above-mentioned (c), it is also possible to carry out the polycondensation reaction in the water system in the presence of an acid catalyst, and then add an organic solvent and an alkali catalyst (ammonia, etc.) to the reaction solution, under neutral conditions or Further polycondensation reaction was carried out under alkaline conditions.

The amount of the solvent used is usually not less than 0.001 liter and not more than 10 liters, preferably not less than 0.01 liter and not more than 0.9 liter, per mol of the total mole (mol) of the silane compound (1).

The temperature for polycondensation of the silane compound (1) is usually in the temperature range from 0°C to the boiling point of the solvent used, preferably in the range of 20°C to 100°C; more preferably 30°C to 95°C range. 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 will be difficult to suppress gelation. The reaction is usually complete within 30 minutes to 30 hours.

Also, depending on the type of monomer used, it may be difficult to increase the molecular weight. For example, when R ¹ is an alkyl monomer having a fluorine atom, the reactivity tends to be lower than when R ¹ is a general alkyl monomer. In this case, by reducing the amount of the catalyst and performing the reaction under mild conditions for a long time, it becomes easy to obtain a polysilsesquioxane compound having a target molecular weight.

After the reaction is completed, if an acid catalyst is used, an alkaline aqueous solution such as sodium bicarbonate is added to the reaction solution, and if an alkali catalyst is used, an acid such as hydrochloric acid is added to the reaction solution to neutralize , The salt generated at this time is removed by filtration, washing with water, etc., to obtain the target polysilsesquioxane compound.

When the polysilsesquioxane compound is produced by the above method, the portion of OR ² or X ¹ of the silane compound (1) that has not undergone hydrolysis and subsequent condensation reaction, etc. remains in the polysilsesquioxane compound middle.

When component (A) is, for example, a polysilsesquioxane compound obtained by polycondensation reaction of silane compound (1), since curing is carried out by condensation reaction, the adhesive paste of the present invention is different from A general heat-curable silicone adhesive that undergoes an addition reaction and cures 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 does not substantially contain the noble metal catalyst, or the content of the noble metal catalyst is very small. Here, the term "substantially does not contain a precious metal catalyst, or the content of a precious metal catalyst is very small" means "except that there is no deliberate addition of components that can be interpreted as a precious metal catalyst, and relative to the amount of active ingredients in the adhesive paste , the content of the noble metal catalyst in terms of the mass of the catalyst metal element is, for example, less than 1 mass ppm". In addition, here, "active ingredient" means "components other than the solvent (S) (described later) contained in an adhesive paste." From the viewpoints of stable production, storage stability, and precious metal catalysts that are expensive in consideration of blending deviations, it is more important that the paste does not substantially contain the precious metal catalyst, or that the content of the precious metal catalyst is very small. good.

[Liquid Component (L)] The liquid component (L) (hereinafter sometimes referred to as "component (L)") constituting the adhesive paste of the present invention satisfies the following requirements 1 and 2. [requirement 1] The viscosity at 25°C is 20,000 mPa・s or less. [Requirement 2] It is a silane compound. Since it is a silane compound, the liquid component (L) is easy to mix well with the component (A), and an adhesive paste with stable performance can be easily obtained. Examples of the liquid component (L) that satisfies the above requirements 1 and 2 include bifunctional silane compounds, trifunctional silane compounds, and silicone oils.

The viscosity of the liquid component (L) at 25°C is 20,000 mPa·s or less, preferably 10,000 mPa·s or less, more preferably 7,000 mPa·s or less, most preferably 5,000 mPa·s or less. Since the adhesive paste containing the liquid component (L) whose viscosity at 25°C is below the above upper limit is less likely to volatilize at room temperature (20°C±15°C), it is possible to easily obtain an adhesive paste with a longer tack-free time . On the other hand, since the viscosity of the adhesive paste containing the liquid component (L) whose viscosity at 25°C is higher than the upper limit value becomes higher, there is a risk of shortening the tack-free time of the adhesive paste. However, by making it Below the above upper limit, the risk can be reduced. Furthermore, by containing the liquid component (L) whose viscosity at 25° C. is not more than the above-mentioned upper limit, it is easy to obtain excellent workability in the coating step, and it is possible to provide Adhesive paste for cured products with excellent adhesiveness under conditions, heat resistance, and crack suppression of cured products. Here, "the cured product is more excellent in crack suppression" means "when the cured product is obtained by heating the adhesive paste, the cured product does not crack due to temperature change".

Examples of bifunctional silane compounds include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dimethoxydimethoxysilane, and dimethoxysilane. Phenylsilane, Diethoxydiphenylsilane, Dimethoxymethylphenylsilane, Diethoxymethylphenylsilane, 3-Glycidoxypropylmethyldimethoxysilane, 3-Glycidoxypropylmethyldiethoxysilane, 3-Methacryloxypropylmethyldimethoxysilane, 3-Methacryloxypropylmethyldiethoxysilane Silane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, etc.

A commercial item can also be used as a bifunctional silane compound. Commercially available products include KBM series such as KBM-22, KBM-202SS, and KBM-402, and KBE series such as KBE-22, KBE-402, and KBE-502 (all of which are manufactured by Shin-Etsu Chemical Co., Ltd.). Among them, KBM-202SS is preferably used from the viewpoint of being easy to mix well with other active ingredients and easily obtaining an adhesive paste with stable performance.

As a trifunctional silane compound, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethylsilane Oxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, benzene phenyltrimethoxysilane, phenyltriethoxysilane, phenyldiethoxymethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxy Hexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methoxysilane Acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl )-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1, 3-Dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 2-trimethoxysilylethylbutyl Diic anhydride, 2-triethoxysilylethyl succinic anhydride, 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-mercaptopropyltrimethyl Oxysilane etc.

A commercial item can also be used as a trifunctional silane type compound. Examples of commercially available products include KBM series such as KBM-103, KBM-303, KBM-503, KBM-5103, KBE series such as KBE-13, KBE-103, KBE-9007N, X-12- 967C and the like (all of the above are manufactured by Shin-Etsu Chemical Co., Ltd.). Among them, it is preferable to use X-12-967C, KBM-103, KBM-503, KBM-5103, KBE-9007N, particularly It is better to use X-12-967C, KBM-5103, KBE-9007N.

Examples of polyfunctional silane compounds include compounds having a nitrogen atom in the molecule and four or more alkoxy groups bonded to silicon atoms in the molecule; and compounds whose main chain is an organic structure and has an organic functional group and four or more bonds. Alkoxy compounds bonded to silicon atoms, etc. The term having 4 or more alkoxy groups bonded to silicon atoms means that the total number of alkoxy groups bonded to the same silicon atom and alkoxy groups bonded to different silicon atoms is 4 or more.

Examples of the polyfunctional silane compound having a nitrogen atom in the molecule and four or more alkoxy groups bonded to silicon atoms in the molecule include isocyanurate compounds, urea compounds, and the like.

Examples of the isocyanurate-based compound include compounds represented by the following formula (1-1), and examples of the urea-based compound include compounds represented by the following formula (1-2).

