TW202237790A - Adhesive paste, method for using adhesive paste, and method for producing semiconductor device - Google Patents

Abstract

The present invention provides an adhesive paste that contains a curable organopolysiloxane compound and a heat conductive filler, wherein: the thermal conductivity of a cured product which is obtained by heat curing of the adhesive paste at 120 DEG C for 4 hours is 0.5 W/(m.K) or more; and the adhesive strength at 100 DEG C between a silver-plated copper plate and a cured product which is obtained by heat curing of the adhesive paste at 170 DEG C for 2 hours is 5 N/mm□ or more. The present invention provides: an adhesive paste which makes it possible to reduce or prevent thermal deterioration in optical components, sensor chips, and the like due to heat generation in a semiconductor element and a semiconductor device including the semiconductor element and to reduce or prevent detachment of a semiconductor element in a wire bonding process; a method for using the adhesive paste as an adhesive agent for a semiconductor element fixing material; and a method for producing a semiconductor device.

Description

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

The present invention relates to an adhesive paste whose cured product obtained by heat curing has high thermal conductivity and has excellent adhesiveness by heating at a high temperature, and uses this adhesive paste as an adhesive for semiconductor element fixing materials A method of use and a method of manufacturing a semiconductor device using the adhesive paste as an adhesive for a semiconductor element fixing material.

Conventionally, adhesive pastes have been variously improved according to their uses, and are widely used industrially as raw materials for optical components and molded articles, adhesives, coating agents, and the like. In addition, 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), light receiving elements such as solar cells, transistors, sensors such as temperature sensors, pressure sensors, etc., and integrated circuits Wait.

In recent years, the brightness and output of semiconductor elements have been greatly improved, and accordingly, the amount of heat generated by semiconductor elements tends to increase further.

However, as the brightness and output of semiconductor elements have increased in recent years, the cured product of the adhesive paste used for fixing elements has been exposed to higher energy light and higher temperature heat energy generated by semiconductor elements for a long time. Therefore, problems such as reduction in adhesion, deterioration and peeling, or performance degradation of semiconductor elements may occur. Therefore, it has become an important issue to improve the thermal conductivity of the cured product of the adhesive paste, efficiently discharge the heat generated by the semiconductor element, and further maintain or further improve the performance of the semiconductor element.

On the other hand, as a method of manufacturing a semiconductor device including a semiconductor element, the following method is known, which includes, for example, the step of fixing the semiconductor element to an adhered body such as a lead frame (lead frame) using an adhesive sheet, using Next, the step of chip curing and the step of wire bonding.

However, with the miniaturization of semiconductor elements in recent years, the ultrasonic waves generated from the wire bonding apparatus vibrate the small semiconductor elements more easily, and the tension of the wires that have been bonded is generated. Therefore, in the wire bonding step, there may also be A problem of delamination of the semiconductor element occurs. Therefore, in order to cope with various wire bonding conditions such as the type of semiconductor element and the curing temperature of the adhesive paste, there is still a need for an adhesive paste that is excellent in adhesiveness and can prevent peeling of the semiconductor element.

Regarding the present invention, for example, Patent Document 1 describes a curable composition whose cured product has excellent adhesiveness. However, the curable composition described in Patent Document 1 does not pay attention to the thermal conductivity of a cured product obtained by heating and curing the curable composition, and does not describe the evaluation results of thermal degradation of semiconductor elements. [Prior Art Literature] [Patent Document]

[Patent Document 1] International Patent Application Publication No. 2020/067451

[Problem to be solved by the invention]

The present invention has been made in view of such circumstances, and an object of the present invention is to provide a device capable of reducing or even preventing heat generation of optical components, sensor chips, etc. caused by heat generation of a semiconductor element or a semiconductor device including the semiconductor element. Adhesive paste capable of reducing or even preventing peeling of semiconductor elements in a wire bonding step; method of using the adhesive paste as an adhesive for semiconductor element fixing materials; and using the adhesive paste as an adhesive for semiconductor element fixing materials A method of manufacturing a semiconductor device. In addition, in the present invention, "high temperature" means "150°C to 190°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, the following characteristics were found, and the present invention was accomplished: (i) A cured product with high thermal conductivity obtained by heating and curing an adhesive paste containing a curable organopolysiloxane compound can reduce or even prevent heat generation caused by a semiconductor element or a semiconductor device equipped with the semiconductor element. thermal degradation of optical components, sensor die, etc.; and (ii) The cured product with specific adhesive strength obtained by heating the adhesive paste containing the curable organopolysiloxane compound at high temperature can reduce or even prevent the peeling of the semiconductor element in the wire bonding step.

Therefore, according to the present invention, the following adhesive pastes [1] to [6], the method of using the adhesive paste in [7], and the method of manufacturing a semiconductor device using the adhesive paste in [8] are provided.

[1] An adhesive paste containing a curable organopolysiloxane compound (A) and a thermally conductive filler (T), a cured product obtained by heating and curing the above adhesive paste at 120°C for 4 hours The thermal conductivity is above 0.5 W/(m.K), and the bonding strength between the cured product obtained by heating and curing the above adhesive paste at 170°C for 2 hours and the silver-plated copper plate at 100°C is above 5 N/mm□.

[2] The adhesive paste as described in [1], wherein the curable organopolysiloxane compound (A) is a polysilsesquioxane compound. [3] The adhesive paste according to [1] or [2], wherein the thermally conductive filler (T) is an inorganic filler having a thermal conductivity of 5 W/(m·K) or higher. [4] The adhesive paste according to [1] or [2], wherein the thermally conductive filler (T) is at least one selected from the group consisting of titanium oxide, aluminum oxide, and aluminum nitride. [5] The adhesive paste as described in [1] or [2], wherein the adhesive paste does not substantially contain a noble metal catalyst. [6] The adhesive paste as described in [1] or [2], wherein the adhesive paste is an adhesive for semiconductor element fixing materials.

[7] A method of use in which the adhesive paste described in any one of [1] to [6] is used as an adhesive for a semiconductor element fixing material. [8] 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 [6] as an adhesive for fixing a semiconductor element, comprising the following steps (B1 ) and step (BII). Step (BI): the 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; and 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 a method that can reduce or even prevent thermal degradation of optical components, sensor chips, etc. caused by heat generation of a semiconductor element or a semiconductor device equipped with the semiconductor element, and can reduce or even prevent thermal degradation in the wire bonding step. Adhesive paste for peeling of semiconductor elements. Furthermore, according to the present invention, there can be provided 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.

[Mode for Carrying Out the Invention]

Hereinafter, the present invention will be described in detail by dividing it into items such as 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 curable organopolysiloxane compound (A) and a thermally conductive filler (T). The rate is 0.5 W/(m.K) or more, and the bonding strength of the cured product obtained by heating and curing the above adhesive paste at 170°C for 2 hours to the silver-plated copper plate at 100°C is 5 N/mm□ or more.

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 workability in a coating process. Here, the so-called "excellent workability 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 immediately interrupted without occurrence of Splashing of resin or contaminating the surrounding area due to spread of liquid droplets after coating.”

In the adhesive paste of the present invention, the thermal conductivity of the cured product obtained by heating and curing the adhesive paste at 120°C for 4 hours is above 0.5 W/(m.K), preferably above 0.7 W/(m.K), and more preferably It is preferably at least 1.0 W/(m.K), more preferably at least 1.5 W/(m.K), and most preferably at least 2.0 W/(m.K). A cured product obtained by heating and curing with a thermal conductivity equal to or greater than the above lower limit can reduce or even prevent thermal degradation of optical components, sensor chips, etc. caused by heat generation of the semiconductor element or a semiconductor device including the semiconductor element. The thermal conductivity of a cured product obtained by heating and curing the adhesive paste of the present invention can be measured and calculated, for example, as follows. That is, the adhesive paste of the present invention was poured into a Teflon (registered trademark) frame, heat-treated at 120° C. for 4 hours, and cured to prepare a test piece. After that, the thermal diffusivity of the test piece was measured by the temperature wave method using a thermal diffusivity measuring device. Furthermore, it is assumed that among the constituents of the cured product obtained by heat-curing the adhesive paste, the specific heat of the components other than the thermally conductive filler (T) is 1 J/(g·K), and the density is 1.2 g/ cm ³ , the thermal conductivity was calculated by the following formula. Thermal conductivity [W/(m.K)] = thermal diffusivity (m ² /s) × specific heat [J/(g.K)] × density (g/cm ³ ) × 10 ⁶ More specifically, it can be borrowed Measured by the method described in the Examples.

