WO2022202845A1

WO2022202845A1 - Adhesive paste, usage method for adhesive paste, and production method for semiconductor device

Info

Publication number: WO2022202845A1
Application number: PCT/JP2022/013289
Authority: WO
Inventors: 明来子佐藤; 学宮脇
Original assignee: リンテック株式会社
Priority date: 2021-03-26
Filing date: 2022-03-22
Publication date: 2022-09-29
Also published as: JPWO2022202845A1; WO2022202844A1; JPWO2022202844A1; TW202244237A; TW202244238A

Abstract

The present invention is an adhesive paste that contains a curable organopolysiloxane compound. The storage elastic modulus at -60°C of a cured product obtained by heating and curing the adhesive paste for 20 hours at 80°C and then further heating and curing the adhesive paste for 20 hours at 100°C is less than 2900 MPa, and the adhesion strength at 100°C between a silver-plated copper sheet and a cured product obtained by heating and curing the adhesive paste for 2 hours at 170°C is at least 5 N/mm□. The present invention provides an adhesive paste that: has highly reliable adhesion that can reduce or prevent peeling at an interface with a cured product of a sealing resin, even after subjection to the temperature changes of the usage environment of a semiconductor package; and can reduce or prevent the peeling of a semiconductor element during a wire bonding step. The present invention also provides: a method for using the adhesive paste as a semiconductor element fixing material adhesive; and a production method for a semiconductor device that uses the adhesive paste as a semiconductor element fixing material adhesive.

Description

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

The present invention provides an adhesive paste that has a low storage elastic modulus at −60° C. of a cured product obtained by heat curing, and a cured product obtained by heating at a high temperature has excellent adhesiveness, and the adhesive paste is used as a semiconductor element fixing material. and a method of manufacturing a semiconductor device using this adhesive paste as an adhesive for a semiconductor element fixing material.

Adhesive pastes have heretofore been improved in various ways according to their intended use, and have been widely used industrially as raw materials for optical parts and moldings, adhesives, coating agents, and the like.
Adhesive pastes are also attracting 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 and light-emitting diodes (LEDs), optical semiconductor elements such as light-receiving elements such as solar cells, transistors, sensors such as temperature sensors and pressure sensors, and integrated circuits.

As a method for manufacturing a semiconductor device having a semiconductor element, for example, a die bonding process including a process of fixing the semiconductor element to an adherend such as a lead frame with an adhesive paste and a process of curing the adhesive paste, and a semiconductor element and the lead frame. and a packaging step of covering the fixed semiconductor element with a sealing resin and thermally curing the sealing resin.

However, this method has the following problems.
That is, when an LED element, which is a kind of semiconductor element, is used as an LED package, the stress (thermal expansion stress, contraction stress) generated by temperature changes (repeated process of high temperature and low temperature) in the usage environment of the LED package is alleviated. However, due to poor adhesion between the cured adhesive paste and the cured sealing resin, the interface between the cured adhesive paste and the sealing resin may peel off. When peeling occurs at the interface, an air layer is formed between the two cured products, which may reduce the brightness of the LED.
Moreover, there is also a problem that the strain caused by peeling of the interface between the two cured products tends to cause peeling between the cured product of the adhesive paste and the LED chip and disconnection of the wire.

Furthermore, with the recent miniaturization of semiconductor elements, ultrasonic waves generated from a wire bonding apparatus tend to vibrate the small semiconductor elements, which causes the problem of peeling of the semiconductor elements during the wire bonding process. rice field.

Therefore, even after the temperature change in the usage environment of the semiconductor package, the adhesion reliability at the interface between the cured adhesive paste and the cured sealing resin is high, and the peeling of the semiconductor element is prevented. There is a demand for an adhesive paste with excellent adhesiveness that allows bonding.

In relation to the present invention, Patent Document 1 describes an insulating semiconductor die attach paste with excellent reliability. This document also describes that the storage elastic modulus at 25° C. of the cured product obtained by curing the paste is 3,000 to 3,500 MPa.

In patent document 2, in order to solve the problem that the substrate warps after bonding the substrates in semiconductor bonding, the storage elastic modulus at 50 ° C. is reduced (10 MPa or less). , describes an adhesive capable of reducing the internal stress generated in the adhesive layer when the resin is cured.

Patent Document 3 describes a condensation-curable resin composition capable of obtaining a molded article that is less likely to be brittle and colored even when exposed to high temperatures for a long period of time. This document also describes that a cured product obtained by curing the composition has a storage modulus of 37,000 to 59,000 Pa at 30°C.

Patent Document 4 describes an adhesive composition with improved durability (maintains optical transparency even after long-term use at high temperatures) and adhesiveness. This document also describes the minimum storage modulus of the adhesive composition in the B-stage state (different from the fully cured "C-stage" of the material).

Patent Documents 5 and 6 describe curable compositions and adhesives for optical elements whose cured products have excellent adhesiveness. However, these documents do not describe the adhesion reliability at the interface between the cured product of the curable composition or the adhesive for optical elements and the cured product of the sealing resin.

Japanese Patent Application Laid-Open No. 2003-347322 JP 2013-82834 A Japanese Patent Application Laid-Open No. 2020-90572 (International Publication No. 2020/116199) Japanese Patent Publication No. 2017-533337 (US2017/0306201 A1) WO2020/067451 JP 2018-168286 A

In the semiconductor package, the cured product of the sealing resin occupies a large volume. The degree of influence of the expansion and contraction behavior is very large compared to the cured product of the adhesive paste, and the cooling shrinkage behavior accompanied by the shrinkage stress of the cured product of the sealing resin that occurs during the cooling process of the semiconductor package from high temperature to low temperature, The inventors have focused on the fact that if the cured adhesive paste can flexibly follow the adhesive paste, it is possible to reduce or prevent separation at the interface between the cured adhesive paste and the cured sealing resin.

As described above, Patent Documents 1 to 3 describe the storage elastic modulus at 25° C. to 50° C. of cured products obtained by curing pastes and compositions.
However, in order to alleviate the contraction stress of the cured product of the sealing resin that occurs in the process of cooling the semiconductor package from high temperature to low temperature, there is a demand for an adhesive paste that has a low elastic modulus at a lower temperature (for example, -60°C). be.
In addition, Patent Documents 5 and 6 describe a curable composition and an adhesive for optical elements, the cured product of which is excellent in adhesiveness.
However, according to the studies of the present inventors, even the curable compositions and optical element adhesives described in Patent Documents 5 and 6 have a low elastic modulus at low temperatures (eg, −60° C.). It was sometimes difficult to obtain a cured product.

The present invention has been made in view of such circumstances,
(i) Adhesion reliability that can reduce or prevent peeling at the interface between the sealing resin and the cured product even after temperature changes (repeated process of high and low temperatures) in the environment in which the semiconductor package is used To provide an adhesive paste which has high properties and which can reduce or prevent peeling of a semiconductor element in a wire bonding process;
(ii) To provide a method of using this adhesive paste as an adhesive for a semiconductor element fixing material, and a method of manufacturing a semiconductor device using this adhesive paste as an adhesive for a semiconductor element fixing material.
In the present invention, "high temperature" means "110.degree. C. to 190.degree. C." and "low temperature" means "-65.degree. C. to -45.degree.
Moreover, "excellent adhesiveness" means "high adhesive strength".

The present inventors have found that if the cured product of the adhesive paste can flexibly follow the cooling shrinkage behavior accompanied by the shrinkage stress of the cured product of the sealing resin that occurs in the process of cooling the semiconductor package from high temperature to low temperature, the adhesive paste The inventors focused on the ability to reduce or prevent peeling at the interface between the cured product of the sealing resin and the cured product of the encapsulating resin, and conducted extensive studies. as a result,
(I) A cured product with a low storage elastic modulus at -60 ° C. obtained by heating and curing an adhesive paste containing a curable organopolysiloxane compound is a sealing resin generated in the cooling process from high temperature to low temperature of the semiconductor package. Because it is possible to flexibly follow the cooling shrinkage behavior accompanied by the shrinkage stress of the cured product, even after the temperature change (repeated process of high and low temperatures) in the usage environment of the semiconductor package, the curing of the sealing resin It is possible to reduce or prevent peeling at the interface with an object, and
(ii) A cured product having a specific adhesive strength obtained by heating an adhesive paste containing a curable organopolysiloxane compound at a high temperature can reduce or prevent peeling of a semiconductor element in a wire bonding process. , and completed the present invention.