[chemical formula 7]

In the formula, R ^a represents an alkoxy group having 1 to 6 carbon atoms such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and the like. A plurality of R ^a may be the same as or different from each other. t1 to t5 each independently represent an integer of 1 to 10, preferably an integer of 1 to 6, particularly preferably 3.

Specific examples of the compound represented by the formula (1-1) include 1,3,5-N-para(3-trimethoxysilylpropyl)isocyanurate, 1,3,5- N-ginseng (3-triethoxysilylpropyl) isocyanurate, 1,3,5-N-ginseng (3-triisopropoxysilylpropyl) isocyanurate, 1 , 3,5-N-paraffin (3-tributoxysilylpropyl) isocyanurate and other 1,3,5-N-paraffin [(three (1 to 6 carbon atoms) alkyl Oxy)silyl (with 1 to 10 carbon atoms) alkyl] isocyanurate; 1,3,5-N-paraffin (3-dimethoxymethylsilylpropyl) isocyanurate, 1,3,5-N-paraffin (3-dimethoxyethylsilylpropyl) ) isocyanurate, 1,3,5-N-paraffin (3-dimethoxyisopropylsilylpropyl) isocyanurate, 1,3,5-N-paraffin (3-two Methoxy-n-propylsilylpropyl) isocyanurate, 1,3,5-N-paraffin (3-dimethoxyphenylsilylpropyl) isocyanurate, 1,3, 5-N-paraffin (3-diethoxymethylsilylpropyl) isocyanurate, 1,3,5-N-paraffin (3-diethoxyethylsilylpropyl) isocyanurate Urate, 1,3,5-N-paraffin (3-diethoxyisopropylsilylpropyl) isocyanurate, 1,3,5-N-paraffin (3-diethoxy n-Propylsilylpropyl) isocyanurate, 1,3,5-N-paraffin (3-diethoxyphenylsilylpropyl) isocyanurate, 1,3,5-N - ginseng (3-diisopropoxymethylsilylpropyl) isocyanurate, 1,3,5-N-ginseng (3-diisopropoxyethylsilylpropyl) isocyanurate ester, 1,3,5-N-paraffin (3-diisopropoxyisopropylsilylpropyl) isocyanurate, 1,3,5-N-paraffin (3-diisopropoxy N-propylsilylpropyl) isocyanurate, 1,3,5-N-paraffin (3-diisopropoxyphenylsilylpropyl) isocyanurate, 1,3,5 -N-ginseng (3-dibutoxymethylsilylpropyl) isocyanurate, 1,3,5-N-ginseng (3-dibutoxyethylsilylpropyl) isocyanurate ester, 1,3,5-N-paraffin (3-dibutoxyisopropylsilylpropyl) isocyanurate, 1,3,5-N-paraffin (3-dibutoxy Propylsilylpropyl) isocyanurate, 1,3,5-N-paraffin (3-dibutoxyphenylsilylpropyl) isocyanurate and other 1,3,5-N - Refer to [(di(1-6 carbon atoms) alkoxy)silyl (1-10 carbon atoms) alkyl]isocyanurate, etc.

Specific examples of the compound represented by the formula (1-2) include N,N'-bis(3-trimethoxysilylpropyl)urea, N,N'-bis(3-triethoxy silylpropyl)urea, N,N'-bis(3-tripropoxysilylpropyl)urea, N,N'-bis(3-tributoxysilylpropyl)urea, N,N N,N'-bis[(tri(1-6 carbon atoms)alkoxysilyl) (1-10 carbon atoms) such as '-bis(2-trimethoxysilylethyl)urea of) alkyl]urea; N,N'-bis(3-dimethoxymethylsilylpropyl)urea, N,N'-bis(3-dimethoxyethylsilylpropyl)urea, N,N'-bis N,N'-bis[(di(1-6 carbon atoms)alkoxy(1-6 carbon atoms)alkane, such as (3-diethoxymethylsilylpropyl)urea Silyl group (alkyl) urea with 1 to 10 carbon atoms; N,N'-bis(3-dimethoxyphenylsilylpropyl)urea, N,N'-bis(3-diethoxyphenylsilylpropyl)urea, etc. Bis[(two (1-6 carbon atoms) alkoxy (6-20 carbon atoms) arylsilyl (1-10 carbon atoms) alkyl) urea, etc.

Commercially available compounds can also be used as compounds having a nitrogen atom in the molecule and four or more alkoxy groups bonded to silicon atoms in the molecule. As a commercial item, for example, KBM-9659 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be cited. Among them, KBM-9659 is preferably used from the viewpoint of being easy to mix well with other active ingredients and easily obtaining an adhesive paste with stable performance.

A commercially available compound can also be used as a compound whose main chain has an organic structure and has an organic functional group and four or more alkoxy groups bonded to silicon atoms. Examples of commercially available products include X-12-1048, X-12-981S, X-12-1159L and the like (all of which are manufactured by Shin-Etsu Chemical Co., Ltd.). Among them, X-12-1159L is preferably used from the viewpoint of being easy to mix well with other active ingredients and easily obtaining an adhesive paste with stable performance.

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

Modified silicone oil has organic groups introduced into polysiloxane side chains, terminals, etc. According to the bonding position of the introduced organic group, the modified silicone oil can be classified into side chain type, double-end type, single-end type, and side chain double-end type. In addition, according to the nature of the introduced organic group, it can be classified into reaction type Reactive silicone oil and non-reactive silicone oil. As an organic group, an amino group, an epoxy group, a methacryl group, an acryl group, a silanol (silanol) group, a carboxyl group etc. are mentioned.

As the silicone oil, a commercially available item can also be used. Examples of commercially available linear silicone oils include KF-96L series, KF-50 series, and KF-99 series (all of which are manufactured by Shin-Etsu Chemical Co., Ltd.). Commercially available modified silicone oils include, for example, KF series such as KF-868 with monoamine introduced into the side chain, X-22-2445 with acrylic group introduced at both ends, and epoxy group introduced at one end. X-22-173 series such as X-22-173BX, etc. (all of the above are manufactured by Shin-Etsu Chemical Co., Ltd.), XF42-334 (manufactured by Momentive・Performance・Materials・Japan). Among them, from the viewpoint of being easy to mix well with other active ingredients and obtaining an adhesive paste with stable performance, it is preferable to use modified silicone oil, especially X-22-2445 and XF42-334.

Among these liquid components (L), bifunctional silane compounds, trifunctional silane compounds, and silicone oils are more preferable from the viewpoint of easily obtaining an adhesive paste with a longer tack-free time, and bifunctional silane compounds, trifunctional silane compounds, and Silicone oil is particularly preferred, and furthermore, trifunctional silane compounds and silicone oil are particularly preferred from the viewpoint of easily obtaining an adhesive paste having excellent adhesive strength of a cured product obtained by heating at a low temperature. The liquid component (L) may be used alone or in combination of two or more.

The content of the liquid component (L) is at least 15% by mass relative to the total mass of the adhesive paste; preferably at least 17% by mass and less than 50% by mass, more preferably at least 19% by mass and less than 40% by mass; More than 21% by mass and less than 35% by mass are particularly preferred. By making content of the liquid component (L) with respect to the gross mass of an adhesive paste into the said range, the effect of using a liquid component (L) can be exhibited further.