In the adhesive paste of the present invention, the bonding strength between the cured product obtained by heating and curing the adhesive paste at 170°C for 2 hours and the silver-plated copper plate at 100°C is 5 N/mm□ or above, preferably 10 N/mm□ or above , more preferably above 13 N/mm□. When the adhesion strength is more than the above-mentioned lower limit value, the cured product obtained by heating and curing at a high temperature can reduce or even prevent peeling of the semiconductor element in the wire bonding step. The adhesive strength of the hardened|cured material obtained by heat-hardening the adhesive paste of this invention can be measured, for example as follows. That is, the adhesive paste of the present invention is coated on the mirror surface of a silicon wafer with a side length of 1 mm square (with an area of 1 mm ² ), and the coated surface is placed on a silver-plated copper plate for pressure bonding (after pressure bonding) The thickness of the adhesive paste: about 3 μm), and heat treatment at 170°C for 2 hours to cure it. Place it on the measuring platform of a bond tester (bond tester) at 100°C for 60 seconds, and apply a horizontal direction (shear) direction) to measure the bonding strength (N/mm□) between the test piece and the adherend. In this specification, "1 mm□" means "1 mm square", that is, "1 mm×1 mm (a square with a side length of 1 mm)". More specifically, it can be measured by the method described in the Examples.

[Curable organopolysiloxane compound (A)] The adhesive paste of the present invention contains a curable organopolysiloxane compound (A) (hereinafter sometimes referred to as "component (A)"). Since the adhesive paste of the present invention contains the component (A), it is easy to obtain a cured product having excellent adhesiveness after heating at a high temperature.

The curable organopolysiloxane compound (A) of the present invention is a compound having a carbon-silicon bond and a siloxane bond (-Si-O-Si-) in the molecule. Furthermore, since component (A) is a thermosetting compound, it preferably has at least one functional group selected from the group consisting of functional groups capable of condensation reaction by heating and functional groups capable of condensation reaction by hydrolysis. 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 curable 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 aryl group of the unsubstituted or substituted aryl group include cycloalkyl groups having 6 to 10 carbon atoms such as phenyl, 1-naphthyl, and 2-naphthyl.

Examples of substituents for the above-mentioned aryl group include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkyl groups having 1 to 6 carbon atoms such as methyl group and ethyl group; Alkoxy groups 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 curable organopolysiloxane compound (A) can be obtained, for example, by a known production method of polycondensation of 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 curable organopolysiloxane compound (A) is usually not less than 800 and not more than 30,000; preferably not less than 1,000 and not more than 20,000; more preferably not less than 1,200 and not more than 15,000; most preferably not less than 3,000 Above, below 10,000. By using the curable 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 curable organopolysiloxane compound (A) is not particularly limited, but is usually not less than 1.0 and not more than 10.0; preferably not less than 1.1 and not more than 6.0. By using the curable organopolysiloxane compound (A) having a molecular weight distribution (Mw/Mn) within the above-mentioned range, it is easy to obtain an adhesive paste that can provide a cured product more excellent in heat resistance and adhesiveness. The mass average molecular weight (Mw) and the number average molecular weight (Mn) can be converted into standard polystyrene conversion values by, for example, gel permeation chromatography (Gel Permeation Chromatography, GPC) using tetrahydrofuran (THF) as a solvent. ask for.

The curable 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), it is easy to obtain a cured product having excellent adhesiveness after heating at a high temperature. Therefore, the wafer can be more effectively fixed in the wire bonding step.

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 compound having a repeating unit represented by the following formula (a-4) as the component (A), it is easy to obtain a cured product having better adhesiveness after heating at a high temperature.

[chemical formula 4]

In formula (a-4), (R ¹ -D) represents an organic group. In the (R ¹ -D) of the organic group, R ¹ is preferably an unsubstituted alkyl group or an alkyl group with a substituent; an unsubstituted alkyl group with 1 to 10 carbon atoms or a substituent group An alkyl group having 1 to 10 carbon atoms is more preferable. D represents a linking group (however, excluding an alkylene group) or a single bond that combines R ¹ and Si.

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 "substituent alkyl group having 1 to 10 carbon atoms" 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 "substituent alkyl group having 1 to 10 carbon atoms" include the same ones as those exemplified as "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: OJ, 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, J 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; trimethylsilyl, triethylsilyl, tertiary butyldimethylsilyl, tertiary butyldiphenylsilyl and other silane series; 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-methyl Ethers such as oxybenzyl, fluorenyl, trityl, and benzhydryl.

Among them, as R ¹ , from the viewpoint of easily obtaining an unsubstituted polysilsesquioxane compound with a stable structure and more stable performance as an adhesive paste, an unsubstituted alkane having 1 to 10 carbon atoms A group or an alkyl group having 1 to 10 carbon atoms having a fluorine atom is preferable, and an alkyl group having 1 to 10 carbon atoms having a fluorine atom is more preferable. 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 ¹ to 10 carbon atoms having a fluorine atom, it is easy to obtain an adhesive paste, a cured product, etc. with a low refractive index. Therefore, it is easy to apply to applications requiring low Refractive index of optical semiconductor elements. Furthermore, when the semiconductor element is an optical semiconductor element, the light extraction efficiency of the optical semiconductor element can be improved, and a decrease in luminous efficiency can be suppressed.

As an alkyl group having a fluorine atom and a carbon number of 1 to 10, the composition formula: C _m H _(2m-n+1) F _n (m is an integer of 1 to 10; n is 2 or more, (2m A group represented by an integer below +1). Moreover, m is preferably an integer of 1-5, more preferably an integer of 1-3.

Examples of the fluoroalkyl group represented by the composition formula: C _m H _(2m-n+1) F _n include CF ₃ , CF ₃ CF ₂ , CF ₃ (CF ₂ ) ₂ , CF ₃ (CF ₂ ) ₃ , CF ₃ (CF ₂ ) ₄ , CF ₃ (CF ₂ ) ₅ , CF ₃ (CF ₂ ) ₆ , CF ₃ (CF ₂ ) ₇ , CF ₃ (CF ₂ ) ₈ , CF ₃ (CF ₂ ) ₉ etc. Fluoroalkyl (perfluoroalkyl); CF ₃ CH ₂ CH ₂ , CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ , etc. Hydrofluoroalkyl (hydrofluoroalkyl). Among them, the CF ₃ CH ₂ CH ₂ group is preferable.

In the formula (a-4), D represents a linking group (but not including an alkylene group) or a single bond that combines R ¹ and Si, preferably a single bond. Examples of the linking group for D include 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,5-naphthylene, etc., having 6 to 20 carbon atoms. Extended aryl (arylene).

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

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.

The repeating unit represented by the above formula (a-4) in the polysilsesquioxane compound may be a repeating unit represented by the following formula (a-5). That is, (R ¹ -D) in the above formula (a-4) may be R ² in the following formula (a-5).

[chemical formula 5]

In the formula (a- ⁵ ), R represents a group selected from unsubstituted cycloalkyl, substituted cycloalkyl, unsubstituted alkenyl, substituted alkenyl, unsubstituted aryl, substituted A group in the group consisting of an aryl group and an alkylsilyl group. Among them, unsubstituted aryl groups having 6 to 12 carbon atoms and substituted aryl groups having 6 to 12 carbon atoms are preferred.

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 R2 is preferably ⁶ .

The number of carbon atoms in the "aromatic group having a substituent and having 6 to 12 carbon atoms" represented by R2 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 ² is "an aromatic group having 6 to 12 carbon atoms having a substituent", the number of carbon atoms in R ² may exceed 12. Examples of the "aromatic group having 6 to 12 carbon atoms having a substituent" include the same ones as those exemplified as "unsubstituted aromatic group having 6 to 12 carbon atoms".

Examples of the substituent of the "aryl group having 6 to 12 carbon atoms having substituents" include halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms; and alkoxy groups such as methoxy and ethoxy groups. 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.

When the polysilsesquioxane compound has a repeating unit represented by formula (a-5), the polysilsesquioxane compound may have one type of R2, or may have ^two or more ^R2 thing.

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; Ester solvents; halogen-containing solvents such as chloroform; and various organic solvents such as mixed solvents of two or more of the above solvents. Therefore, using these solvents, it is possible to measure ²⁹ Si-NMR in the 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-6).