Thus, according to the present invention, the following adhesive pastes [1] to [8], the method of using the adhesive paste of [9], and the method of manufacturing a semiconductor device using the adhesive paste of [10] are provided.

[1] An adhesive paste containing a curable organopolysiloxane compound (A), which is cured by heating at 80° C. for 20 hours and then cured by heating at 100° C. for 20 hours. , a storage modulus at −60° C. of less than 2900 MPa, and an adhesive strength at 100° C. of 5 N/mm□ or more between a cured product obtained by heating and curing the adhesive paste at 170° C. for 2 hours and a silver-plated copper plate. Adhesive paste that is.

[2] The adhesive paste according to [1], wherein the curable organopolysiloxane compound (A) is a polysilsesquioxane compound.
[3] The adhesive paste according to [1] or [2], which further contains a solvent (S) and has a solid content concentration of 70% by mass or more and less than 100% by mass.
[4] The adhesive paste according to any one of [1] to [3], further containing 5% by mass or more and less than 30% by mass of the following component (B) with respect to the total mass of the solid content of the adhesive paste. .
Component (B): fine particles having an average primary particle size of 8 μm or less [5] Further, the following component (C) is contained in an amount of 2% by mass or more and less than 19% by mass, based on the total mass of the solid content of the adhesive paste. The adhesive paste according to any one of [1] to [4].
(C) component: silane coupling agent

[6] The adhesive paste according to any one of [1] to [5], which does not substantially contain a noble metal catalyst.
[7] The adhesive paste is cured by heating at 80° C. for 20 hours, and then cured by heating at 100° C. for 20 hours. ] to [6].
[8] The adhesive paste according to any one of [1] to [7], which is an adhesive for a semiconductor element fixing material.

[9] A method of using the adhesive paste according to any one of [1] to [8] as an adhesive for a semiconductor element fixing material.
[10] A method for manufacturing a semiconductor device using the adhesive paste according to any one of [1] to [8] as an adhesive for a semiconductor element fixing material, comprising the steps (BI) and (BII) below. A method for manufacturing a semiconductor device having
Step (BI): Applying the adhesive paste to the bonding surface of one or both of the semiconductor element and the support substrate, and press-bonding Step (BII): Heating and curing the adhesive paste of the crimped product obtained in Step (BI) and fixing the semiconductor element to the support substrate

According to the present invention, it is possible to reduce or prevent peeling at the interface between the sealing resin and the cured product even after temperature changes (repeated process of high temperature and low temperature) in the usage environment of the semiconductor package. Provided is an adhesive paste that has high adhesion reliability and can reduce or prevent peeling of a semiconductor element in a wire bonding process.
Further, according to the present invention, there are provided a method of using this adhesive paste as an adhesive for a semiconductor element fixing material, and a method of manufacturing a semiconductor device using this adhesive paste as an adhesive for a semiconductor element fixing material.

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

1) Adhesive Paste The adhesive paste of the present invention is an adhesive paste containing a curable organopolysiloxane compound (A), which is cured by heating at 80° C. for 20 hours and then heated at 100° C. for 20 hours. The cured product obtained by curing has a storage modulus of less than 2900 MPa at −60° C., and adhesion between the cured product obtained by heating and curing the adhesive paste at 170° C. for 2 hours and a silver-plated copper plate at 100° C. It has a strength of 5 N/mm square or more.

In the present invention, the "adhesive paste" means "a viscous liquid at room temperature (23°C) and in a fluid state".
Since the adhesive paste of the present invention has the properties described above, it is excellent in workability in the coating process.
Here, "excellent workability in the coating process" means "in the coating process, when the adhesive paste is discharged from the discharge pipe and then the discharge pipe is pulled up, the amount of stringiness is small or is interrupted immediately, and the resin It must not contaminate the surroundings due to splashing or spread of droplets after application.”

The adhesive paste of the present invention is a cured product obtained by heating and curing the adhesive paste at 80 ° C. for 20 hours and then further heating and curing at 100 ° C. for 20 hours. 2800 MPa or more, more preferably 2200 MPa or more and less than 2700 MPa, particularly preferably 2300 MPa or more and less than 2600 MPa.
Since the storage elastic modulus at −60° C. is less than the above upper limit, the cured product obtained by heat curing is accompanied by shrinkage stress of the cured product of the sealing resin that occurs during the cooling process from high temperature to low temperature of the semiconductor package. Because it can flexibly follow the cooling shrinkage behavior, peeling at the interface between the encapsulating resin and the cured product can be prevented even after temperature changes (repetition of high and low temperatures) in the environment where the semiconductor package is used. It has high adhesion reliability that can be reduced or prevented. Moreover, when it is at least the above lower limit, it becomes easier to obtain a cured product having excellent adhesiveness and heat resistance.
The storage elastic modulus at −60° C. of the cured product obtained by heating and curing the adhesive paste of the present invention can be measured, for example, as follows. Specifically, the adhesive paste of the present invention is cured by heating at 80° C. for 20 hours and then cured by heating at 100° C. for 20 hours to prepare a test piece. By heat-curing under the above conditions, a test piece for dynamic viscoelasticity measurement can be more stably produced by suppressing chipping due to curing shrinkage or the like. The storage elastic modulus of this is measured using a known dynamic viscoelasticity measuring device, and the value at -60°C is extracted.
More specifically, it can be measured by the method described in Examples.

The adhesive paste of the present invention has an adhesive strength of 5 N/mm square or more, preferably 10 N/mm square or more, between a cured product obtained by heating and curing the adhesive paste at 170° C. for 2 hours and a silver-plated copper plate at 100° C. More preferably, it is 13 N/mm square or more.
When the adhesive strength is equal to or higher than the above lower limit, the cured product obtained by heating and curing at a high temperature can reduce or prevent peeling of the semiconductor element in the wire bonding process.
The adhesive strength of the cured product obtained by heating and curing the adhesive paste of the present invention can be measured, for example, as follows. That is, the adhesive paste of the present invention is applied to the mirror surface of a square silicon chip with a side length of 1 mm (area is 1 mm ² ), and the coated surface is placed on a silver-plated copper plate and crimped (adhesive paste after crimping). thickness: about 2 μm) and cured by heat treatment at 170° C. for 2 hours. This is left on the measurement stage of a bond tester at 100 ° C. for 30 seconds, and stress is applied in the horizontal direction (shear direction) to the adhesive surface at a speed of 200 μm / s from a position 100 μm above the adherend, The adhesive strength (N/mm□) at 100° C. between the test piece and the adherend is measured.
In this specification, "1 mm square" means "1 mm square", that is, "1 mm x 1 mm (square with a side length of 1 mm)".
More specifically, it can be measured by the method described in 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), a cured product having excellent adhesiveness can be easily obtained by 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 its molecule.
In addition, since component (A) is a thermosetting compound, 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 through hydrolysis It is preferred to have a group.
Such a functional group is preferably at least one selected from the group consisting of a hydroxyl group and an alkoxy group, more preferably a hydroxyl group and an alkoxy group having 1 to 10 carbon atoms.
The main chain structure of the curable organopolysiloxane compound (A) is not particularly limited, and may be linear, ladder-like, or cage-like.
For example, the structure represented by the following formula (a-1) is used as the linear main chain structure, and the structure represented by the following formula (a-2) is used as the ladder-like main chain structure. Examples of the main chain structure include structures represented by the following formula (a-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 includes an unsubstituted or substituted alkyl group, an unsubstituted A substituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or an alkylsilyl group is preferred. The plurality of Rx in formula (a-1), the plurality of Ry in formula (a-2), and the plurality of Rz in formula (a-3) may be the same or different. However, both Rx in formula (a-1) are not hydrogen atoms.