[other ingredients] The adhesive paste of the present invention contains a thermosetting organopolysiloxane compound (A) and a liquid component (L), but may also contain the components shown below. (1) Solvent(S) The solvent (S) contained in the adhesive paste of the present invention is not particularly limited as long as it can dissolve or disperse the components of the adhesive paste of the present invention. The solvent (S) preferably contains an organic solvent (SL) having a boiling point of not less than 100°C and less than 254°C. Here, the "boiling point" means "the boiling point at 1013 hectopascals (hPa)" (it is the same in this specification). The boiling point of the organic solvent (SL) is above 100°C and below 254°C; preferably above 100°C and below 200°C; more preferably above 105°C and below 185°C; above 110°C and below 170°C ℃ is particularly preferred.

When such an organic solvent (SL) is heated at a low temperature, the solvent can be volatilized more efficiently than a high-boiling organic solvent having a boiling point of 254°C to 300°C. Therefore, by containing the organic solvent (SL) as the solvent (S), it is possible to easily obtain an adhesive paste having a mass loss rate of _{170° C. 2 h} - a mass loss rate of _{100° C. 2 h} (described later) of less than 14%. Furthermore, compared with low-boiling organic solvents with a boiling point of less than 100° C., such an organic solvent (SL) has a slower volatilization rate. In this way, when the adhesive paste containing organic solvent (SL) is heated at low temperature, it can be volatilized more efficiently without leaving a large amount of solvent, so it is easy to obtain sufficient adhesive strength. The concentration of active ingredients in the paste rises quickly, so it becomes easy to solidify. Therefore, even after it is applied on an object to be coated and left to stand for a long time, the semiconductor element can be favorably mounted, and the obtained cured product has excellent adhesiveness.

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), and dipropylene glycol monobutyl ether acetate (boiling point 209°C). 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) °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), 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), phenylethyl alcohol (boiling point 219～221°C), ethylene glycol Alcohol 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), cyclic Pentanone (boiling point 130°C), cyclohexanone (boiling point 157°C), cycloheptanone (boiling point 180°C), cyclooctanone (boiling point 195-197°C), cyclohexanol (boiling point 161°C), cyclohexadiene Ketones (boiling point 104-104.5°C), etc. Among them, as the organic solvent (SL), diethylene glycol monoethyl ether acetate and cyclohexanone are preferred from the viewpoint of further exerting the effect of using the organic solvent (SL) and being easy to mix the active ingredients well; Cyclohexanone is more preferred. The organic solvent (SL) may be used alone or in combination of two or more.

The content of the organic solvent (SL) of the adhesive paste of the present invention, relative to the total mass of the adhesive paste, is preferably more than 10% by mass and less than 50% by mass; more preferably more than 13% by mass and less than 40% by mass; More than 15% by mass and less than 30% by mass are particularly preferred. By making the content of the organic solvent (SL) relative to the total mass of the adhesive paste within the above-mentioned range, the processability in the step of filling the syringe with the adhesive paste or the step of coating is excellent, and the use of the organic solvent (SL) can be further utilized. )Effect. Here, "excellent workability in the step of filling the syringe with the adhesive paste" means "can be filled in the syringe in an appropriate amount without air bubbles".

The adhesive paste of the present invention may contain solvents other than the organic solvent (SL). Solvents other than the organic solvent (SL) are preferably organic solvents having a boiling point of 254° C. to 300° C. (hereinafter sometimes referred to as “organic solvent (SH)”). The organic solvent (SH) is not particularly limited as long as it has a boiling point of 254° C. to 300° C. and can dissolve or disperse the components of the adhesive paste of the present invention. By using organic solvent (SL) in combination with solvents other than organic solvent (SL), it is possible to more precisely adjust the temperature range in which the adhesive paste is heated to obtain a cured product, and it is possible to reduce the impact of heating on optical components and sensitive parts that are easily affected by heat. The impact caused by the tester chip, etc.

As the organic solvent (SH), specifically, 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. °C), triethylene glycol butyl methyl ether (boiling point 261 °C), polyethylene glycol dimethyl ether (boiling point 264-294 °C), tetraethylene glycol dimethyl ether (boiling point 275 °C), polyethylene glycol monomethyl ether Ether (boiling point 290-310°C), etc. Among them, as the organic solvent (SH), tripropylene glycol n-butyl ether, 1,6-hexanediol diacrylate better.

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

The organic solvent (SL) preferably accounts for 60% by mass or more of the solvent (S), more preferably 65% by mass or more, particularly preferably 70% by mass or more. By making the organic solvent (SL) of the whole solvent (S) into the said range, the effect of using an organic solvent (SL) can be exhibited further.

The adhesive paste of the present invention preferably contains the solvent (S) in an amount such that the solid content concentration is 50% by mass to 90% by mass; more preferably, the solid content concentration is 70% by mass to 90% by mass. The amount contains solvent (S). When the solid content concentration is within this range, the active ingredients can be easily and well mixed, the processability in the step of filling the adhesive paste into the syringe or the step of coating is excellent, and the effect of using the organic solvent (SL) can be further exhibited. In addition, during die bonding, it is possible to suppress generation of voids between the bonding paste and the substrate to be bonded, thereby improving the reliability of the package.

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

By containing fine particles (B1), it is easy to obtain an adhesive paste that is excellent in processability in the coating process, and can provide a cured product that is more excellent in adhesiveness and heat resistance under either high-temperature heating or low-temperature heating . From the viewpoint of easily obtaining this effect, the average primary particle diameter of the microparticles (B1) is preferably 5 nm or more and 30 nm or less; more preferably 5 nm or more and 20 nm or less. The average primary particle diameter of the fine particle (B1) can be obtained by observing the shape of the fine particle using a transmission electron microscope.

The specific surface area of the microparticles (B1) is preferably not less than 10 m ² /g and not more than 500 m ² /g; more preferably not less than 20 m ² /g and not more than 300 m ² /g. When the specific surface area is within the above range, it is easy to obtain an adhesive paste more excellent in workability in the coating step. The specific surface area can be obtained by the BET multi-point method.

The shape of the microparticles (B1) may be spherical, chain-like, needle-like, plate-like, flake-like, rod-like, or fibrous, but spherical shape is preferred. Here, the term "spherical" means "a substantially spherical shape that can approximate polyhedral shapes such as an ellipsoid, an egg shape, a gold flat sugar shape, and a cocoon shape, in addition to a true spherical shape."

The constituents of the microparticles (B1) are not particularly limited, and include metals; metal oxides; minerals; metal carbonates; metal sulfates; metal hydroxides; metal silicates; inorganic components; organic components; silicone, etc. . Furthermore, the fine particles (B1) used may be those whose surface has been modified.

The so-called metals refer to those belonging to Group 1 (excluding hydrogen (H)), Groups 2 to 11, Group 12 (excluding mercury (Hg)) and Group 13 (excluding boron (Hg)) in the periodic table of elements. B)), group 14 (excluding carbon (C) and silicon (Si)), group 15 (excluding nitrogen (N), phosphorus (P), arsenic (As) and antimony (Sb)) or group 16 Group (excluding oxygen (O), sulfur (S), selenium (Se), tellurium (Te) and polonium (Po)) elements.