[chemical formula 6]

In formula (a-6), G represents (R ¹ -D), and R ¹ and D represent the same meanings as R ¹ and D 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.

As shown in formula (a-6), the polysilsesquioxane compound has three oxygen atoms bonded to a silicon atom commonly called a T site, and one other bonded to this silicon atom Partial structure of the group (group represented by G).

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 formula (a-6) 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-6), Whether all three * in the above formula (a-6) are repeating units of Si atoms can be confirmed by measuring ²⁹ Si-NMR. In addition, if the assignment of the peak and the integration of the area of ²⁹ Si-NMR are feasible, it can be estimated that the repeating unit represented by the above formula (a-4) in the polysilsesquioxane compound (T site ) in the above formula (a-6) of the total number of 3 * all are the total number of repeating units of Si atoms. The above formula (a-6) relative to the total number of repeating units (T sites) represented by the repeating units (T sites) represented by the above formula (a-4) in the polysilsesquioxane compound The total number of repeating units in which 3 * all are Si atoms is more preferably 30 to 95 mol%, and 40 to 90 mol from the viewpoint of easily obtaining an adhesive paste that can provide a cured product with better heat resistance. % is better.

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, the following formula (a-7) can be

[chemical formula 7]

(In the formula, R ¹ and D represent the same meaning as R ¹ and D in the above formula (a-4). R ³ represents an alkyl group with 1 to 10 carbon atoms, X ¹ represents a halogen atom, and p represents 0 ~3 integers. Plural R ³ may be the same or different from each other, and multiple X ¹ may be the same or different from each other.) At least one of the represented silane compounds (1) is polycondensed, whereby Manufacture of polysilsesquioxane compounds. Examples of the alkyl group having 1 to 10 carbon atoms for R ³ include the same ones as those exemplified as the alkyl group having 1 to 10 carbon atoms for * in the above formula (a-6). Examples of the halogen atom for X1 include ^a chlorine atom and a bromine atom.

Specific examples of the silane compound (1) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltrimethoxysilane, n-propyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane , n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, isooctyltriethoxysilane and other alkyltrialkoxysilane compounds;

Methylchlorodimethoxysilane, Methylchlorodiethoxysilane, Methyldichloromethoxysilane, Methylbromodimethoxysilane, Ethylchlorodimethoxysilane, Ethylchlorodiethylsilane Oxysilane, ethyldichloromethoxysilane, ethylbromodimethoxysilane, n-propylchlorodimethoxysilane, n-propyldichloromethoxysilane, n-butylchlorodimethoxysilane Alkyl halogenoalkoxysilane compounds such as silane and n-butyldichloromethoxysilane;

Methyltrichlorosilane, methyltribromosilane, ethyltrichlorosilane, ethyltribromosilane, n-propyltrichlorosilane, n-propyltribromosilane, n-butyltrichlorosilane, isobutyltrichlorosilane Alkyl trihalogenosilane compounds such as silane, n-pentyltrichlorosilane, n-hexyltrichlorosilane, and isooctyltrichlorosilane;

CF ₃ Si(OCH ₃ ) ₃ , CF ₃ CF ₂ Si(OCH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ Si(OCH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ CF ₂ Si(OCH ₃ ) ₃ , CF ₃ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , CF ₃ (C ₆ H ₄ )Si(OCH ₃ ) ₃ , CF ₃ Si(OCH ₂ CH ₃ ) ₃ , CF ₃ CF ₂ Si(OCH ₂ CH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ Si(OCH ₂ CH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ CF ₂ Si(OCH ₂ CH ₃ ) ₃ , CF ₃ CH ₂ CH ₂ Si(OCH ₂ CH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ Si(OCH ₂ CH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ Si(OCH ₂ CH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ Si(OCH ₂ CH ₃ ) ₃ , CF ₃ (C ₆ H ₄ )Si (OCH ₂ CH ₃ ) ₃ and other fluoroalkyl trialkoxysilane (fluoroalkyl trialkoxysilane) compounds;

CF ₃ SiCl(OCH ₃ ) ₂ , CF ₃ CF ₂ SiCl(OCH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ SiCl(OCH ₃ ) ₂ , CF ₃ SiBr(OCH ₃ ) ₂ , CF ₃ CF ₂ SiBr(OCH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ SiBr(OCH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ CF ₂ SiCl(OCH ₃ ) ₂ , CF ₃ CH ₂ CH ₂ SiCl(OCH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl(OCH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl(OCH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl(OCH ₃ ) ₂ , CF ₃ (C ₆ H ₄ )SiCl(OCH ₃ ) ₂ , CF ₃ SiCl(OCH ₂ CH ₃ ) ₂ , CF ₃ CF ₂ SiCl(OCH ₂ CH ₃ ) _2. CF ₃ CF ₂ CF ₂ SiCl(OCH ₂ CH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ CF ₂ SiCl(OCH ₂ CH ₃ ) ₂ , CF ₃ CH ₂ CH ₂ SiCl(OCH ₂ CH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl(OCH ₂ CH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl(OCH ₂ CH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl(OCH ₂ CH ₃ ) ₂ , CF ₃ (C ₆ H ₄ )SiCl(OCH ₂ CH ₃ ) ₂ etc. Fluoroalkylhalogenated dialkoxy Silane (fluoroalkyl halogenodialkoxysilane) compounds;

CF ₃ SiCl ₂ (OCH ₃ ), CF ₃ CF ₂ SiCl ₂ (OCH ₃ ), CF ₃ CF ₂ CF ₂ SiCl ₂ (OCH ₃ ), CF ₃ CF ₂ CF ₂ CF ₂ SiCl ₂ (OCH ₃ ), CF ₃ CH ₂ CH ₂ SiCl ₂ (OCH ₃ ), CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₂ (OCH ₃ ), CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₂ (OCH ₃ ), CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₂ (OCH ₃ ), CF ₃ (C ₆ H ₄ )SiCl ₂ (OCH ₃ ), CF ₃ SiCl ₂ ( OCH ₂ CH ₃ ), CF ₃ CF ₂ SiCl ₂ (OCH ₂ CH ₃ ), CF ₃ CF ₂ CF ₂ SiCl ₂ (OCH ₂ CH ₃ ), CF ₃ CF ₂ CF ₂ CF ₂ SiCl ₂ (OCH ₂ CH ₃ ) , CF ₃ CH ₂ CH ₂ SiCl ₂ (OCH ₂ CH ₃ ), CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₂ (OCH ₂ CH ₃ ), CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₂ (OCH ₂ CH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₂ (OCH ₂ CH ₃ ), CF ₃ (C ₆ H ₄ ) Fluoroalkyl dihalogenoalkoxysilane (fluoroalkyl dihalogenoalkoxysilane) compounds such as SiCl ₂ (OCH ₂ CH ₃ );

CF ₃ SiCl ₃ , CF ₃ CF ₂ SiCl ₃ , CF ₃ SiBr ₃ , CF ₃ CF ₂ SiBr ₃ , CF ₃ CF ₂ CF ₂ SiCl ₃ , CF ₃ CF ₂ CF ₂ CF ₂ SiCl ₃ , CF ₃ CH ₂ CH ₂ SiCl ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ Fluoroalkyl trihalogenosilane (fluoroalkyl trihalogenosilane) compounds such as CF ₂ CH ₂ CH ₂ SiCl ₃ , CF ₃ (C ₆ H ₄ ) SiCl ₃ ;

Phenyltrialkoxysilane compounds such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyldiethoxymethoxysilane, phenylethoxydimethoxysilane, etc.; Phenyl halogenoalkoxysilane compounds such as dimethoxyphenylsilane chloride and diethoxyphenylsilane chloride; Phenyl trihalogenosilane compounds such as phenyltrichlorosilane and phenyltribromosilane, 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.