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

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

Alkenyl groups of unsubstituted or substituted alkenyl groups include, for example, vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, and the like. Ten alkenyl groups are mentioned.

Examples of substituents of the alkyl group, cycloalkyl group and alkenyl group include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a hydroxyl group; a thiol group; an epoxy group; a glycidoxy group; unsubstituted or substituted aryl groups such as phenyl group, 4-methylphenyl group and 4-chlorophenyl group; and the like.

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

The substituents of the aryl group include halogen atoms such as fluorine, chlorine, bromine and iodine atoms; alkyl groups having 1 to 6 carbon atoms such as methyl and ethyl groups; 1 to 6 alkoxy groups; nitro group; cyano group; hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group; an aryl group having a substituent; and the like.

The alkylsilyl group includes trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, tri-t-butylsilyl group, methyldiethylsilyl group, dimethylsilyl group, diethylsilyl group, methylsilyl group, ethylsilyl group and the like.

Among these, Rx, Ry, and Rz are preferably a hydrogen atom, an unsubstituted or substituted C 1-6 alkyl group, or a phenyl group, and an unsubstituted or substituted C 1-6 Alkyl groups are particularly preferred.

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

The silane compound to be used may be appropriately selected according to the desired structure of the curable organopolysiloxane compound (A). Preferred specific examples include bifunctional silane compounds such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, and diethyldiethoxysilane;
methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyldiethoxymethoxysilane, etc. a trifunctional silane compound of;
Tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-t-butoxysilane, tetra-s-butoxysilane, methoxytriethoxysilane, dimethoxydiethoxysilane, trimethoxyethoxysilane tetrafunctional silane compounds such as silane; and the like.

The weight average molecular weight (Mw) of the curable organopolysiloxane compound (A) is usually 800 or more and less than 30,000, preferably 1,000 or more and less than 15,000, more preferably 1,200 or more and less than 10,000. Particularly preferably, it is 2,000 or more and less than 9,000. By using the curable organopolysiloxane compound (A) having a mass average molecular weight (Mw) within the above range, it becomes easier to obtain an adhesive paste that gives a cured product with superior heat resistance and adhesiveness. Further, when the weight average molecular weight (Mw) is less than the above upper limit, it becomes easier to obtain a cured product having a storage elastic modulus of less than 2900 MPa at -60°C.

Although the molecular weight distribution (Mw/Mn) of the curable organopolysiloxane compound (A) is not particularly limited, it is usually 1.0 or more and 10.0 or less, preferably 1.1 or more and 6.0 or less. By using a curable organopolysiloxane compound (A) having a molecular weight distribution (Mw/Mn) within the above range, it becomes easier to obtain an adhesive paste that gives a cured product with superior heat resistance and adhesiveness.
The mass average molecular weight (Mw) and number average molecular weight (Mn) of the curable organopolysiloxane compound (A) are, for example, standard polystyrene conversion values obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. can be obtained as

The curable organopolysiloxane compound (A) of the present invention is preferably a polysilsesquioxane compound obtained by polycondensation of a trifunctional organosilane compound.
Since the adhesive paste of the present invention contains a polysilsesquioxane compound as the component (A), it becomes easier to obtain a cured product having excellent adhesiveness by heating at a high temperature. Therefore, the chip can be held more efficiently in the wire bonding process.

The polysilsesquioxane compound of the present invention is a compound having a repeating unit represented by the following formula (a-4).
The adhesive paste of the present invention contains, as the component (A), a polysilsesquioxane compound having a repeating unit represented by the following formula (a-4), whereby a cured product that is excellent in adhesiveness when heated at a high temperature becomes easier to obtain.

In formula (a-4), R ¹ represents an organic group. Examples of organic groups include unsubstituted alkyl groups, substituted alkyl groups, unsubstituted cycloalkyl groups, substituted cycloalkyl groups, unsubstituted alkenyl groups, substituted alkenyl groups, and unsubstituted aryl groups. aryl groups having substituents, and groups selected from the group consisting of alkylsilyl groups, unsubstituted alkyl groups having 1 to 10 carbon atoms, substituted alkyl groups having 1 to 10 carbon atoms, unsubstituted A group selected from the group consisting of a substituted C6-C12 aryl group and a C6-C12 aryl group having a substituent is more preferred.

The "unsubstituted alkyl group having 1 to 10 carbon atoms" includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n- pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group and the like.
The number of carbon atoms in the “unsubstituted alkyl group having 1 to 10 carbon atoms” represented by R ¹ is preferably 1 to 6.

The number of carbon atoms in the “substituted alkyl group having 1 to 10 carbon atoms” represented by R ¹ is preferably 1 to 6. The number of carbon atoms means the number of carbon atoms in the portion (alkyl group portion) excluding the substituents. Therefore, when R ¹ is a “substituted alkyl group having 1 to 10 carbon atoms”, the number of carbon atoms in R ¹ may exceed 10 in some cases.
Examples of the alkyl group of the "substituted alkyl group having 1 to 10 carbon atoms" include the same groups as the "unsubstituted alkyl group having 1 to 10 carbon atoms".

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

Examples of the “unsubstituted aryl group having 6 to 12 carbon atoms” include phenyl group, 1-naphthyl group, 2-naphthyl group and the like.
The "unsubstituted aryl group having 6 to 12 carbon atoms" represented by R ¹ preferably has 6 carbon atoms.

The number of carbon atoms in the “substituted aryl group having 6 to 12 carbon atoms” represented by R ¹ is preferably 6. The number of carbon atoms means the number of carbon atoms in the portion (aryl group portion) excluding the substituents. Therefore, when R ¹ is a “substituted aryl group having 6 to 12 carbon atoms”, the number of carbon atoms in R ¹ may exceed 12 in some cases.
Examples of the aryl group of the "substituted aryl group having 6 to 12 carbon atoms" include the same aryl groups as the "unsubstituted aryl group having 6 to 12 carbon atoms".

Examples of the substituents of the "substituted aryl group having 6 to 12 carbon atoms" include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group and t-butyl. Alkyl groups such as group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and isooctyl group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkoxy such as methoxy group and ethoxy group group; and the like.
The number of substituent atoms (excluding the number of hydrogen atoms) of the "substituted C6-C12 aryl group" is usually 1-30, preferably 1-20.

Among these, R ¹ is an unsubstituted alkyl group having 1 to 10 carbon atoms, or fluorine, from the viewpoint of easily obtaining a polysilsesquioxane compound with a stable structure and more stable performance as an adhesive paste. An alkyl group having 1 to 10 carbon atoms having atoms 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 becomes easier to obtain an adhesive paste that gives a cured product with superior heat resistance and adhesiveness.
By using a polysilsesquioxane compound in which R ¹ is an alkyl group having 1 to 10 carbon atoms and having a fluorine atom, it becomes easier to obtain an adhesive paste or a cured product having a low refractive index. It becomes easy to be suitably used for the desired optical semiconductor device. In addition, there is a tendency that the maintenance rate of the total light transmittance before and after thermal history, which will be described later, can be increased.

In addition, it is easy to obtain a cured product having a storage elastic modulus of less than 2900 MPa at -60 ° C., and when the semiconductor element is an optical semiconductor element, the light extraction efficiency of the optical semiconductor element is improved, and the luminous efficiency is prevented from decreasing. From the viewpoint of being able to suppress this, R ¹ is more preferably an alkyl group having 1 to 10 carbon atoms and having a fluorine atom.
Furthermore, the alkyl group having 1 to 10 carbon atoms and having a fluorine atom is preferably a bulky alkyl group having a molecular weight of 26 or more from the viewpoint of easily obtaining a cured product having a lower storage modulus at -60°C. More preferably, the molecular weight is 40 or more.
As the alkyl group having 1 to 10 carbon atoms and having a fluorine atom, a group represented by the composition formula: C _m H _(2m−n+1) F _n (m is an integer of 1 to 10, n is 1 or more, (2m+1) are the following integers). Among these, a 3,3,3-trifluoropropyl group is preferred.