Examples of metal oxides include titanium oxide, aluminum oxide, boehmite, chromium oxide, nickel oxide, copper oxide, zirconium oxide, indium oxide, zinc oxide, and composite oxides thereof. Fine particles of metal oxides also include sol particles made of these metal oxides.

Minerals include smectite, bentonite and the like. Examples of smectite include montmorillonite, beidellite, hectorite, saponite, stevensite, nontronite, and sauconite (sauconite) etc.

As the metal carbonate, calcium carbonate, magnesium carbonate, etc. can be listed; as the metal sulfate, calcium sulfate, barium sulfate, etc. can be listed; as the metal hydroxide, aluminum hydroxide can be listed; as the metal silicate, silicon can be listed. Aluminum, Calcium Silicate, Magnesium Silicate, etc. In addition, silicon oxide etc. are mentioned as an inorganic component. Examples of silicon oxide include dry silicon oxide, wet silicon oxide, surface-modified silicon oxide (surface-modified silicon oxide), and the like. An acrylic polymer etc. are mentioned as an organic component.

The so-called silicone refers to an artificial polymer compound having a main skeleton formed by siloxane bonds. For example, dimethylpolysiloxane, diphenylpolysiloxane, methylphenylpolysiloxane, etc. are mentioned.

Fine particles (B1) may be used alone or in combination of two or more. Among them, in the present invention, silicon oxide, metal oxides, and minerals are preferable, and silicon oxide is more preferable from the viewpoint of easily obtaining an adhesive paste excellent in transparency.

Among silicon oxides, surface-modified silicon oxide is preferable from the viewpoint of being relatively easy to mix as an adhesive paste, and that it is easier to obtain an adhesive paste with better workability in the coating step, and hydrophobic one is preferred. Surface modified silicon oxide is more preferable. Examples of hydrophobic surface-modified silicon oxide include trialkylsilyl groups with 1 to 20 carbon atoms such as trimethylsilyl groups bonded to the surface; trialkylsilyl groups with 1 to 20 carbon atoms such as dimethylsilyl groups Silicon oxides of alkylsilyl groups with 1 to 20 carbon atoms such as alkylsilyl groups of ~20, octylsilyl groups, etc.; silicon oxides whose surface is treated with silicone oil; etc. Hydrophobic surface-modified silicon oxide can be obtained by, for example, using a trialkylsilyl group with three carbon atoms of 1 to 20; an alkylsilyl group with two carbon atoms of 1 to 20; It is obtained by modifying the surface of silicon oxide particles with a silane coupling agent such as an alkylsilyl group of ~20, or by treating silicon oxide particles with silicone oil.

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

By containing fine particles (B2), it is easy to obtain an adhesive paste that is excellent in processability in the coating process, and can provide a cured product that is more excellent in adhesiveness and heat resistance under either high-temperature heating or low-temperature heating . From the viewpoint of obtaining this effect more easily, the average primary particle size of the microparticles (B2) is preferably greater than 0.06 μm and not more than 7 μm; more preferably greater than 0.3 μm and not more than 6 μm; further preferably greater than 1 μm and 4 μm μm or less.

Microparticles ( B2) Average primary particle size.

The shape of the fine particle (B2) may be the same as that exemplified as the shape of the fine particle (B1), but a spherical shape is preferable. In addition, as a constituent component of a fine particle (B2), the same thing as what was exemplified as a constituent component of a fine particle (B1) is mentioned. Fine particles (B2) may be used alone or in combination of two or more.

Among them, the microparticles (B2) are selected from metal oxides whose surfaces are coated with silicone from the viewpoint of being relatively easy to mix as an adhesive paste and easily obtaining a cured product with excellent adhesiveness and heat resistance. Preferably at least one kind of microparticles from the group consisting of silicon oxide, silicon oxide and silicone; more preferably silicon oxide and silicone.

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

(3) Other additives The adhesive paste of this invention may contain the other component [(C) component] other than said (A), (L) and (B) component in the range which does not impair the object of this invention. As (C)component, antioxidant, a ultraviolet absorber, a light stabilizer, etc. are mentioned.

Antioxidants are added for the purpose of preventing oxidative deterioration during heating. Examples of antioxidants include phosphorus antioxidants, phenolic antioxidants, sulfur antioxidants, and the like.

Examples of phosphorus-based antioxidants include phosphites, oxaphosphaphenanthrene oxides, and the like. Examples of the phenolic antioxidant include monophenols, bisphenols, high molecular weight phenols, and the like. Examples of sulfur antioxidants include 3,3'-dilauryl thiodipropionate, 3,3'-dimyristyl thiodipropionate, 3,3'-bis(decyl thiodipropionate) Octyl) esters, etc.

These antioxidants may be used alone or in combination of two or more. The usage-amount of an antioxidant is 10 mass % or less normally with respect to (A) component.

The ultraviolet absorber is added in order to improve the light resistance of the obtained adhesive paste. Salicylic acid, benzophenone (benzophenone), benzotriazole (benzotriazole), hindered amine (hindered amine) etc. are mentioned as a ultraviolet absorber. These ultraviolet absorbents may be used alone or in combination of two or more. The usage-amount of an antioxidant is 10 mass % or less normally with respect to (A) component.

The light stabilizer is added for the purpose of improving the light resistance of the obtained adhesive paste. As a light stabilizer, poly[{6-(1,1,3,3,-tetramethylbutyl)amino-1,3,5-tri-2,4-diyl}{(2 ,2,6,6-tetramethyl-4-piperidinyl)imino}hexamethylene {(2,2,6,6-tetramethyl-4-piperidinyl)imino}] etc. hindered amines. These light stabilizers may be used alone or in combination of two or more. (C) The total usage-amount of a component is 20 mass % or less normally with respect to (A) component.

Adhesive paste of the present invention can be by, for example, have the manufacturing method of following step (AI) and step (AII): Step (AI): performing polycondensation of at least one of the compounds represented by the above formula (a-6) in the presence of a polycondensation catalyst to obtain a polysilsesquioxane compound; step (AII): The polysilsesquioxane compound obtained in the step (AI) is dissolved in the solvent (S), and in the solution containing the obtained polysilsesquioxane compound, the total mass of the paste is 15 A step of adding the above-mentioned liquid component (L) in a mass % or more.

In the step (AI), as a method of polycondensing at least one of the compounds represented by the above-mentioned formula (a-6) in the presence of a polycondensation catalyst to obtain a polysilsesquioxane compound, examples include 1) The same method as exemplified in the paragraph related to the item following paste. Furthermore, the solvent (S) and the liquid component (L) used in the step (AII) can be exemplified in the paragraphs related to the item of 1) the adhesive paste (S) and the liquid component (L). same thing.

In the step (AII), as a method of dissolving the polysilsesquioxane compound in the solvent (S), for example, a polysilsesquioxane compound and a liquid component (L), and optionally A method in which the added components (B) and (C) are mixed with the solvent (S), defoamed and dissolved. The mixing method and defoaming method are not particularly limited, and known methods can be used. The order of mixing is not particularly limited. According to the manufacturing method which has said process (AI) and process (AII), the adhesive paste of this invention can be manufactured efficiently and simply.