Examples of base catalysts include ammonia water; trimethylamine, triethylamine, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, pyridine, 1,8-diacril Bicyclo[5.4.0]undeca-7-ene (1,8-diazabicyclo[5.4.0]-7-undecene), aniline, picoline, 1,4-diazabicyclo[2.2.2]octane Alkanes (1,4-diazabicyclo [2.2.2] octane), imidazole and other organic bases; tetramethylammonium hydroxide, tetraethylammonium hydroxide and other organic salt hydroxides; sodium methoxide, sodium ethoxide, Metal alkoxides such as sodium tertiary butoxide and potassium tertiary butoxide; metal hydrides such as sodium hydride and calcium hydride; metal hydrides such as sodium hydroxide, potassium hydroxide and calcium hydroxide Oxides; 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 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 (c), it is also possible to carry out polycondensation reaction in water system in the presence of an acid catalyst, and then add an organic solvent and an excessive amount of alkali catalyst (ammonia, etc.) to the reaction solution. Further polycondensation reaction under the 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. 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 ³ 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 a polysilsesquioxane compound obtained by, for example, polycondensation reaction of silane compound (1), the curing is by condensation reaction including the reaction with the silane coupling agent described later. Therefore, the present invention is different from general thermosetting silicone adhesives that undergo addition reaction and cure in the presence of noble metal catalysts such as platinum catalysts. 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 "a component other than the solvent (S) 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.

[Thermally conductive filler (T)] The thermally conductive filler (T) (hereinafter sometimes referred to as "component (T)") constituting the adhesive paste of the present invention is a filler having high thermal conductivity. The thermal conductivity of the thermally conductive filler (T) is preferably at least 5 W/(m.K) at 25°C; more preferably at least 8 W/(m.K) and less than 300 W/(m.K) ; The best is more than 10 W/(m.K) and less than 100 W/(m.K). By using the heat conductive filler (T) whose heat conductivity is more than the said lower limit, the hardened|cured material with heat conductivity of 0.5 W/(m·K) or more can be obtained more easily. The thermal conductivity of the thermally conductive filler (T) can be measured, for example, by a laser flash method using a laser flash method calorific constant measuring device (for example, manufactured by NETZSCH-Geratebau GmbH; LFA477 Nanoflash, etc.).

The constituent components of the thermally conductive filler (T) are not particularly limited as long as the thermal conductivity can be improved, and examples thereof include metals; metal oxides; carbides; nitrides, and the like.

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 magnesium oxide, titanium oxide, zinc oxide, aluminum oxide, boehmite, chromium oxide, nickel oxide, copper oxide, zirconium oxide, indium oxide, and composite oxides thereof.

Examples of carbides include magnesium carbonate, silicon carbide, calcium carbonate, and the like; examples of nitrides include boron nitride, aluminum nitride, and the like.

The thermally conductive filler (T) may be used alone or in combination of two or more. Among them, in the present invention, titanium oxide, aluminum oxide, Aluminum nitride is preferred, and aluminum oxide is more preferred.

The shape of the thermally conductive filler (T) may be any of spherical shape, chain shape, needle shape, plate shape, flake shape, rod shape, fiber shape, etc., but spherical shape is preferred. Here, "spherical" means "not only a true spherical shape, but also a substantially spherical shape that can approximate a polyhedron shape such as an ellipsoid, an egg shape, a flat candy shape, and an eyebrow shape."

The average particle size of the thermally conductive filler (T) is preferably at least 0.1 μm and less than 5 μm; more preferably at least 0.2 μm and less than 4 μm; more preferably at least 0.4 μm and less than 3.5 μm; most preferably at least 0.8 μm Above, less than 3 μm. By setting the average particle size of the component (T) within the above range, it is easy to mix well with the component (A), and it is relatively easy to mix it as an adhesive paste, and it is easy to obtain a cured product obtained by heating and curing. Excellent adhesive paste. Furthermore, the coating film thickness of the adhesive paste is usually not less than 0.5 μm and not more than 10 μm. From the viewpoint of being able to horizontally mount the semiconductor element on the applied adhesive paste, the average particle diameter is preferably smaller than the above upper limit. . In addition, in order to make the cured product obtained by heating and curing the adhesive paste of the present invention exhibit high adhesive strength, it is necessary to increase the contact between the (T) component and the (A) component as much as possible, not the contact between the thermally conductive fillers (T) . That is, in each heat conductive filler (T), it is preferable that the whole surface is covered with (A) component as much as possible. From this point of view, when the average particle diameter is less than the above-mentioned lower limit, the cohesive force of the thermally conductive filler (T) increases, and the contact portions of the thermally conductive fillers (T) that cannot be covered by the component (A) increase, so that it may not be possible. High adhesive strength is exerted, but when the average particle diameter is more than the above-mentioned lower limit value, the area ratio of the thermally conductive filler (T) that can be covered with (A) component increases, so the risk can be reduced. The average particle size of the thermally conductive filler (T) can be observed, for example, by a transmission electron microscope. The primary particle size measurement by image analysis was calculated by the X-ray transmission sedimentation method using a particle size distribution measuring device (SediGraph).

Next, the volume filling rate of the thermally conductive filler (T) in the solid content of the paste is preferably 10 vol% or more and less than 80 vol%; more preferably 20 vol% or more and less than 70 vol%; particularly preferably 30 vol% or more , less than 60 vol%. Containing the component (T) so that the volume filling rate is within the above-mentioned range can improve thermal conductivity, so it is easy to obtain a cured product with high thermal conductivity. The volume filling factor can be measured and calculated as follows, for example. That is, calculate the volume of (T) component from the mass and density of (T) component, and then calculate the solid content of the adhesive paste from the mass and density of components other than (T) component in the solid content of the adhesive paste The volume of components other than the (T) component in the formula can be used to calculate the volume filling rate by the following formula. Volume filling rate (vol%) = {volume (cm ³ ) of (T) component/[volume (cm ³ ) of (T) component + volume of components other than (T) component in the solid content of the next paste (cm ³ )]}×100 More specifically, it can be measured and calculated by the method described in the examples.

The content of the component (T) is not particularly limited, but is preferably at least 30 parts by mass and less than 90 parts by mass relative to 100 parts by mass of the solid content of the adhesive paste; more preferably at least 35 parts by mass and less than 85 parts by mass; further More preferably, it is 40 mass parts or more and less than 80 mass parts. By using (T) component in the said range by this, thermal conductivity is high, and the hardened|cured material excellent in the adhesiveness by heating at high temperature can be obtained.

In addition, the content of (T) component is not specifically limited, Its content is preferably 40 mass parts or more and less than 1000 mass parts with respect to 100 mass parts of solid content of (A) component; More preferably 60 mass parts or more, It is less than 900 parts by mass; more preferably at least 80 parts by mass and less than 800 parts by mass; particularly preferably at least 100 parts by mass and less than 600 parts by mass. By using the (T) component in the above-mentioned range, a cured product having high thermal conductivity and excellent adhesiveness by heating at a high temperature can be obtained.

[other ingredients] The adhesive paste of the present invention contains a curable organopolysiloxane compound (A) and a thermally conductive filler (T), but may also contain components exemplified below.

(1) Solvent (S) The adhesive paste of this invention may contain a solvent (S). The solvent (S) is not particularly limited as long as it can dissolve or disperse the components of the adhesive paste of the present invention. As the solvent (S), it is preferable to contain an organic solvent having a boiling point of 254° C. or higher (hereinafter sometimes referred to as “organic solvent (SH)”). Here, the "boiling point" means "the boiling point of 1013 hectopascals (hPa)" (it is the same in this specification). The boiling point of the organic solvent (SH) is preferably above 254°C; more preferably above 254°C and below 300°C.

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. ℃), triethylene glycol butyl methyl ether (boiling point 261 ℃), polyethylene glycol dimethyl ether (boiling point 264 ~ 294 ℃), tetraethylene glycol dimethyl ether (tetraethylene glycol dimethyl ether) (boiling point 275 ℃) , Polyethylene glycol monomethyl ether (boiling point 290-310°C), etc. Among them, as the organic solvent (SH), tripropylene glycol n-butyl ether and 1,6-hexanediol diacrylate are preferable from the viewpoint of more easily obtaining the effect of the present invention. The organic solvent (SH) may be used alone or in combination of two or more.

The adhesive paste of the present invention may contain solvents other than the organic solvent (SH). Solvents other than the organic solvent (SH) are preferably solvents having a boiling point of 100° C. or higher and lower than 254° C. (hereinafter sometimes referred to as “organic solvent (SL)”). The organic solvent (SL) is not particularly limited as long as it has a boiling point of 100° C. or higher and lower than 254° C. and can dissolve or disperse the components of the adhesive paste of the present invention. By combining the organic solvent (SH) with a solvent other than the organic solvent (SH), the temperature range of the cured product obtained by heating the adhesive paste can be adjusted more precisely, and the effect of heating on optical parts and sensitive parts that are easily affected by heat can be reduced. The effect caused by the tester chip.