The content of the repeating unit represented by the formula (a-4) (that is, the T site described later) in the polysilsesquioxane compound is usually 50 to 100 mol% of the total repeating units, and 70 It is more preferably up to 100 mol %, still more preferably 90 to 100 mol %, and particularly preferably 100 mol %.
By using a polysilsesquioxane compound in which the content ratio of the repeating unit (T site) represented by the formula (a-4) is the above ratio, heat resistance, adhesiveness, and refractive index performance are easily expressed. An adhesive paste can be obtained.
The content ratio of the repeating unit (T site) represented by the formula (a-4) in the polysilsesquioxane compound is, for example, ²⁹ Si- when NMR peak assignment and area integration are possible. It can be determined by measuring NMR and ¹ H-NMR.

Polysilsesquioxane compounds include ketone solvents such as acetone; aromatic hydrocarbon solvents such as benzene; sulfur-containing solvents such as dimethylsulfoxide; ether solvents such as tetrahydrofuran; ester solvents such as ethyl acetate; soluble in various organic solvents such as halogen-containing solvents such as; and mixed solvents comprising two or more of these. Therefore, these solvents can be used to measure the ²⁹ Si-NMR of the polysilsesquioxane compound in solution.

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

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

In formula (a-5), R ¹ has the same meaning as R ¹ in 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 of * include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group and t-butyl group. A plurality of * may all be the same or different.

In addition, the polysilsesquioxane compound is a thermosetting compound, and is a compound capable of undergoing condensation reaction and/or hydrolysis by heating. Therefore, at least one of * in the above formula (a-5) of the plurality of repeating units (T sites) possessed by the polysilsesquioxane compound is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. is preferred, and a hydrogen atom is more preferred.
In addition, when the polysilsesquioxane compound is soluble in the solvent for measurement, by measuring ²⁹ Si-NMR, the hydrogen atom or the number of carbon atoms in * in the above formula (a-5) is 1 to 1 It is possible to confirm the presence of 10 alkyl groups and whether or not the three * in the above formula (a-5) are all Si atoms in the repeating unit.
Furthermore, when assignment of ²⁹ Si-NMR peaks and integration of areas are possible, with respect to the total number of repeating units (T sites) represented by the formula (a-4) in the polysilsesquioxane compound, The total number of repeating units in which all three * in the formula (a-5) are Si atoms can be roughly calculated.
The total number of repeating units (T sites) represented by the formula (a-4) in the polysilsesquioxane compound, and the number of repeating units in which all three * in the formula (a-5) are Si atoms. The total number is preferably 30 to 95 mol %, more preferably 40 to 90 mol %, from the viewpoint of easily obtaining an adhesive paste that gives a cured product with excellent heat resistance.

The polysilsesquioxane compound may have one type of R ¹ (homopolymer) or may have two or more types of R ¹ (copolymer). A copolymer is preferable from the viewpoint of achieving the desired mass average molecular weight of the oxane compound and the effect of imparting properties to the polysilsesquioxane compound by having each ^R1 .

When the polysilsesquioxane compound is a copolymer, the polysilsesquioxane compound may be any of random copolymers, block copolymers, graft copolymers, alternating copolymers, and the like. , random copolymers are preferred from the viewpoint of ease of production.
Moreover, the structure of the polysilsesquioxane compound may be any one of a ladder structure, a double decker structure, a cage structure, a partially cleaved cage structure, a cyclic structure, and a random structure.

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

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

(In the formula, R ¹ has the same meaning as R ¹ in the formula (a-4), R ² represents an alkyl group having 1 to 10 carbon atoms, X ¹ represents a halogen atom, p is 0 to represents an integer of 3. Multiple R ² and multiple X ¹ may be the same or different.)
A polysilsesquioxane compound can be produced by polycondensing at least one of the silane compounds (1) represented by.
Examples of the alkyl group having 1 to 10 carbon atoms for R ² include the same groups as the alkyl group having 1 to 10 carbon atoms represented by * in the above formula (a-5).
A chlorine atom, a bromine atom, etc. are mentioned as ^a halogen atom of X1.

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

substituted alkyltrialkoxysilane compounds such as 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 2-cyanoethyltrimethoxysilane, 2-cyanoethyltriethoxysilane;
3,3,3-trifluoropropylchlorodimethoxysilane, 3,3,3-trifluoropropylchlorodiethoxysilane, 3,3,3-trifluoropropyldichloromethoxysilane, 3,3,3-trifluoropropyldichloro substituted alkylhalogenoalkoxysilane compounds such as ethoxysilane, 2-cyanoethylchlorodimethoxysilane, 2-cyanoethylchlorodiethoxysilane, 2-cyanoethyldichloromethoxysilane, 2-cyanoethyldichloroethoxysilane;
substituted alkyltrihalogenosilane compounds such as 3,3,3-trifluoropropyltrichlorosilane, 2-cyanoethyltrichlorosilane;

Phenyltrialkoxysilane compounds with or without substituents, such as phenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane;
phenylhalogenoalkoxysilane compounds with or without substituents, such as phenylchlorodimethoxysilane, phenyldichloromethoxysilane, 4-methoxyphenylchlorodimethoxysilane, 4-methoxyphenyldichloromethoxysilane;
phenyltrihalogenosilane compounds with or without substituents, such as phenyltrichlorosilane and 4-methoxyphenyltrichlorosilane; and the like.
These silane compounds (1) can be used singly or in combination of two or more.

The method of polycondensing the silane compound (1) is not particularly limited. For example, a method of adding a predetermined amount of a polycondensation catalyst to the silane compound (1) in a solvent or without a solvent and stirring the mixture at a predetermined temperature can be used. More specifically, (a) a method of adding a predetermined amount of acid catalyst to the silane compound (1) and stirring at a predetermined temperature, (b) adding a predetermined amount of a base catalyst to the silane compound (1). (c) adding a predetermined amount of an acid catalyst to the silane compound (1) and stirring at a predetermined temperature; and then adding an excess amount of a base catalyst to make the reaction system basic. , a method of stirring at a predetermined temperature, and the like. Among these, the method (a) or (c) is preferable because the desired polysilsesquioxane compound can be obtained efficiently.

The polycondensation catalyst to be used may be either an acid catalyst or a base catalyst. Two or more polycondensation catalysts may be used in combination, but at least an acid catalyst is preferably used.
Acid catalysts include inorganic acids such as phosphoric acid, hydrochloric acid, boric acid, sulfuric acid and nitric acid; organic acids such as citric acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid; are mentioned. Among these, at least one selected from phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, citric acid, acetic acid, and methanesulfonic acid is preferred.

Base catalysts include aqueous ammonia; trimethylamine, triethylamine, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, pyridine, 1,8-diazabicyclo[5.4.0]-7-undecene, aniline, picoline, 1,4- Organic bases such as diazabicyclo[2.2.2]octane and imidazole; Organic salt hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium t-butoxide Metal alkoxides such as; Metal hydrides such as sodium hydride and calcium hydride; Metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide; Metal carbonates such as sodium carbonate, potassium carbonate and magnesium carbonate; metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate;

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

When a solvent is used during polycondensation, the solvent to be used can be appropriately selected according to the type of silane compound (1). For example, water; aromatic hydrocarbons such as benzene, toluene and xylene; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate and methyl propionate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, s-butyl alcohol and t-butyl alcohol; These solvents can be used singly or in combination of two or more. Further, when the above method (c) is employed, after the polycondensation reaction is carried out in an aqueous system in the presence of an acid catalyst, an organic solvent and a base catalyst (ammonia water, etc.) are added to the reaction solution, and neutral conditions are obtained. Alternatively, a polycondensation reaction may be further performed under basic conditions.

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

The temperature at which the silane compound (1) is polycondensed is usually in the temperature range from 0°C to the boiling point of the solvent used, preferably in the range of 20°C or higher and 100°C or lower. If the reaction temperature is too low, the polycondensation reaction may proceed insufficiently. On the other hand, if the reaction temperature is too high, it becomes difficult to suppress gelation. The reaction is usually completed in 30 minutes to 30 hours.