For the adhesive paste of the present invention, after heating the adhesive paste at 170°C for 2 hours, the mass reduction rate of the above-mentioned adhesive paste before and after heating is _{170°C for 2 hours} , preferably less than 55%; more preferably more than 10% and less than 45%; The best is more than 15% and less than 30%. Since the volume of the adhesive paste decreases as the mass decreases, if the mass reduction rate _{170°C 2h} is above the above upper limit, there is a risk that the horizontally mounted wafer will be tilted after the adhesive paste is cured. If it is less than the above-mentioned upper limit, this risk can be reduced.

Furthermore, for the adhesive paste of the present invention, after heating the adhesive paste at 100°C for 2 hours, the mass reduction rate of the above-mentioned adhesive paste before and after heating is _{100°C 2h} , preferably more than 10%; more preferably more than 12%, less than 50%; especially good is more than 13% but less than 45%. By making the mass loss rate _{100 degreeC 2h} more than the said lower limit, the hardened|cured material obtained by heating at low temperature can be made into what is more excellent in adhesiveness. On the other hand, if the rate of mass loss at _{100°C for 2 hours} is above the above upper limit, there is a risk that high adhesive strength cannot be exhibited due to the reduction of active ingredients that exert the adhesive function of the cured product obtained by heating at low temperature. The above upper limit value can reduce this risk.

Furthermore, the mass loss rate of the adhesive paste of the present invention is _{preferably less} than 14%, more preferably less than 12%, particularly preferably more than 1% and less than 10%. By making the mass loss rate _{170°C 2h} -mass loss rate _{100°C 2h} less than the above-mentioned upper limit value, since the solvent can be effectively volatilized when heating at a low temperature as in the case of heating at a high temperature, it is possible to make the The cured product obtained by heating at low temperature has better adhesiveness, so the temperature range for heating and curing the adhesive paste can be adjusted, and the influence of heating on optical components, sensor chips, etc. can be reduced. The mass loss rate at _{170° C. for 2 hours} and the mass loss rate at _{100° C. for 2 hours} can be measured by the method described in the examples.

A cured product can be obtained by heating the adhesive paste to volatilize the solvent (S) and solidify it. The heating temperature for curing is usually 80 to 190°C, preferably 80 to 120°C or 150 to 190°C. Furthermore, the heating time for curing is usually 30 minutes to 10 hours, preferably 30 minutes to 5 hours, more preferably 30 minutes to 3 hours.

The cured product obtained by curing the adhesive paste of the present invention has excellent adhesiveness. The cured product obtained by curing the adhesive paste of the present invention is excellent in adhesiveness, which can be confirmed, for example, as follows. That is, the bonding paste of the present invention is coated on the mirror surface of a silicon wafer with a side length of 1 mm square (area is 1 mm ² ), and the coated surface is placed on a silver-plated copper plate for pressure bonding (pressure bonding The final adhesive paste thickness: about 2 μm), and heat treatment (for example, 2 hours at 100° C., 2 hours at 170° C.) to be cured. Place it on the measuring table of the bond tester (bond tester) adjusted to the predetermined temperature (23°C, 100°C) in advance for 60 seconds. The speed applied a stress in the horizontal direction (shear direction) to the bonding surface, and measured the bonding strength (N/mm□) between the test piece and the bonded body.

The adhesive strength of the cured product obtained by curing the adhesive paste of the present invention is preferably at least 7 N/mm□ at 23°C, more preferably at least 10 N/mm□, and even more preferably at least 13 N/mm□. More preferably, more than 15 N/mm□ is especially preferred. Furthermore, the adhesive strength of the cured product obtained by curing the adhesive paste of the present invention is preferably 7 N/mm□ or above at 100°C, more preferably 10 N/mm□ or above, and 13 N/mm□ The above is more preferable, and more than 15 N/mm□ is especially preferable. In this specification, "1 mm□" means "1 mm square", that is, "1 mm×1 mm (a square with a side length of 1 mm)".

Since it has the said characteristic, the adhesive paste of this invention can be used suitably as an adhesive agent for semiconductor element fixing materials.

2) How to use the adhesive paste and the method of manufacturing semiconductor devices using the adhesive paste The method of manufacturing a semiconductor device using the adhesive paste of the present invention as an adhesive for a semiconductor element fixing material is a method having the following steps (BI) and step (BII): Step (BI): applying the adhesive paste to the semiconductor element Step (BII): heat and cure the above-mentioned adhesive paste of the pressure-bonded body obtained in step (BI) to fix the above-mentioned semiconductor element on the bonding surface of one or both of the supporting substrates Steps above on the support substrate.

As the semiconductor element, a light emitting element such as a laser, a light emitting diode (LED), an optical semiconductor element such as a light receiving element of a solar cell, a transistor, a sensor such as a temperature sensor, a pressure sensor, etc., can be cited. Measuring devices, integrated circuits, etc. Among them, an optical semiconductor device is preferable from the viewpoint of more easily exhibiting the effect of using the adhesive paste of the present invention.

As the material for the support substrate to be bonded to the semiconductor element, glass such as soda-lime glass and heat-resistant hard glass; ceramics; sapphire; iron, copper, aluminum, gold, silver, platinum, chromium, titanium, and metals such as Metals such as alloys, stainless steel (SUS302, SUS304, SUS304L, SUS309, etc.); polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene-acetic acid Vinyl ester copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfide, polyphenylene sulfide, polyetherimide, polyimide, polyamide , synthetic resins such as acrylic resins, norcamphene-based resins, cycloolefin resins, glass epoxy resins, etc.

The adhesive paste of the present invention is preferably filled in a syringe. By filling the syringe with the adhesive paste, the workability in the coating step can be excellent. The material of the syringe can be any one of synthetic resin, metal, glass, but preferably synthetic resin. The capacity of the syringe is not particularly limited, and can be appropriately determined according to the amount of the adhesive paste to be filled or applied. In addition, as a syringe, a commercially available product can also be used. Commercially available products include, for example, SS-01T series (manufactured by TERUMO), PSY series (manufactured by Musashi Engineering), and the like.

In the manufacturing method of the semiconductor device of the present invention, the syringe filled with the bonding paste is vertically lowered to approach the supporting substrate, and after a predetermined amount of bonding paste is discharged from the front end of the syringe, the syringe is raised to leave the supporting substrate, and at the same time, the supporting substrate is moved laterally. move. Then, by repeating this operation, the adhesive paste is continuously applied onto the support substrate. Thereafter, the semiconductor element is mounted on the applied adhesive paste and bonded on the support substrate by pressure.

The application amount of the adhesive paste is not particularly limited, as long as it is an amount capable of firmly bonding the semiconductor element to be bonded and the supporting substrate by curing. Usually, the thickness of the coating film of the adhesive paste is 0.5 μm or more and 5 μm or less, preferably 1 μm or more and 3 μm or less.

Thereafter, the semiconductor element is fixed on the support substrate by heating and curing the obtained adhesive paste of the pressure bonding body. The heating temperature and heating time are as described in the relevant paragraphs of 1) following the paste item.