Specific examples of the organic solvent (SL) include diethylene glycol monobutyl ether acetate (boiling point 247° C.), dipropylene glycol n-butyl ether (boiling point 229° C.), dipropylene glycol methyl ether acetate (boiling point 209° C. ℃), diethylene glycol butyl methyl ether (boiling point 212 ℃), dipropylene glycol n-propyl ether (boiling point 212 ℃), tripropylene glycol dimethyl ether (boiling point 215 ℃), triethylene glycol dimethyl ether (boiling point 216 ℃), 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 monobutyl ether acetate (boiling point 192°C), ethylene glycol monoethyl ether (boiling point 134.8°C), ethylene glycol monomethyl ether (boiling point 124.5°C), propylene glycol monomethyl ether acetate (boiling point 146°C), cyclopentanone (boiling point 130°C) , Cyclohexanone (boiling point 157°C), cycloheptanone (boiling point 180°C), cyclooctanone (boiling point 195-197°C), cyclohexanol (boiling point 161°C), cyclohexadienone (boiling point 104-104.5°C )Wait. Among them, as the organic solvent (SL), from the viewpoint of being easy to mix the active ingredients well, glycol-based solvents are preferred, and diethylene glycol monobutyl ether acetate and dipropylene glycol n-butyl ether are preferred. , more preferably diethylene glycol monobutyl ether acetate.

When an organic solvent (SH) and an organic solvent (SL) are used in combination, specifically, tripropylene glycol n-butyl ether (solvent (SH)) and diethylene glycol monobutyl ether acetate (solvent (SL) ) combination; 1,6-hexanediol diacrylate (solvent (SH)) and diethylene glycol monobutyl ether acetate (solvent (SL)); tripropylene glycol n-butyl ether (solvent (SH) ) with dipropylene glycol n-butyl ether (solvent (SL)); 1,6-hexanediol diacrylate (solvent (SH)) in combination with dipropylene glycol n-butyl ether (solvent (SL)).

The adhesive paste of the present invention preferably contains the solvent (S) at a solid content concentration of 50% by mass to 99% by mass; more preferably at a solid content concentration of 70% by mass to 97% by mass. Instead, the solvent (S) is contained. When the solid content concentration is within the above range, the active ingredients can be mixed easily and favorably, and the workability in the step of filling the adhesive paste into the syringe and the step of applying it is excellent. 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". In addition, during die bonding, it is possible to suppress generation of voids between the bonding paste and the substrate to be bonded, and improve the reliability of packaging.

(2) Silane coupling agent (B)) The adhesive paste of this invention may contain a silane coupling agent as (B) component. Examples of the silane coupling agent include a silane coupling agent (B1) having a nitrogen atom in the molecule (hereinafter sometimes referred to as "silane coupling agent (B1)"), and a silane coupling agent (B2) having an acid anhydride structure in the molecule (hereinafter Sometimes called "silane coupling agent (B2)"), etc.

The adhesive paste containing the silane coupling agent (B1) has excellent processability in the coating process, and has excellent curability in the condensation reaction with the (A) component when heated, and can provide adhesiveness and heat resistance when heated at high temperature. A cured product that is more excellent in resistance to cracking and cracking of the cured product. Here, "the cured product is more excellent in crack suppression" means "when the cured product obtained by adhering the paste is adhered, the cured product does not crack due to temperature change".

The silane coupling agent (B1) is not particularly limited as long as it has a nitrogen atom in the molecule. For example, a trialkoxysilane compound represented by the following formula (b-1), a dialkoxyalkylsilane compound represented by the following formula (b-2), or a dialkoxyaryl silane compounds, etc.

[chemical formula 8]

In the above formula, R ^a represents an alkoxy group having 1 to 6 carbon atoms such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and tert-butoxy. A plurality of R ^a may be the same as or different from each other. R ^b represents an alkyl group with 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, etc.; or phenyl, 4-chlorophenyl, A substituted or unsubstituted aromatic group such as 4-methylphenyl and 1-naphthyl.

R ^c represents an organic group having a nitrogen atom and having 1 to 10 carbon atoms. Furthermore, ^Rc may be bonded to a group containing another silicon atom. Specific examples of organic groups having 1 to 10 carbon atoms in R ^c include N-2-(aminoethyl)-3-aminopropyl, 3-aminopropyl, N-(1 ,3-Dimethyl-butylidene) aminopropyl (N-(1,3-dimethyl-butylidene) aminopropyl), 3-ureidopropyl (3-ureidopropyl), N-phenyl-aminopropyl Wait.

Among the compounds represented by the above-mentioned formula (b-1) or (b-2), when R ^c is an organic group bonded to a group containing other silicon atoms, examples of compounds obtained by isocyanuric acid An isocyanurate-based silane coupling agent is formed by bonding an isocyanurate skeleton to other silicon atoms, or a urea-based silane coupling agent is bonded to other silicon atoms by a urea skeleton Wait.

Among them, as the silane coupling agent (B1), isocyanurate-based silane coupling agents and urea-based silane coupling agents are preferred from the viewpoint of easily obtaining a cured product with higher adhesive strength. A thing having 4 or more alkoxy groups bonded to a silicon atom is more preferable. 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.

As an isocyanurate-based silane coupling agent having 4 or more alkoxy groups bonded to silicon atoms, compounds represented by the following formula (b-3) can be cited; Examples of the urea-based silane coupling agent of an alkoxy group to a silicon atom are compounds represented by the following formula (b-4).

[chemical formula 9]

In the formula, R ^a represents the same meaning as R ^a in the above formulas (b-1) and (b-2). 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 (b-3) 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) base) isocyanurate, 1,3,5-N-paraffin (3-dimethoxyisopropylsilylpropyl) isocyanurate, 1,3,5-N-paraffin (3- Dimethoxy-n-propylsilylpropyl) isocyanurate, 1,3,5-N-paraffin (3-dimethoxyphenylsilylpropyl) isocyanurate, 1,3 ,5-N-ginseng (3-diethoxymethylsilylpropyl) isocyanurate, 1,3,5-N-ginseng (3-diethoxyethylsilylpropyl) isocyanurate Cyanurate, 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-paraffin (3-diisopropoxymethylsilylpropyl) isocyanurate, 1,3,5-N-paraffin (3-diisopropoxyethylsilylpropyl) isocyanurate Urate, 1,3,5-N-paraffin (3-diisopropoxyisopropylsilylpropyl) isocyanurate, 1,3,5-N-paraffin (3-diisopropyl Oxy-n-propylsilylpropyl) isocyanurate, 1,3,5-N-paraffin (3-diisopropoxyphenylsilylpropyl) isocyanurate, 1,3, 5-N-paraffin (3-dibutoxymethylsilylpropyl) isocyanurate, 1,3,5-N-paraffin (3-dibutoxyethylsilylpropyl) isocyanurate Urate, 1,3,5-N-paraffin (3-dibutoxyisopropylsilylpropyl) isocyanurate, 1,3,5-N-paraffin (3-dibutoxy 1,3,5-N-propylsilylpropyl) isocyanurate, 1,3,5-N-paraffin (3-dibutoxyphenylsilylpropyl) isocyanurate N-paraffin [(two (1-6 carbon atoms) alkoxy) silyl (1-10 carbon atoms) alkyl] isocyanurate, etc.

Specific examples of the compound represented by the formula (b-4) 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 (3-diethoxymethylsilylpropyl) urea and other N,N'-bis[(two (1 to 6 carbon atoms) alkoxy groups (1 to 6 carbon atoms) Alkylsilyl (with 1 to 10 carbon atoms) alkyl] urea; 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 and the like. A silane coupling agent (B1) can be used individually by 1 type or in combination of 2 or more types.

Among them, as the silane coupling agent (B1), it is preferable to use 1,3,5-N-paraffin (3-trimethoxysilylpropyl) isocyanurate, 1,3,5-N-paraffin ( 3-triethoxysilylpropyl)isocyanurate (hereafter, the above two are collectively referred to as "isocyanurate compound"), N,N'-bis(3-trimethoxysilyl) Propyl)urea, N,N'-bis(3-triethoxysilylpropyl)urea (hereinafter, the above two are collectively referred to as "urea compound"), and the above-mentioned isocyanurate compound and urea The combination of compounds is more preferably an isocyanurate compound.

When the above-mentioned isocyanurate compound and urea compound are used in combination, the mass ratio of the two (isocyanurate compound) to (urea compound) is preferably 100:1 to 100:200, preferably 100 : 10-100: 110 is more preferable. By using the isocyanurate compound and the urea compound in such a ratio in combination, an adhesive paste that can provide a cured product with higher adhesive strength and excellent heat resistance can be obtained.