In addition, depending on the kind of monomer to be used, it may be difficult to increase the molecular weight. For example, a monomer in which R ¹ is an alkyl group having a fluorine atom tends to be less reactive than a monomer in which R ¹ is a normal alkyl group. In such a case, a polysilsesquioxane compound having a desired molecular weight can be easily obtained by reducing the amount of catalyst and conducting the reaction under mild conditions for a long time.

After the completion of the reaction, when an acid catalyst is used, an aqueous alkali solution such as sodium hydrogen carbonate is added to the reaction solution, and when a base catalyst is used, an acid such as hydrochloric acid is added to the reaction solution. The resulting salt is removed by filtration or washing with water to obtain the intended polysilsesquioxane compound.

When the polysilsesquioxane compound is produced by the above method, the portion of OR ² or X ¹ of the silane compound (1) that did not undergo hydrolysis and the subsequent condensation reaction is the polysilsesquioxane compound remain inside.

When the component (A) is, for example, a polysilsesquioxane compound obtained by the polycondensation reaction of the silane compound (1), curing proceeds through a condensation reaction, including reaction with the silane coupling agent described below. Therefore, the adhesive paste of the present invention is different from general heat-curable silicone adhesives that are cured by an addition reaction in the presence of a noble metal catalyst such as a platinum catalyst.
Accordingly, the adhesive paste containing the polysilsesquioxane compound of the present invention contains substantially no noble metal catalyst or contains only a small amount of noble metal catalyst.
Here, "substantially contains no noble metal catalyst or has a low noble metal catalyst content" means that "a component that can be interpreted as a noble metal catalyst is not intentionally added, and an effective It means that the content of the noble metal catalyst is, for example, less than 1 ppm by mass in terms of the mass of the catalytic metal element with respect to the amount of the components.
Here, the term "active ingredient" refers to "a component excluding the solvent (S) contained in the adhesive paste".
The adhesive paste does not substantially contain a noble metal catalyst, or contains a noble metal catalyst, from the viewpoint of stable production in consideration of formulation variations, etc., storage stability, and the viewpoint that noble metal catalysts are expensive. is preferably less.

[Other ingredients]
The adhesive paste of the present invention contains the curable organopolysiloxane compound (A), and may contain the following components.

(1) Solvent (S)
The adhesive paste of the present 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.
The solvent (S) preferably contains an organic solvent having a boiling point of 254° C. or higher (hereinafter sometimes referred to as “organic solvent (SH)”).
Here, "boiling point" refers to "boiling point at 1013 hPa" (same in this specification).
The boiling point of the organic solvent (SH) is preferably 254° C. or higher, more preferably 254° C. or higher and 300° C. or lower.

Specific examples of the organic solvent (SH) include tripropylene glycol-n-butyl ether (boiling point 274° C.), 1,6-hexanediol diacrylate (boiling point 260° C.), diethylene glycol dibutyl ether (boiling point 256° C.), triethylene glycol butyl methyl ether (boiling point 261° C.), polyethylene glycol dimethyl ether (boiling point 264-294° C.), tetraethylene glycol dimethyl ether (boiling point 275° C.), polyethylene glycol monomethyl ether (boiling point 290-310° C.) and the like.
Among these, tripropylene glycol-n-butyl ether and 1,6-hexanediol diacrylate are preferable as the organic solvent (SH) from the viewpoint of easy mixing of the active ingredient.
The organic solvent (SH) may be used singly or in combination of two or more.

The adhesive paste of the present invention may contain a solvent other than the organic solvent (SH).
As a solvent other than the organic solvent (SH), a solvent having a boiling point of 100° C. or more and less than 254° C. (hereinafter sometimes referred to as “organic solvent (SL)”) is preferable.
The organic solvent (SL) is not particularly limited as long as it has a boiling point of 100° C. or more and less than 254° C. and can dissolve or disperse the components of the adhesive paste of the present invention.
By using an organic solvent (SH) together with a solvent other than the organic solvent (SH), the temperature range for heating the adhesive paste to obtain a cured product can be adjusted more precisely. It is possible to reduce the influence of heating on parts and sensor chips.

Specific examples of the organic solvent (SL) include diethylene glycol monobutyl ether acetate (boiling point 247° C.), dipropylene glycol-n-butyl ether (boiling point 229° C.), dipropylene glycol methyl ether acetate (boiling point 209° C.), and diethylene glycol butyl methyl ether. (boiling point 212°C), dipropylene glycol-n-propyl ether (boiling point 212°C), tripropylene glycol dimethyl ether (boiling point 215°C), triethylene glycol dimethyl ether (boiling point 216°C), diethylene glycol monoethyl ether acetate (boiling point 218°C) , diethylene glycol-n-butyl ether (boiling point 230° C.), ethylene glycol monophenyl ether (boiling point 245° C.),
Tripropylene glycol methyl ether (boiling point 242°C), propylene glycol phenyl ether (boiling point 243°C), triethylene glycol monomethyl ether (boiling point 249°C), benzyl alcohol (boiling point 204.9°C), phenethyl alcohol (boiling point 219-221°C) ), ethylene glycol monobutyl ether acetate (boiling point 192°C), ethylene glycol monoethyl ether (boiling point 134.8°C), ethylene glycol monomethyl ether (boiling point 124.5°C), propylene glycol monomethyl ether acetate (boiling point 146°C), cyclo Pentanone (boiling point 130°C), cyclohexanone (boiling point 157°C), cycloheptanone (boiling point 180°C), cyclooctanone (boiling point 195-197°C), cyclohexanol (boiling point 161°C), cyclohexadienone (boiling point 104- 104.5°C) and the like.
Among them, the organic solvent (SL) is preferably a glycol-based solvent, preferably diethylene glycol monobutyl ether acetate or dipropylene glycol-n-butyl ether, more preferably diethylene glycol monobutyl ether acetate, from the viewpoint of easily mixing the active ingredient. preferable.

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

The adhesive paste of the present invention preferably contains the solvent (S) in such an amount that the solid content concentration is preferably 70% by mass or more and less than 100% by mass, more preferably 75% by mass or more and less than 95% by mass.
When the solid content concentration is within this range, it is easy to mix the active ingredient well, and the workability in the process of filling the syringe with the adhesive paste and the coating process is excellent.
Here, "excellent workability in the step of filling the syringe with the adhesive paste" means "capable of filling an appropriate amount into the syringe without air bubbles".
In addition, when performing die bonding, it is possible to suppress the formation of voids between the adhesive paste and the substrate or the like to which it is to be adhered, thereby increasing the reliability of the package.

(2) Microparticles (B)
The adhesive paste of the present invention may contain fine particles (B) having an average primary particle size of 8 μm or less as the component (B).
Component (B) includes fine particles (B1) having an average primary particle size of 5 nm or more and 40 nm or less (hereinafter sometimes referred to as "(B1) component"), and fine particles having an average primary particle size of more than 0.04 µm and not more than 8 µm. (B2) (hereinafter sometimes referred to as "(B2) component").

By containing the fine particles (B1), it becomes easy to obtain an adhesive paste that is excellent in workability in the coating step and gives a cured product that is excellent in adhesiveness and heat resistance when heated at a high temperature.
Since this effect can be obtained more easily, the average primary particle size of the fine particles (B1) is preferably 5 nm or more and 30 nm or less, more preferably 5 nm or more and 20 nm or less.
The average primary particle size of fine particles (B1) can be obtained by observing the shape of fine particles using a transmission electron microscope.

The specific surface area of the fine particles (B1) is preferably 10 m ² /g or more and 500 m ² /g or less, more preferably 20 m ² /g or more and 300 m ² /g or less. When the specific surface area is within the above range, it becomes easier to obtain an adhesive paste with better workability in the coating process.
The specific surface area can be determined by the BET multipoint method.

The shape of the fine particles (B1) may be spherical, chain-like, needle-like, plate-like, flake-like, rod-like, fiber-like, etc., but is preferably spherical. Here, "spherical" means "generally spherical, as well as nearly spherical, including polyhedral shapes that can be approximated to spheres such as spheroids, ovoids, confetti-like, and cocoon-like".