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

Hereinafter, examples will be given to illustrate the present invention in more detail. However, the present invention is not limited to the following Examples. Unless otherwise stated, the parts and percentages in each example are based on mass.

[Measurement of average molecular weight] The mass average molecular weight (Mw) and number average molecular weight (Mn) of the thermosetting organopolysiloxane compound (A) obtained in the production example were measured using the following apparatus and conditions as standard polystyrene conversion values. Device name: HLC-8220GPC, manufactured by Tosoh Co., Ltd. Chromatography column: TSKgelGMHXL, TSKgelGMHXL and TSKgel2000HXL connected sequentially Solvent: THF Injection volume: 20 μl Measuring temperature: 40°C Flow rate: 1 ml/min Detector: Differential refractometer

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

[Viscosity evaluation] In a rheometer (manufactured by Anton Paar, product name "MCR301"), a cone-plate with a radius of 50 mm and a cone angle of 0.5° was used to measure the shear rate at 25°C at a shear rate of 1 s ^-1 viscosity.

(Manufacturing example 1) After putting 71.37 g (400 mmol) of methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) into a 300 ml eggplant-shaped flask, dissolve 0.10 g of 35% hydrochloric acid in distilled water while stirring. The aqueous solution formed in 21.6 ml (relative to the total amount of silane compound is 0.25 mol%), the whole solution 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), add 140 g of propyl acetate. 0.12 g of 28% ammonia water (0.5 mol% relative to the total amount of silane compounds) was added thereto, and the entire solution was added while stirring, and the temperature was raised to 70° C., followed by stirring for 3 hours. Pure water was added to the reaction liquid, and the liquid separation was repeated until the pH of the aqueous layer became 7.0. The organic layer was concentrated with an evaporator, and the concentrate was vacuum-dried to obtain 55.7 g of a thermosetting organopolysiloxane compound (A1). The mass average molecular weight (Mw) of thermosetting organopolysiloxane compound (A1) was 7,800, and the molecular weight distribution (Mw/Mn) was 4.52. In addition, the IR spectrum data of a thermosetting organopolysiloxane compound (A1) are shown below. Si-CH ₃ : 1272 cm ^-1 , 1409 cm ^-1 , Si-O: 1132 cm ^-1

(Manufacturing example 2) 17.0 g (77.7 mmol) of 3,3,3-trifluoropropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 32.33 g (181.3 mmol) of methyltriethoxysilane were charged. After pouring into a 300 ml eggplant-shaped flask, add an aqueous solution (0.65 mmol of HCl; 0.25 mol% relative to the total amount of silane compounds) of 0.0675 g of 35% hydrochloric acid dissolved in 14.0 ml of distilled water while stirring, The entire solution was stirred at 30°C for 2 hours, then heated up to 70°C and stirred for 20 hours. While continuing to stir the contents, a mixed solution of 0.0394 g of 28% ammonia water (the amount of _NH3 is 0.65 mmol) and 46.1 g of propyl acetate was added thereto to make the pH of the reaction solution 6.9, and it was heated at 70 ° C. Stir for 40 minutes. After cooling the reaction solution to room temperature (23° C.), 50 g of propyl acetate and 100 g of water were added thereto for liquid separation treatment to obtain an organic layer containing a reaction product. Magnesium sulfate was added to this organic layer and dried. After removing magnesium sulfate by filtration, the organic layer was concentrated with an evaporator, and the concentrate was vacuum-dried to obtain 22.3 g of a thermosetting organopolysiloxane compound (A2). The mass average molecular weight (Mw) of a thermosetting organopolysiloxane compound (A2) was 5,500, and the molecular weight distribution (Mw/Mn) was 3.40. In addition, the IR spectrum data of a thermosetting organopolysiloxane compound (A2) are shown below. Si-CH ₃ : 1272 cm ^-1 , 1409 cm ^-1 , Si-O: 1132 cm ^-1 , CF: 1213 cm ^-1

(Manufacturing example 3) After putting 28.91 g (145.8 mmol) of phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) into a 300 ml eggplant-shaped flask, dissolve 0.0376 g of 35% hydrochloric acid in distilled water 7.874 g while stirring. The aqueous solution formed in ml (0.25 mol% relative to the total amount of silane compounds), the whole solution 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), 50 g of propyl acetate and 100 g of water were added, and a liquid separation treatment was performed to obtain an organic layer containing a reaction product. Magnesium sulfate was added to this organic layer and dried. After removing magnesium sulfate by filtration, the organic layer was concentrated with an evaporator, and the concentrate was vacuum-dried 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. In addition, the IR spectrum data of a thermosetting organopolysiloxane compound (A3) are shown below. Si-C ₆ H ₅ : 698 cm ^-1 , Si-O: 1132 cm ^-1

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

The compounds used in Examples and Comparative Examples are as follows. [(A) ingredient] Thermosetting organopolysiloxane compound (A1): organopolysiloxane compound obtained in Production Example 1 (solid at 25°C) Thermosetting organopolysiloxane compound (A2): organopolysiloxane compound obtained in Production Example 2 (solid at 25°C) Thermosetting organopolysiloxane compound (A3): organopolysiloxane compound obtained in Production Example 3 (solid at 25°C)

[Liquid Component (L)] (L1) Bifunctional silane compound Dimethoxydiphenylsilane: Shin-Etsu Chemical Co., Ltd.; product name "KBM-202SS" (viscosity 8 mPa・S) (L2) Trifunctional silane compound (L2-1) 3-(trimethoxysilyl)propyl succinic anhydride: manufactured by Shin-Etsu Chemical Co., Ltd.; product name "X-12-967C" (viscosity 30 mPa・S) (L2-2) 3-Methacryloxypropyltrimethoxysilane: manufactured by Shin-Etsu Chemical Co., Ltd.; product name "KBM-503" (viscosity 8 mPa・S) (L2-3) 3-Acryloxypropyltrimethoxysilane: Shin-Etsu Chemical Co., Ltd.; product name "KBM-5103" (viscosity 15 mPa・S) (L2-4) 3-Isocyanatopropyltriethoxysilane: Shin-Etsu Chemical Co., Ltd.; product name "KBE-9007N" (viscosity 10 mPa・S) (L2-5) Phenyltrimethoxysilane: manufactured by Shin-Etsu Chemical Co., Ltd.; product name "KBM-103" (viscosity 10 mPa・S) (L3) Multifunctional silane compound (L3-1) 1,3,5-N-ginseng[3-(trimethoxysilyl)propyl]isocyanurate: manufactured by Shin-Etsu Chemical Co., Ltd.; product name "KBM-9659" (viscosity 800 mPa・S) (L3-2) Polyfunctional silane-based compound having a methoxy group and an isocyanurate group whose main chain is an organic structure: manufactured by Shin-Etsu Chemical Co., Ltd.; product name "X-12-1159L" (viscosity 4,000 mPa・S ) (L4) Silicone oil (L4-1) Two-terminal acrylic modified silicone oil: Shin-Etsu Chemical Co., Ltd.; product name "X-22-2445" (viscosity 60 mPa・S) (L4-2) Alkyl・Aralkyl Modified Silicone Oil: Manufactured by Momentive・Performance・Materials・Japan; product name "XF42-334" (viscosity 1000 mPa・s) [Liquid components (L5) other than liquid components (L)] Liquid polysilsesquioxane: polysilsesquioxane obtained in Production Example 4 (viscosity 197,000 mPa・s)

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

[Component (B)] Microparticles (B1): Silicon oxide microparticles (manufactured by Aerosil Japan, trade name "AEROSIL RX300", average primary particle size: 7 nm, specific surface area: 210 m ² /g) Microparticles (B2): Silicon Ketone (manufactured by Nikko-Rika, trade name "MSP-SN08", average primary particle size: 0.8 μm, shape: spherical)

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

(Examples 2-24, Comparative Examples 1-3) In addition to changing the types and blending ratios of the compounds (components) as shown in Table 1 below, prepare adhesive pastes 2-24 and adhesive pastes 1r-3r in the same manner as in Example 1 Moreover, in Examples 23 and 24, before adding EDGAC (SL) and each liquid component (L1-L3), microparticles (B1) and microparticles (B2) were added.