When the adhesive paste of the present invention contains a silane coupling agent (B1) [component (B1)], the content of the component (B1) is not particularly limited, but its content is preferably 0.7 parts by mass relative to 100 parts by mass of the solid content of the adhesive paste More than 15 parts by mass; more preferably 1 part by mass to less than 13 parts by mass; more preferably 1.3 parts by mass to less than 11 parts by mass; particularly preferably 1.5 parts by mass to less than 9 parts by mass. By using the component (B1) in the above range, the effect of adding the component (B1) can be further exhibited, and a cured product having a thermal conductivity of 0.5 W/(m·K) or more can be obtained more easily.

The adhesive paste containing the silane coupling agent (B2) is excellent in workability in the coating step, and can provide a cured product that is more excellent in adhesiveness and heat resistance when heated at a high temperature.

Examples of the silane coupling agent (B2) include 2-(trimethoxysilyl)ethylsuccinic anhydride, 2-(triethoxysilyl)ethylsuccinic anhydride, 3-(trimethoxysilyl) Propyl succinic anhydride, 3-(triethoxysilyl) propyl succinic anhydride, etc. Tris (1 to 6 carbon atoms) alkoxysilyl (2 to 8 carbon atoms) alkanes Succinic anhydride; 2-(dimethoxymethylsilyl) ethyl succinic anhydride and other bis (1 to 6 carbon atoms) alkoxymethylsilyl (2 to 8 carbon atoms) alkylbutyl dianhydride; (1-6 carbon atoms) alkoxydimethylsilyl (2-8 carbon atoms) alkylbutyl group such as 2-(methoxydimethylsilyl) ethyl succinic anhydride dianhydride;

2-(trichlorosilyl) ethyl succinic anhydride, 2-(tribromosilyl) ethyl succinic anhydride, etc. trihalogenated silyl (with 2 to 8 carbon atoms) alkyl succinic anhydride; 2-(Dichloromethylsilyl)ethylsuccinic anhydride and other dihalogenated methylsilyl (with 2 to 8 carbon atoms) alkylsuccinic anhydrides; Halogenated dimethylsilyl (with 2 to 8 carbon atoms) alkyl succinic anhydride such as 2-(chlorodimethylsilyl) ethyl succinic anhydride. A silane coupling agent (B2) can be used individually by 1 type or in combination of 2 or more types.

Among them, as the silane coupling agent (B2), it is better to use three (carbon number of 1 to 6) alkoxysilyl (carbon number of 2 to 8) alkyl succinic anhydride; oxysilyl)propylsuccinic anhydride or 3-(triethoxysilyl)propylsuccinic anhydride is particularly preferred.

When the adhesive paste of the present invention contains a silane coupling agent (B2) [component (B2)], the content of the component (B2) is not particularly limited, but its content is preferably 0.05 parts by mass relative to 100 parts by mass of the solid content of the adhesive paste More than 5 parts by mass; more preferably 0.1 parts by mass to less than 3 parts by mass; more preferably 0.2 parts by mass to less than 2 parts by mass; particularly preferably 0.3 parts by mass to less than 1.5 parts by mass. By using the component (B2) in the above range, the effect of adding the component (B2) can be further exhibited, and a cured product having a thermal conductivity of 0.5 W/(m·K) or more can be obtained more easily.

Furthermore, when the adhesive paste of the present invention contains component (B), the content of component (B) is not particularly limited, but its content is preferably at least 0.7 parts by mass and less than 20 parts by mass relative to 100 parts by mass of the solid content of the adhesive paste. Part; more preferably 1 mass part or more and less than 15 mass parts; further preferably 1.3 mass parts or more and less than 12 mass parts; particularly preferably 1.5 mass parts or more and less than 9 mass parts. By using the component (B) in the above range, the effect of adding the component (B) can be further exhibited, and a cured product having a thermal conductivity of 0.5 W/(m·K) or more can be obtained more easily.

(3) Other additives The adhesive paste of this invention may contain the other component [(C) component] other than said (A), (T) 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 to prevent 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.

A light stabilizer is added to improve the light resistance of the obtained adhesive paste. As the light stabilizer, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2, 2,6,6-Tetramethyl-4-piperidine)imino}hexamethylene {(2,2,6,6-tetramethyl-4-piperidine)imino}], etc. 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.

The adhesive paste of this invention can be manufactured by the manufacturing method which has the following process (AI) and process (AII), for example. Step (AI): a step of polycondensing at least one compound represented by the above formula (a-7) in the presence of a polycondensation catalyst to obtain a polysilsesquioxane compound; and Step (AII): Dissolving the polysilsesquioxane compound obtained in the step (AI) in a solvent (S), and adding a thermally conductive filler (T )A step of.

In step (AI), as a method of polycondensing at least one of the compounds represented by the above-mentioned formula (a-7) in the presence of a polycondensation catalyst to obtain a polysilsesquioxane compound, the following are listed. 1) Follow the same method as exemplified in the paragraph related to the item of paste. Furthermore, the solvent (S) and thermally conductive filler (T) used in the step (AII) can be exemplified the same as those exemplified in the relevant paragraphs of the solvent (S) and thermally conductive filler (T) in the item of the paste. things.

In the step (AII), as a method of dissolving the polysilsesquioxane compound in the solvent (S), for example, a polysilsesquioxane compound and a thermally conductive filler (T) and optionally adding The method of component (B) and component (C) is 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.

According to the present invention, a cured product can be obtained by heating the adhesive paste to volatilize the solvent (S) and solidify it. The heating temperature at the time of hardening is 100-190 degreeC normally, Preferably it is 120-190 degreeC. 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.

Since the adhesive paste of this invention has the said characteristic, it 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 manufacturing method of the semiconductor device which uses the adhesive paste of this invention as the adhesive agent for semiconductor element fixing materials is a method which has the following process (BI) and process (BII). Step (BI): a step of applying the bonding paste on the bonding surface of one or both of the semiconductor element and the supporting substrate and bonding under pressure; and 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.

As the semiconductor element, light-emitting elements such as lasers, light-emitting diodes (LEDs), etc., light-receiving elements such as solar cells, transistors, sensors such as temperature sensors, pressure sensors, etc., and 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.

Examples of materials for supporting substrates to be bonded to semiconductor elements include glass such as soda-lime glass and heat-resistant hard glass; ceramics; sapphire; iron, copper, aluminum, gold, silver, platinum, chromium, titanium, and alloys of these metals Metals such as stainless steel (SUS302, SUS304, SUS304L, SUS309, etc.); polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene-vinyl acetate Ester copolymer, polystyrene, polycarbonate, polymethylpentene, polyether ether ketone, polyether ether ketone, polyphenylene sulfide, polyetherimide, polyimide, polyamide, Synthetic resins such as acrylic resins, norbornene-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 process becomes excellent. The material of the syringe can be any of synthetic resin, metal, and glass, but synthetic resin is preferred. The capacity of the syringe is not particularly limited, and can be appropriately determined according to the amount of 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 not less than 0.5 μm and not more than 5 μm, preferably not less than 1 μm and not more than 3 μm.

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) the item next to the paste.

In the semiconductor device obtained by the manufacturing method of the semiconductor device of the present invention, the semiconductor element is well mounted on the adhesive paste, fixed with high adhesive strength in the wire bonding step, and furthermore, thermal deterioration can be reduced or even prevented. [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 the number average molecular weight (Mn) of the curable organopolysiloxane compound (A) obtained in the production example were taken as standard polystyrene conversion values, and the following equipment and conditions were used. Determination. Device name: HLC-8220GPC, manufactured by Tosoh Co., Ltd. Chromatography column: TSKgelGMHXL, TSKgelGMHXL and TSKgel2000HXL connected sequentially Solvent: THF Injection volume: 80 μl Measuring temperature: 40°C Flow rate: 1 ml/min Detector: Differential refractometer

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

(Manufacturing example 1) 37 g (400 mmol) of methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was put into a 300 ml eggplant-shaped flask, and 10 g of 35% hydrochloric acid was added to dissolve it while stirring. An aqueous solution (0.25 mol% relative to the total amount of silane compounds) formed in 21.6 ml of distilled water was stirred at 30°C for 2 hours, then heated up to 70°C and stirred for 5 hours. After that, the reaction solution was returned to room temperature. Warm (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. Purified 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 curable organopolysiloxane compound (A1). The curable organopolysiloxane compound (A1) had a mass average molecular weight (Mw) of 7,800, and a molecular weight distribution (Mw/Mn) of 4.52. In addition, the IR spectrum data of curable organopolysiloxane compound (A1) are shown below. Si-CH ₃ : 1272 cm ^-1 , 1409 cm ^-1 , Si-O: 1132 cm ^-1

The compounds used in Examples and Comparative Examples are as follows. [(A) ingredient] Curable organopolysiloxane compound (A1): the organopolysiloxane compound obtained in Production Example 1.