The components of the fine particles (B1) are not particularly limited, and include metals, metal oxides, minerals, metal carbonates, metal sulfates, metal hydroxides, metal silicates, inorganic components, organic components, silicones, and the like. mentioned.
Further, the fine particles (B1) to be used may have a modified surface.

Metals are group 1 (excluding H), groups 2 to 11, group 12 (excluding Hg), group 13 (excluding B), group 14 (excluding C and Si), group 15 (excluding C and Si) in the periodic table. N, P, As and Sb) or Group 16 elements (excluding O, S, Se, Te and Po).

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

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

Examples of metal carbonates include calcium carbonate, magnesium carbonate, etc. Examples of metal sulfates include calcium sulfate, barium sulfate, etc. Examples of metal hydroxides include aluminum hydroxide, etc. Examples of metal silicates include aluminum silicate, Examples include calcium silicate and magnesium silicate.
Moreover, silica etc. are mentioned as an inorganic component. Examples of silica include dry silica, wet silica, surface-modified silica (surface-modified silica), and the like.
Organic components include acrylic polymers and the like.

"Silicone" means an artificial polymer compound with a main skeleton made up of siloxane bonds. Examples include dimethylpolysiloxane, diphenylpolysiloxane, methylphenylpolysiloxane, and the like.

Fine particles (B1) can be used singly or in combination of two or more.
Among these, in the present invention, silica, metal oxides, and minerals are preferable, and silica is more preferable, because an adhesive paste having excellent transparency can be easily obtained.

Among silica, surface-modified silica is preferable, and hydrophobic surface-modified silica is more preferable, from the viewpoint that it is relatively easy to mix as an adhesive paste and that an adhesive paste having excellent workability in the coating process can be easily obtained.
Hydrophobic surface-modified silica includes, on the surface, a trialkylsilyl group having 1 to 20 tricarbon atoms such as a trimethylsilyl group; an alkylsilyl group having 1 to 20 dicarbon atoms such as a dimethylsilyl group; Silica bound with alkylsilyl groups of number 1 to 20; Silica surface-treated with silicone oil; and the like.
Hydrophobic surface-modified silica is, for example, a silica particle having a trialkylsilyl group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 dicarbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or the like. It can be obtained by surface modification using a coupling agent, or by treating silica particles with silicone oil.

When the adhesive paste of the present invention contains fine particles (B1) [component (B1)], the content of component (B1) is not particularly limited, but the amount is preferably 1 % by mass or more and less than 10 mass %, more preferably 3 mass % or more and less than 8 mass %, still more preferably 4 mass % or more and less than 7 mass %.
By using the component (B1) within the above range, the effect of adding the component (B1) can be further expressed.

In addition, the content of component (B1) is preferably 3% by mass or more and less than 15% by mass, more preferably 4% by mass or more and less than 12% by mass, still more preferably 6% by mass or more, relative to the total mass of the solid content of the adhesive paste. It is an amount that is equal to or more than 10% by mass and less than 10% by mass.
When the content of component (B1) is equal to or higher than the above lower limit, the effect of adding component (B1) is more likely to be exhibited. When the content of component (B1) is less than the above upper limit, it becomes easier to obtain a cured product having a storage elastic modulus of less than 2900 MPa at -60°C.
In addition, by using the component (B1) within the above range, it becomes easier to obtain an adhesive paste with high adhesion reliability that can reduce or prevent peeling of semiconductor elements by relieving stress generated during thermal shock.

By containing the fine particles (B2), it becomes easier to obtain an adhesive paste that gives a cured product with excellent adhesiveness and heat resistance when heated at a high temperature.
Since this effect is more likely to be obtained, the average primary particle size of the fine particles (B2) is preferably more than 0.06 μm and 7 μm or less, more preferably more than 0.3 μm and 6 μm or less, still more preferably more than 1 μm and 4 μm or less.

The average primary particle diameter of the fine particles (B2) is measured by a laser scattering method using a laser diffraction/scattering particle size distribution analyzer (for example, product name “LA-920” manufactured by Horiba, Ltd.). can be obtained by performing

The shape of the fine particles (B2) may be the same as those exemplified as the shape of the fine particles (B1), but a spherical shape is preferable.
Further, as the component of the fine particles (B2), the same components as those exemplified as the components of the fine particles (B1) can be mentioned.
The fine particles (B2) can be used singly or in combination of two or more.

Among these, as the fine particles (B2), from the viewpoint of being relatively easy to mix as an adhesive paste, and from the fact that a cured product having excellent adhesiveness and heat resistance can be easily obtained, a metal oxide whose surface is coated with silicone At least one kind of fine particles selected from the group consisting of silica, silica and silicone are preferred, and silica and silicone are more preferred.

When the adhesive paste of the present invention contains fine particles (B2) [component (B2)], the content of component (B2) is not particularly limited, but the amount is preferably 1 % by mass or more and less than 10 mass %, more preferably 3 mass % or more and less than 9 mass %, and still more preferably 4 mass % or more and less than 8 mass %.
By using the component (B2) within the above range, the effect of adding the component (B2) can be further expressed.

In addition, the content of component (B2) is preferably 2% by mass or more and less than 15% by mass, more preferably 3% by mass or more and less than 12% by mass, still more preferably 4% by mass, based on the total mass of the solid content of the adhesive paste. It is an amount that is equal to or more than 10% by mass and less than 10% by mass.
When the content of the component (B2) is equal to or higher than the above lower limit, the effect of adding the component (B2) is more readily manifested. When the content of component (B2) is less than the above upper limit, it becomes easier to obtain a cured product having a storage modulus of less than 2900 MPa at -60°C.
In addition, by using the component (B2) within the above range, it becomes easy to obtain an adhesive paste with high adhesion reliability that can reduce or prevent peeling of semiconductor elements by relieving stress generated during thermal shock.

When the adhesive paste of the present invention contains component (B), the content of component (B) is not particularly limited, but the amount is preferably 2% by mass or more and 20% by mass with respect to the total mass of the adhesive paste. less than, more preferably 6% by mass or more and less than 17% by mass, and still more preferably 8% by mass or more and less than 15% by mass.
By using the component (B) within the above range, the effect of adding the component (B) can be further expressed.

The content of component (B) is preferably 5% by mass or more and less than 30% by mass, more preferably 7% by mass or more and less than 24% by mass, still more preferably 10% by mass, relative to the total mass of the solid content of the adhesive paste. It is an amount that is not less than 20% by mass and less than 20% by mass.
When the content ratio of the component (B) is equal to or higher than the above lower limit, the effect of adding the component (B) becomes more likely to manifest. When the content of component (B) is less than the above upper limit, it becomes easier to obtain a cured product having a storage elastic modulus of less than 2900 MPa at -60°C.
Further, by using the component (B) within the above range, the adhesive paste is applied to the mirror surface of the silicon chip, pressed against an adherend (for example, an electroless silver-plated copper plate), and heat-treated to cure the adhesive paste. When pressed, a good (well-shaped) fillet portion (portion protruding from the silicon chip) is easily formed, so it tends to be easier to obtain an adhesive paste that gives a cured product with higher adhesive strength.
Here, the ``good fillet portion'' means ``from the edge of the chip to a position of 5 to 35% of the length of one side of the chip (for example, a position of 50 to 350 μm when one side of the chip is 1 mm). The protruding portions of are present on all four sides of the chip.

(3) Silane coupling agent (C)
The adhesive paste of the present invention may contain a silane coupling agent as the (C) component.
As the silane coupling agent, a silane coupling agent (C1) having a nitrogen atom in the molecule (hereinafter sometimes referred to as "component (C1)") or a silane coupling agent having an acid anhydride structure in the molecule. (C2) (hereinafter sometimes referred to as "component (C2)"), and preferably contains at least one of silane coupling agent (C1) and silane coupling agent (C2).

By containing the silane coupling agent (C1), excellent workability in the coating process, and excellent curability due to condensation reaction with the component (A) during heating, adhesion when heated at high temperature, It becomes easy to obtain an adhesive paste that gives an excellent cured product due to heat resistance and crack suppression of the cured product.
Here, the phrase "excellent crack suppression of the cured product" means that "when the adhesive paste is heated to obtain a cured product, cracking does not occur in the cured product due to temperature changes".