Using the adhesive pastes 1 to 24 and the adhesive pastes 1r to 3r obtained in Examples and Comparative Examples, the following tests were respectively performed. The results are shown in Table 2 below.

[Evaluation of tack free time] Discharge the adhesive paste obtained in Examples and Comparative Examples on a stainless steel plate (SUS304, surface No. 600 grinding) so that its diameter becomes 0.5 mm, and let it stand in a standard environment (temperature: 23 ° C ± 1 ℃, relative humidity: 50±5%). After a certain period of time, scrape the coated adhesive paste in half with a needle, and observe whether the scratches of the needle disappear within 10 seconds and become invisible. If the scratches of the needle disappear within 10 seconds, continue to stand still until the scratches of the needle will not disappear within 10 seconds, repeat the same observation every 2 minutes from the start of measurement until 10 minutes, and then Or, repeat the same observation every 5 minutes from the start of the measurement until 10 minutes. Finally, the standing time N (minutes) until the scratch of the needle does not disappear within 10 seconds was measured.

[Evaluation of Chip Mountability] The adhesive paste obtained in Examples and Comparative Examples was discharged onto an electroless-plated silver-plated copper plate (average roughness Ra of the silver-plated surface: 0.025 μm) so that the diameter thereof became 0.5 mm. , placed in a standard environment (temperature: 23°C±1°C, relative humidity: 50±5%). After 30 minutes, install a silicon wafer with a side length of 1 mm (with an area of 1 mm ² ), and observe the inclination of the wafer. If the wafer can be installed without inclination, it is evaluated as "good". If there is no problem, it is rated as "bad".

[adhesion strength evaluation (1)] Apply the bonding paste obtained in the examples and comparative examples on the mirror surface of a silicon wafer with a side length of 1 mm square (area 1 mm2), and place it in a standard environment (temperature: 23°C ± 1°C; relative Humidity: 50±5%). After 30 minutes, place the coated surface on the adherend [electroless-plated silver-plated copper plate (average roughness Ra of silver-plated surface: 0.025 μm)] so that the thickness of the adhesive paste after pressure bonding becomes about 2 μm Pressurization is carried out in this way. Then, it heat-processed at 170 degreeC for 2 hours, it hardened, and the to-be-adhered body to which the test piece was stuck was obtained. The bonded body to which the test piece was attached was placed on the measuring table of an adhesive strength tester (manufactured by Dage; Series 4000) at 100°C for 60 seconds. A stress in the horizontal direction (shear direction) is applied to the bonding surface at a speed of /s, and the bonding strength (N/mm□) between the test piece and the bonded body at 100°C is measured.

[adhesion strength evaluation (2)] In the adhesive strength evaluation (1), the temperature condition for curing by heat treatment was changed to 100°C, and the heating temperature and measurement temperature of the adhesive strength testing machine were changed to 23°C, in order to evaluate the adhesive strength. (1) The adhesion strength (N/mm□) between the test piece and the adherend was measured in the same manner.

[Measurement of mass loss rate] 15 mg of the adhesive paste obtained in Examples and Comparative Examples was placed in a differential thermal/thermogravimetric simultaneous measuring device (manufactured by Shimadzu Corporation; product name "DTG-60"), and the measurement start temperature was 40°C, the heating rate is 10°C/min, and heated at 100°C for 2 hours, measure the mass of the above-mentioned bonding paste before and after heating, and calculate the mass reduction rate before and after heating _{100°C 2h} (%) [{[(heating 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, the heating condition was changed to heating at 170°C for 2 hours, and the mass loss rate of the adhesive paste before and after heating was calculated in the same manner as the measurement method of the mass loss rate of _{100°C 2h} (%) _{170°C 2h} (%) [{[(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]. In addition, mass loss rate _{170°C 2h} - mass loss rate _{100°C 2h} (%) was calculated from the measured mass loss rate.

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

[Table 2] Tack free time Chip mountability follow strength (1) Follow up strength (2) Decrease rate _{100℃ 2h} Reduction rate _{170℃ 2h} Mass reduction rate at _{170°C for 2h} - mass reduction rate at _{100°C for 2h} (minute) (N/mm□) (N/mm□) (%) (%) (%) Example 1 80 good 20 12 20 twenty three 3 Example 2 40 good 18 13 18 twenty two 4 Example 3 30 good 19 15 19 twenty three 4 Example 4 40 good 19 15 17 20 3 Example 5 90 good 19 11 20 twenty four 4 Example 6 80 good 16 15 20 twenty two 2 Example 7 80 good 18 16 19 twenty three 4 Example 8 130 good twenty two 15 18 20 2 Example 9 120 good twenty one 13 18 twenty one 3 Example 10 30 good 17 13 18 20 2 Example 11 70 good 18 10 20 twenty two 2 Example 12 90 good 17 12 twenty one twenty three 2 Example 13 110 good 20 18 19 twenty two 3 Example 14 80 good 17 17 twenty one twenty four 3 Example 15 25 good 18 12 20 twenty four 4 Example 16 60 good 16 14 20 twenty three 3 Example 17 90 good twenty one 11 19 twenty three 4 Example 18 120 good 15 0 2 18 16 Example 19 30 good 16 11 19 twenty two 3 Example 20 120 good 17 6 7 twenty two 15 Example 21 90 good 19 9 15 twenty three 8 Example 22 40 good 20 10 40 42 2 Example 23 70 good 18 14 18 twenty one 3 Example 24 50 good twenty one 13 20 twenty two 2 Comparative example 1 2 bad Unable to measure due to poor installation Unable to measure due to poor installation 19 20 1 Comparative example 2 10 bad Unable to measure due to poor installation Unable to measure due to poor installation 17 twenty one 4 Comparative example 3 10 bad Unable to measure due to poor installation Unable to measure due to poor installation 18 20 2

From Table 1 and Table 2, the following contents can be understood. Adhesive pastes 1 to 24 of Examples 1 to 24 had a long time for tack removal and were excellent in wafer mountability, and also had excellent adhesive strength of cured products obtained by heating the adhesive paste at high temperature. Adhesive pastes containing bifunctional silane compounds, trifunctional silane compounds, and silicone oil as liquid components (L) have longer tack-free times than adhesive pastes containing polyfunctional silane compounds as liquid components (L). time, the chip can be mounted for a long time (embodiments 2-4, 12-17). Furthermore, compared to the adhesive paste containing a bifunctional silane compound as a liquid component (L), the adhesive paste containing a trifunctional silane compound and silicone oil as a liquid component (L) is obtained by heating the adhesive paste at a low temperature. The adhesive strength of cured|cured material was excellent (Examples 5-9). That is to say, by selecting the liquid component (L), considering the tack-free time (the standing time after applying the adhesive paste to the object to be coated) and the temperature range for heating the adhesive paste to obtain a cured product, the optimum Suitable adhesive paste.