[(T) ingredient] Thermally conductive filler (T1): Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd.; trade name "CR-90-2", average particle size: 0.25 μm, thermal conductivity: 8 W/(m.K)) Thermally conductive filler (T2): alumina (manufactured by Sumitomo Chemical Co., Ltd.; trade name "AA-03F", average particle size: 0.25 μm, thermal conductivity: 30 W/(m.K)) Thermally conductive filler (T3): alumina (manufactured by Sumitomo Chemical Co., Ltd.; trade name "AA-04", average particle size: 0.50 μm, thermal conductivity: 30 W/(m.K)) Thermally conductive filler (T4): alumina (manufactured by Sumitomo Chemical Co., Ltd.; trade name "AA-2", average particle size: 2.1 μm, thermal conductivity: 30 W/(m.K)) Thermally conductive filler (T5): Magnesium carbonate (manufactured by Kamijima Chemical Co., Ltd.; trade name "MS-S", average particle size: 1.2 μm, thermal conductivity: 15 W/(m.K)) Thermally conductive filler (T6): aluminum nitride (manufactured by Showa Denko; trade name "AlN0201", average particle size: 2.0 μm, thermal conductivity: 285 W/(m.K))

[Solvent (S)] Diethylene glycol monobutyl ether acetate (BDGAC) (SL) (manufactured by Tokyo Chemical Industry Co., Ltd.; boiling point: 247°C) and tripropylene glycol n-butyl ether (TPnB) (SH) (manufactured by Dow Chemical Company; boiling point : 274°C) mixed solvent [BDGAC:TPnB=40:60 (mass ratio)] [(B) Ingredients] Silane coupling agent (B1): 1,3,5-N-para[3-(trimethoxysilyl)propyl]isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd.; trade name "KBM-9569") ) Silane coupling agent (B2): 3-(trimethoxysilyl)propyl succinic anhydride (manufactured by Shin-Etsu Chemical Co., Ltd.; trade name "X-12-967C")

(Example 1) Add 73 parts of solvent (S), 160 parts of thermally conductive filler (T1), 30 parts of silane coupling agent (B1), and 3 parts of silane to 100 parts of curable organopolysiloxane compound (A1). For the coupling agent (B2), the entire solution was thoroughly mixed and defoamed to obtain adhesive paste 1 with a solid content concentration of 80%.

(Examples 2-8, Comparative Examples 1-4) Adhesive pastes 2-8 and adhesive pastes 1r-4r were prepared in the same manner as in Example 1 except that the types and compounding ratios of the compounds (components) were changed as shown in Table 1.

Using the adhesive pastes 1 to 8 and the adhesive pastes 1r to 4r obtained in Examples and Comparative Examples, the following tests were performed, respectively. The results are shown in Table 1 and Table 2.

[Calculation of volume filling rate] Calculate the volume of the (T) component from the mass and density of the (T) component, and further calculate the mass and density of the components other than the (T) component in the solid content of the adhesive paste. The volume of the components other than the (T) component in the solid content of the paste is calculated by the following formula to calculate the volume filling rate of the (T) component in the solid content of the next paste. Volume filling rate (vol%) = {volume (cm ³ ) of (T) component/[volume (cm ³ ) of (T) component + volume of components other than (T) component in the solid content of the next paste (cm ³ )]}× 100 In addition, the density of the components other than the (T) component in the solid content of the adhesive paste is set to 1.2 g/cm ³ . Doujin Publishing; First Edition; Issued on October 20, 1989), the density of titanium oxide ((T1) component) was set to 4.17 g/cm ³ ; the alumina ((T2) component, (T3) component and ( The density of T4) component) is set to 4.0 g/cm ³ ; the density of magnesium carbonate ((T5) component) is set to 3.04 g/cm ³ ; the density of aluminum nitride ((T6) component) is set to 3.05 g/cm 3 cm ³ .

[Measurement of Thermal Conductivity] That is, the adhesive paste obtained in Examples and Comparative Examples was poured into a Teflon (registered trademark) frame of length 10 mm x width 10 mm x height 0.2 mm, and heat-treated at 120° C. It was cured for 4 hours to obtain a test piece with a smooth surface. Thereafter, the thermal diffusivity of this test piece was measured by a temperature wave method using a thermal diffusivity measuring device (manufactured by ai-Phase Corporation; ai-Phase Mobile 1). In addition, among the constituents of the cured product obtained by heat-curing the adhesive paste, the specific heat of the components other than the thermally conductive filler (T) was set to 1 J/(g·K), and the density was set to 1.2 g. /cm ³ , the thermal conductivity was calculated by the following formula. Thermal conductivity [W/(m.K)] = thermal diffusivity (m ² /s) × specific heat [J/(g.K)] × density (g/cm ³ ) × 10 ⁶

[Evaluation of bonding strength] Apply the bonding paste obtained in Examples and Comparative Examples to the mirror surface of a square (area: 1 mm ² ) silicon wafer with a side length of 1 mm, and place it in a standard environment (temperature: 23 ℃±1℃; relative humidity: 50±5%). After 5 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 3 μm Pressurized and then followed. Thereafter, it was heat-treated at 170° C. for 2 hours to be cured to obtain an adherend to which the test piece was attached. 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.

[Evaluation of Thermal Deterioration of Semiconductor Elements] The adhesive paste obtained in Examples and Comparative Examples was applied to a substrate for fixing optical elements (manufactured by ENOMOTO Corporation; OP-04) so that the thickness of the adhesive paste after pressure bonding was about 3 μm. The optical semiconductor element (manufactured by Genelite; B2020BCI0) was bonded under pressure. Thereafter, it was heat-treated at 170° C. for 2 hours to be cured. Thereafter, the optical semiconductor element and the substrate for fixing the optical element were bonded with two wires and electrically conducted to obtain a test piece for thermal degradation evaluation. Thereafter, the optical semiconductor element in the test piece for thermal deterioration evaluation was made to emit light at a current value of 250 mA, and the initial luminous flux and the luminous flux after energization for 1000 hours were measured using a measuring device (manufactured by Mentor Graphics; T3Ster/TeraLED). From the measured luminous flux, calculate the luminous flux maintenance rate (%) {[luminous flux after energized for 1000 hours (lm)/initial luminous flux (lm)]×100}, and conduct thermal degradation of semiconductor elements based on the following criteria Evaluation. Excellent: The maintenance rate of luminous flux is over 97%. Good: The maintenance rate of luminous flux is more than 95% and less than 97%. Yes: The maintenance rate of luminous flux is more than 93% and less than 95%. Impossible: The maintenance rate of luminous flux is less than 93%.

[Evaluation of wire bonding] The adhesive pastes obtained in Examples and Comparative Examples were applied to the mirror surface of a square (area: 1 mm ² ) silicon wafer (#2000 grinding, 200 μm thick) with a side length of 1 mm, respectively. , 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 is about 3 μm. Pressurize then. Thereafter, it was heat-treated at 170° C. for 2 hours to be cured to obtain an adherend to which the test piece was attached. After that, using a wire bonder [manufactured by Shinkawa Corporation; UTC-2000Super (φ25 μm, Au wire, manufactured by K&S)], under the conditions of 170°C, 0.01 second, load 25 gf, and ultrasonic output 30 PLS, the silicon was bonded using four wires. Bond between the wafer and the copper plate, and observe "whether the test piece (the cured product of the adhesive paste) is peeled off from the electroless-plated silver-plated copper plate." About each adhesive paste obtained by the Example and the comparative example, the same evaluation and observation were performed about 20 repeated wafers, and it evaluated based on the following criteria. Good: Among the 20 wafers, 0 wafers were peeled off or misplaced. Yes: Among the 20 wafers, 1 to 3 wafers were delaminated or displaced. Impossible: Among 20 wafers, 4 or more wafers were peeled off or misaligned.