The silane coupling agent (C1) is not particularly limited as long as it is a silane coupling agent having a nitrogen atom in its molecule. Examples thereof include a trialkoxysilane compound represented by the following formula (c-1), and a dialkoxyalkylsilane compound or dialkoxyarylsilane compound represented by the formula (c-2).

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 t-butoxy. A plurality of R ^a may be the same or different.
R ^b is an alkyl group having 1 to 6 carbon atoms such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group; or a phenyl group, 4-chlorophenyl group, 4- An aryl group with or without a substituent such as a methylphenyl group and a 1-naphthyl group;

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

Among the compounds represented by the above formula (c-1) or (c-2), the compound in which R ^c is an organic group bonded to another group containing a silicon atom includes an isocyanurate skeleton. Examples include those that form an isocyanurate-based silane coupling agent by bonding with other silicon atoms, and those that form a urea-based silane coupling agent by bonding with other silicon atoms via a urea skeleton.

Among these, the silane coupling agent (C1) is preferably an isocyanurate-based silane coupling agent and a urea-based silane coupling agent, since a cured product having higher adhesive strength can be easily obtained. In addition, those having 4 or more silicon-bonded alkoxy groups are preferred.
Having 4 or more silicon-bonded alkoxy groups 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 the isocyanurate-based silane coupling agent having 4 or more silicon-bonded alkoxy groups, a compound represented by the following formula (c-3) is a urea-based silane cup having 4 or more silicon-bonded alkoxy groups. Ring agents include compounds represented by the following formula (c-4).

In the formula, R ^a has the same meaning as R ^a in the formulas (c-1) and (c-2). Each of t1 to t5 independently represents an integer of 1 to 10, preferably an integer of 1 to 6, and particularly preferably 3.

Specific examples of the compound represented by formula (c-3) include 1,3,5-N-tris(3-trimethoxysilylpropyl) isocyanurate, 1,3,5-N-tris(3-tri ethoxysilylpropyl) isocyanurate, 1,3,5-N-tris(3-tri-i-propoxysilylpropyl) isocyanurate, 1,3,5-N-tris(3-tributoxysilylpropyl) isocyanurate, etc. 1,3,5-N-tris[(tri(C1-C6)alkoxy)silyl(C1-C10)alkyl]isocyanurate;
1,3,5-N-tris (3-dimethoxymethylsilylpropyl) isocyanurate, 1,3,5-N-tris (3-dimethoxyethylsilylpropyl) isocyanurate, 1,3,5-N-tris ( 3-dimethoxy i-propylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-dimethoxy n-propylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-dimethoxyphenylsilylpropyl) ) isocyanurate, 1,3,5-N-tris(3-diethoxymethylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-diethoxyethylsilylpropyl) isocyanurate, 1,3, 5-N-tris (3-diethoxy i-propylsilylpropyl) isocyanurate, 1,3,5-N-tris (3-diethoxy n-propylsilylpropyl) isocyanurate, 1,3,5-N-tris ( 3-diethoxyphenylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-di i-propoxymethylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-di i-propoxy ethylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-di-i-propoxy i-propylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-di-i-propoxy n- propylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-di-i-propoxyphenylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dibutoxymethylsilylpropyl)isocyanurate , 1,3,5-N-tris(3-dibutoxyethylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-dibutoxy i-propylsilylpropyl) isocyanurate, 1,3,5- 1,3,5-N-tris [(di (C1-6)alkoxy)silyl(C1-10)alkyl]isocyanurate; and the like.

Specific examples of the compound represented by formula (c-4) include N,N'-bis(3-trimethoxysilylpropyl)urea, N,N'-bis(3-triethoxysilylpropyl)urea, N , N'-bis(3-tripropoxysilylpropyl)urea, N,N'-bis(3-tributoxysilylpropyl)urea, N,N'-bis(2-trimethoxysilylethyl)urea, etc. N'-bis[(tri(C1-C6)alkoxysilyl)(C1-C10)alkyl]urea;
N,N'-bis(3-dimethoxymethylsilylpropyl)urea, N,N'-bis(3-dimethoxyethylsilylpropyl)urea, N,N'-bis(3-diethoxymethylsilylpropyl)urea, etc. N,N'-bis[(di(C1-C6)alkoxy(C1-C6)alkylsilyl(C1-C10)alkyl)urea;
N,N'-bis[(di(C1-6) such as N,N'-bis(3-dimethoxyphenylsilylpropyl)urea, N,N'-bis(3-diethoxyphenylsilylpropyl)urea alkoxy (6 to 20 carbon atoms) arylsilyl (1 to 10 carbon atoms) alkyl) urea;
The silane coupling agents (C1) can be used singly or in combination of two or more.

Among these, the silane coupling agent (C1) includes 1,3,5-N-tris(3-trimethoxysilylpropyl) isocyanurate, 1,3,5-N-tris(3-triethoxysilylpropyl) ) isocyanurate (the above two are hereinafter referred to as “isocyanurate compounds”), N,N′-bis(3-trimethoxysilylpropyl)urea, N,N′-bis(3-triethoxysilylpropyl)urea (The above two are hereinafter referred to as "urea compounds"), and a combination of the isocyanurate compound and the urea compound is preferably used.

When the isocyanurate compound and the urea compound are used in combination, the ratio of the two to be used is preferably 100:1 to 100:200 in mass ratio of (isocyanurate compound) to (urea compound), and 100: 10 to 100:110 is more preferred. By using the isocyanurate compound and the urea compound in combination in such a ratio, it is possible to obtain an adhesive paste that gives a cured product having higher adhesive strength and superior heat resistance.

When the adhesive paste of the present invention contains a silane coupling agent (C1) [(C1) component], the content of the (C1) component is not particularly limited, but the amount is based on the total mass of the solid content of the adhesive paste. On the other hand, the amount is preferably 2% by mass or more and less than 15% by mass, more preferably 2% by mass or more and less than 8% by mass, and still more preferably 2% by mass or more and less than 6% by mass.
By using the component (C1) within the above range, the effect of adding the component (C1) can be further exhibited, and a cured product having a storage elastic modulus at -60°C of less than 2900 MPa can be easily obtained.

By containing the silane coupling agent (C2), it becomes easier to obtain an adhesive paste that has excellent workability in the coating process and gives a cured product with excellent adhesiveness and heat resistance when heated at a high temperature.

Silane coupling agents (C2) include 2-(trimethoxysilyl)ethyl succinic anhydride, 2-(triethoxysilyl)ethyl succinic anhydride, 3-(trimethoxysilyl)propyl succinic anhydride, 3-(tri tri(C1-6)alkoxysilyl(C2-8)alkyl succinic anhydrides such as ethoxysilyl)propyl succinic anhydride;
di(C1-6)alkoxymethylsilyl(C2-8)alkyl succinic anhydrides such as 2-(dimethoxymethylsilyl)ethyl succinic anhydride;
(1-6 carbon atoms) alkoxydimethylsilyl (2-8 carbon atoms) alkyl succinic anhydrides, such as 2-(methoxydimethylsilyl)ethyl succinic anhydride;

trihalogenosilyl (2-8 carbon atoms) alkyl succinic anhydrides such as 2-(trichlorosilyl)ethyl succinic anhydride and 2-(tribromosilyl)ethyl succinic anhydride;
dihalogenomethylsilyl (2-8 carbon atoms) alkyl succinic anhydride such as 2-(dichloromethylsilyl)ethyl succinic anhydride;
and halogenodimethylsilyl (2-8 carbon atoms) alkyl succinic anhydride such as 2-(chlorodimethylsilyl)ethyl succinic anhydride.
The silane coupling agents (C2) can be used singly or in combination of two or more.

Among them, the silane coupling agent (C2) is preferably tri(C 1-6) alkoxysilyl (C 2-8) alkyl succinic anhydride, 3-(trimethoxysilyl) propyl succinic anhydride or 3-(Triethoxysilyl)propyl succinic anhydride is particularly preferred.