When an organic solvent (SL) with a low boiling point is contained as the solvent (S), the tack-free time of the adhesive paste is shortened, and the cured product obtained by heating the adhesive paste at a low temperature has excellent adhesive strength (Examples 5 and 10). Furthermore, compared to the adhesive paste containing only organic solvent (SH) as solvent (S), the adhesive paste containing only organic solvent (SL) as solvent (S) has shorter tack-free time, but heating the adhesive paste at low temperature On the other hand, the obtained cured products were excellent in adhesive strength (Examples 18 and 19). In addition, when the mixed solvent of the organic solvent (SL) and the organic solvent (SH) is included as the solvent (S), the tack-free time of the adhesive paste with a large content of the organic solvent (SH) becomes longer. On the other hand, the adhesive paste containing a large proportion of organic solvent (SL) shortens the tack-free time, and the adhesiveness of the cured product obtained by heating the adhesive paste under either high-temperature heating or low-temperature heating is uniform. Excellent (Examples 20 and 21). That is, through the selection of organic solvent (SL) and organic solvent (SH), consider the tack-free time (time after applying the adhesive paste to the object to be coated) and the temperature range of heating the adhesive paste to obtain a cured product , you can get the most suitable paste.

Adhesive pastes with a high solid content concentration (accompanying this, the proportion of the (L) component to the total mass of the adhesive paste is relatively large) have a longer time for tack removal, and adhesive pastes that are cured by heating the adhesive paste at a low temperature Excellent properties (Examples 1 and 22). Compared with the adhesive paste (B) without microparticles, the adhesive paste containing microparticles (B), although the proportion of (L) component relative to the total mass of the adhesive paste is less, its tack-free time is still longer, and the chip mounting Even under the temperature conditions of any one of high-temperature heating and low-temperature heating, cured products with good adhesiveness were provided (Examples 23 and 24). Even if the type of the heat-curable organopolysiloxane compound (A) is changed (the type of the side chain of the polysilsesquioxane compound), the tack-free time is still long, and the chip mountability is still excellent, and even under high temperature heating and The adhesive strength of the hardened|cured material obtained by heating the adhesive paste on any temperature condition of low-temperature heating was excellent (Examples 1, 5, 11, etc.).

On the other hand, in the adhesive paste 1r of Comparative Example 1, since the content of the liquid component (L) is as low as 10% relative to the total mass of the adhesive paste, the tack-free time is short, which is not conducive to chip mounting in a short time. Furthermore, after the silicon wafer was mounted, there was a defect that the wafer was tilted, and the bonding strength could not be measured due to the poor mountability of the wafer. The adhesive paste 2r of Comparative Example 2 contains a high-viscosity liquid component (L). Since the viscosity of the adhesive paste becomes higher, the viscosity-relieving time is shorter, which is not conducive to chip mounting in a short time. Furthermore, after the silicon wafer was mounted, there was a defect that the wafer was tilted, and the bonding strength could not be measured due to the poor mountability of the wafer. The adhesive paste 3r of Comparative Example 3 contains only the organic solvent (SL) as the solvent (S), and the content of the liquid component (L) is as little as 10% relative to the total mass of the adhesive paste, so the tack-free time is relatively short. It is not conducive to wafer mounting in a short time. Furthermore, after the silicon wafer was mounted, there was a defect that the wafer was tilted, and the bonding strength could not be measured due to the poor mountability of the wafer.

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Claims (14)

An adhesive paste comprising a thermosetting organopolysiloxane compound (A) and a liquid component (L) satisfying the following requirements 1 and 2, wherein The content of the above-mentioned liquid component (L) is 15% by mass or more relative to the total mass of the above-mentioned adhesive paste, and the tack-free time of the above-mentioned adhesive paste is 20 minutes or more: [requirement 1] The viscosity at 25°C is below 20,000 mPa·s; [Requirement 2] It is a silane compound. The adhesive paste according to Claim 1, wherein the above-mentioned thermosetting organopolysiloxane compound (A) is a polysilsesquioxane compound. The adhesive paste according to claim 1 or 2, wherein the liquid component (L) is at least one selected from the group consisting of bifunctional silane compounds, trifunctional silane compounds, and silicone oil. The adhesive paste according to claim 1 or 2 further contains a solvent (S), wherein the solvent (S) contains an organic solvent (SL) with a boiling point of 100°C or more and less than 254°C. The adhesive paste according to claim 4, wherein the above-mentioned organic solvent (SL) has a boiling point above 100°C and below 200°C. The adhesive paste according to Claim 4, wherein the content of the above-mentioned organic solvent (SL) is not less than 10% by mass and not more than 50% by mass relative to the total mass of the adhesive paste. The adhesive paste as described in Claim 1 or 2 further contains the following (B) components: (B) Component: Microparticles. The adhesive paste according to claim 1 or 2, wherein the solid content concentration is 50% by mass or more and 90% by mass or less. The bonding paste according to claim 1 or 2, wherein, after heating the bonding paste at 170°C for 2 hours, the mass loss rate of the bonding paste before and after heating is less than 55% at _170°C for 2 hours. The bonding paste as described in Claim 1 or 2, wherein, when the bonding paste is heated at 170°C for 2 hours, the mass loss rate of the above-mentioned bonding paste before and after heating is set as the mass loss rate of _{170°C 2h} , and the above-mentioned bonding paste After the paste is heated at 100°C for 2 hours, when the mass loss rate of the above adhesive paste before and after heating is set as the mass loss rate of _{100 °C for 2} hours, the mass loss rate of _{170 °C for 2 hours} - the mass loss rate of _{100 °C for 2 hours} is less than 14%. The adhesive paste according to claim 1 or 2, wherein substantially no precious metal catalyst is contained. The adhesive paste according to claim 1 or 2, which is an adhesive for fixing materials of semiconductor elements. A method of using the adhesive paste as described in any one of Claims 1 to 12 as an adhesive for semiconductor element fixing materials. A method of manufacturing a semiconductor device, which is a method of manufacturing a semiconductor device using the adhesive paste as described in any one of claims 1 to 12 as a semiconductor element fixing material adhesive, comprising the following steps (B1) and ( BII): Step (BI): a step of applying the above-mentioned bonding paste on the bonding surface of one or both of the semiconductor element and the supporting substrate and bonding under pressure; Step (BII): a step of heating and curing the above-mentioned adhesive paste of the pressure bonding body obtained in the step (BI), and fixing the above-mentioned semiconductor element on the above-mentioned support substrate.