[Table 1] (A) Ingredients (T) component (B) Ingredients (T) Volume filling rate of component Content of component (T) relative to 100 parts by mass of solid content of adhesive paste Content of component (B1) relative to 100 parts by mass of solid content of adhesive paste Content of component (B) relative to 100 parts by mass of solid content of adhesive paste Content of (T) component with respect to 100 mass parts of (A) component Solid content concentration A1 T1 T2 T3 T4 T5 T6 B1 B2 (parts by mass) (vol%) (parts by mass) (parts by mass) (parts by mass) (parts by mass) (wt%) Example 1 100 160 0 0 0 0 0 30 3 22.6 54.6 10.2 11.3 160 80 Example 2 100 0 160 0 0 0 0 15 3 28.9 57.6 5.4 6.5 160 80 Example 3 100 0 0 160 0 0 0 15 3 28.9 57.6 5.4 6.5 160 80 Example 4 100 0 0 0 160 0 0 15 3 28.9 57.6 5.4 6.5 160 92 Example 5 100 0 0 0 400 0 0 15 3 50.4 77.2 2.9 3.5 400 93 Example 5 100 0 0 0 800 0 0 15 3 67.0 87.1 1.6 2.0 800 90 Example 7 100 0 400 0 0 0 0 17.5 5.5 49.4 76.5 3.3 4.4 400 80 Example 8 100 0 0 0 0 0 160 15 3 34.8 57.6 5.4 6.5 160 84 Comparative example 1 100 0 0 0 0 0 0 15 3 0.0 0.0 12.7 15.3 0 83 Comparative example 2 100 0 0 0 20 0 0 15 3 4.8 14.5 10.9 13.0 20 85 Comparative example 3 100 0 0 0 0 160 0 15 3 34.9 57.6 5.4 6.5 160 80 Comparative example 4 100 0 400 0 0 0 0 15 3 50.4 77.2 2.9 3.5 400 80

[Table 2] Thermal conductivity Followed by strength Thermal Deterioration Evaluation of Semiconductor Elements Evaluation of Wire Bonding (W/(m.K)) N/mm□ Example 1 0.554 10.0 Can Can Example 2 0.744 5.0 good Can Example 3 0.779 5.0 good Can Example 4 0.868 20.6 good good Example 5 2.297 20.3 excellent good Example 5 2.986 6.1 excellent Can Example 7 1.334 5.0 excellent Can Example 8 0.895 20.0 good good Comparative example 1 0.213 25.0 can't good Comparative example 2 0.187 16.7 can't good Comparative example 3 0.681 2.0 Can can't Comparative example 4 1.683 2.0 excellent can't

From Table 1 and Table 2, the following contents can be understood. Adhesive pastes 1 to 8 of Examples 1 to 8 have high thermal conductivity of cured products obtained by heating and curing, and excellent adhesiveness of cured products obtained by heating at high temperatures. Therefore, when the cured products obtained by heating the bonding pastes 1 to 8 are used, thermal deterioration of the semiconductor element can be reduced, and peeling of the semiconductor element in the wire bonding step can be reduced or prevented. Since the thermal conductivity of alumina is higher than that of titanium oxide, adhesive paste 2 containing alumina (T2) as the component (T) can obtain a higher thermal conductivity than adhesive paste 1 containing titanium oxide (T1). Cured. Therefore, when a cured product obtained by heat-curing the adhesive paste 2 is used, thermal degradation of the semiconductor element can be further reduced or even prevented. On the other hand, since titanium oxide is more easily mixed with the (A) component prepared in Production Example 1 than aluminum oxide, and the area of the thermally conductive filler (T) that can be covered by (A) component is large, Therefore, compared with the adhesive paste 2, the cured product obtained by heating the adhesive paste 1 at a high temperature has better adhesiveness (Examples 1 and 2). That is, the most suitable adhesive paste can be obtained by selecting the type of thermally conductive filler (T) in consideration of the type of semiconductor element, the temperature at which the adhesive paste is cured, and the like.

The adhesive paste containing the thermally conductive filler (T) with a large average particle size can obtain a cured product with high thermal conductivity, and the cured product obtained by heating at a high temperature has excellent adhesive strength. Therefore, when a cured product obtained by heating and curing an adhesive paste containing a thermally conductive filler (T) having a large average particle size is used, it is possible to further reduce or even prevent peeling of the semiconductor element in the wire bonding step. Can accomplish (embodiment 2～4). Furthermore, with respect to the solid content of 100 parts by mass of the adhesive paste, the adhesive paste 5 and the adhesive paste 6 with a higher content of the (T) component can obtain heat conduction compared to the adhesive paste 4 with a lower content of the (T) component. Higher curing rate. Therefore, when a cured product obtained by heat-hardening the adhesive paste 5 and the adhesive paste 6 is used, it is possible to further reduce or even prevent thermal degradation of the semiconductor element. On the other hand, although the content of the (T) component of the adhesive paste 6 is large, the content of the (B) component and the (B1) component is relatively small relative to the solid content of 100 parts by mass of the adhesive paste. The adhesiveness of the cured product obtained by heating was slightly lowered (Examples 4-6). Even if it is the adhesive paste containing the thermally conductive filler (T2) with a small average particle diameter, the adhesive paste 7 and the adhesive paste 4r with a large content can obtain the hardened|cured material with high thermal conductivity. In addition, with respect to the solid content of 100 parts by mass of the adhesive paste, the content ratio of the (B) component and (B1) component of the adhesive paste 7 is relatively large, so the cured product obtained by heating the adhesive paste at a high temperature has more Excellent adhesion. (Example 7 and Comparative Example 4). Even the adhesive paste 8 containing aluminum nitride (T6) as the component (T) can obtain a cured product with high thermal conductivity similar to the adhesive paste 4 containing aluminum oxide (T4), and the obtained product can be heated at a high temperature. The cured product has excellent adhesiveness (Examples 4 and 8). That is, the most suitable adhesive paste can be obtained by selecting the content of the thermally conductive filler (T) in consideration of the type of semiconductor element, the temperature at which the adhesive paste is cured, and the like.

On the other hand, since the adhesive paste 1r of Comparative Example 1 does not contain the thermally conductive filler (T), the thermal conductivity of the cured product obtained by thermal curing is low. Therefore, when this cured product was used, thermal deterioration of the semiconductor element was observed. Since the adhesive paste 2r of Comparative Example 2 contained very little content of the (T) component with respect to 100 parts by mass of the solid content of the adhesive paste, the thermal conductivity of the cured product obtained by heat curing was low. Therefore, when this cured product was used, thermal deterioration of the semiconductor element was observed. The adhesive paste 3r of Comparative Example 3 contains magnesium carbonate as the thermally conductive filler (T), which is relatively difficult to mix with the component (A) prepared in Production Example 1, and can be protected by the thermally conductive filler (T) covered by the component (A). Since the area becomes small, a cured product obtained by heating the adhesive paste at a high temperature cannot exhibit sufficient adhesive strength. Therefore, when this cured product was used, peeling of the semiconductor element was observed in the wire bonding step.

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Claims (8)

An adhesive paste, which is an adhesive paste containing a curable organopolysiloxane compound (A) and a thermally conductive filler (T), wherein The thermal conductivity of the cured product obtained by heating and curing the above adhesive paste at 120°C for 4 hours is above 0.5 W/(m.K), The bonding strength of the cured product obtained by heating and curing the adhesive paste at 170° C. for 2 hours to the silver-plated copper plate at 100° C. was 5 N/mm□ or more. The adhesive paste according to claim 1, wherein the curable organopolysiloxane compound (A) is a polysilsesquioxane compound. The adhesive paste according to claim 1 or 2, wherein the thermally conductive filler (T) is an inorganic filler with a thermal conductivity of 5 W/(m.K) or higher. The adhesive paste according to claim 1 or 2, wherein the thermally conductive filler (T) is at least one selected from the group consisting of titanium oxide, aluminum oxide, and aluminum nitride. The adhesive paste as described in claim 1 or 2, wherein the above-mentioned adhesive paste does not substantially contain a noble metal catalyst. The adhesive paste as described in claim 1 or 2, wherein the above-mentioned adhesive paste is an adhesive for fixing materials of semiconductor elements. A method of use, wherein the method of use uses the adhesive paste as described in any one of Claims 1 to 6 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 6 as an adhesive for fixing a semiconductor element, 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; and 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.