When the adhesive paste of the present invention contains a silane coupling agent (C2) [(C2) component], the content of the (C2) component is not particularly limited, but the amount is based on the total mass of the solid content of the adhesive paste. On the other hand, the amount is preferably 0.1% by mass or more and less than 4% by mass, more preferably 0.2% by mass or more and less than 3% by mass, and still more preferably 0.3% by mass or more and less than 2% by mass.
By using the component (C2) within the above range, the effect of adding the component (C2) can be further exhibited, and a cured product having a storage elastic modulus at -60°C of less than 2900 MPa can be easily obtained.

When the adhesive paste of the present invention contains component (C), the content of component (C) is not particularly limited. less than, more preferably 2% by mass or more and less than 13% by mass, still more preferably 3% by mass or more and less than 12% by mass.
By using the component (C) within the above range, the effect of adding the component (C) can be further exhibited, and a cured product having a storage elastic modulus of less than 2900 MPa at -60°C can be easily obtained.

In addition, the content of component (C) is preferably 2% by mass or more and less than 19% by mass, more preferably 2% by mass or more and less than 11% by mass, still more preferably 2% by mass or more, based on the total mass of the solid content of the adhesive paste. It is an amount that is not less than 8% by mass and less than 8% by mass.
When the content of component (C) is at least the above lower limit, the effect of adding component (C) can be further expressed, and the maintenance rate of total light transmittance before and after heat history, which will be described later, is increased. tend to be able to When the content of component (C) is less than the above upper limit, it becomes easier to obtain a cured product having a storage elastic modulus of less than 2900 MPa at −60° C., and an adhesive paste or cured product having a low refractive index is obtained. The optical semiconductor element is an LED element, and when used as an LED package, the light extraction efficiency of the LED element is improved. It is possible to suppress a decrease in luminous efficiency.

(4) Other additive components The adhesive paste of the present invention may contain other components [(D) component] other than the above components (A) to (C) within a range that does not impede the purpose of the present invention. .
Component (D) includes antioxidants, ultraviolet absorbers, light stabilizers, and the like.

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

Phosphorus antioxidants include phosphites, oxaphosphaphenanthrene oxides and the like.
Phenolic antioxidants include monophenols, bisphenols, polymeric phenols, and the like.
Examples of sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate and the like.

These antioxidants can be used singly or in combination of two or more. The amount of antioxidant to be used is generally 10% by mass or less relative to the component (A).

A UV absorber is added for the purpose of improving the light resistance of the resulting adhesive paste.
Examples of UV absorbers include salicylic acids, benzophenones, benzotriazoles, hindered amines and the like.
These ultraviolet absorbers can be used singly or in combination of two or more.
The amount of the ultraviolet absorber to be used is generally 10% by mass or less relative to the component (A).

A light stabilizer is added for the purpose of improving the light resistance of the resulting adhesive paste.
Light stabilizers include, for example, 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}] and other hindered amines.
These light stabilizers can be used singly or in combination of two or more.
The total amount of component (D) used is generally 20% by mass or less relative to component (A).

The adhesive paste of the present invention can be produced, for example, by a production method comprising the following steps (AI) and (AII).
Step (AI): Polycondensation of at least one compound represented by the above formula (a-6) in the presence of a polycondensation catalyst to obtain a polysilsesquioxane compound Step (AII): Step (AI) ), dissolving the polysilsesquioxane compound obtained in step (S) in the solvent (S) to obtain a solution containing the polysilsesquioxane compound

As a method of obtaining a polysilsesquioxane compound by polycondensing at least one compound represented by the above formula (a-6) in the step (AI) in the presence of a polycondensation catalyst, 1) adhesive paste The same methods as those exemplified in the section can be mentioned. The solvent (S) used in step (AII) includes the same solvents as those exemplified as the solvent (S) in the section 1) Adhesive paste.

In the step (AII), as a method of dissolving the polysilsesquioxane compound in the solvent (S), for example, the polysilsesquioxane compound and optionally the components (B) to (D) are dissolved in the solvent (S ), defoaming, and dissolving.
A mixing method and a defoaming method are not particularly limited, and known methods can be used.
The order of mixing is not particularly limited.
According to the production method including the steps (AI) and (AII), the adhesive paste of the present invention can be produced efficiently and simply.

Since the adhesive paste of the present invention contains a polysilsesquioxane compound, it becomes easier to lower the refractive index.
The refractive index (nD) of the adhesive paste of the present invention at 25° C. is preferably less than 1.420, more preferably less than 1.418, and preferably 1.405 or more and less than 1.416. Especially preferred.
By using an adhesive paste having a refractive index (nD) within the above range at 25° C., the refractive index can be lowered even after curing of the adhesive paste. In addition, the light extraction efficiency of the semiconductor device can be improved, and a decrease in luminous efficiency can be suppressed.
The refractive index (nD) of the adhesive paste can be measured by the method described in Examples.

A cured product can be obtained by heating the adhesive paste to volatilize the solvent (S) and cure it.
The heating temperature for curing is usually 80 to 190°C, preferably 150 to 190°C. The heating time for curing is usually 30 minutes to 40 hours, preferably 30 minutes to 10 hours, more preferably 30 minutes to 5 hours, particularly preferably 30 minutes to 3 hours.

The adhesive paste of the present invention is a cured product obtained by heating and curing the adhesive paste at 80 ° C. for 20 hours and then further heating and curing at 100 ° C. for 20 hours. The loss tangent tan δ at -60 ° C. is preferably 0.11. Above, more preferably 0.12 or more and 0.18 or less, particularly preferably 0.125 or more and 0.15 or less.
Since the loss tangent tan δ at −60° C. is at least the above lower limit, the cured product obtained by heat curing is accompanied by contraction stress of the cured product of the sealing resin that occurs during the cooling process of the semiconductor package from high temperature to low temperature. Because it can flexibly follow the cooling shrinkage behavior, peeling at the interface between the encapsulating resin and the cured product can be prevented even after temperature changes (repetition of high and low temperatures) in the environment where the semiconductor package is used. It has higher adhesion reliability that can be further reduced or prevented.
The loss tangent tan δ at -60°C can be calculated as a value of (loss modulus/storage modulus) from the storage modulus and loss modulus at -60°C.
The storage modulus is as described in 1) Adhesive Paste. Also, the loss modulus can be measured by the storage modulus method using a known dynamic viscoelasticity measuring device, as described in the section 1) Adhesive Paste.
Specifically, it can be measured and calculated by the method described in Examples.

A cured product obtained by heating and curing the adhesive paste at 150° C. for 3 hours, and a cured product obtained by further heating at 200° C. for 100 hours have a total light transmittance maintenance rate of preferably 70 before and after the heat history. % or more, more preferably 80% or more, and particularly preferably 90% or more.
When the semiconductor element is an LED element, the LED package has high performance because the maintenance rate of the total light transmittance before and after the thermal history is equal to or higher than the lower limit value.
The maintenance rate of total light transmittance can be measured and calculated by the method described in Examples.

Due to the above properties, the adhesive paste of the present invention can be suitably used as an adhesive for semiconductor element fixing materials.

2) Method of using the adhesive paste and method of manufacturing a semiconductor device using the adhesive paste The method of manufacturing a semiconductor device using the adhesive paste of the present invention as an adhesive for optical element fixing material includes the following steps (BI) and ( BII).
Step (BI): Applying an adhesive paste to the bonding surface of one or both of the semiconductor element and the support substrate and press-bonding Step (BII): Heating and curing the adhesive paste of the pressure-bonded product obtained in Step (BI) and fixing the semiconductor element to the support substrate.

Examples of semiconductor elements include optical semiconductor elements such as light-emitting elements such as lasers and light-emitting diodes (LEDs) and light-receiving elements such as solar cells; transistors; sensors such as temperature sensors and pressure sensors; Among these, an optical semiconductor element is preferable from the viewpoint that the effect of using the adhesive paste of the present invention is likely to be exhibited more preferably.

Materials for supporting substrates for bonding semiconductor elements include glasses such as soda lime glass and heat-resistant hard glass; ceramics; sapphire; iron, copper, aluminum, gold, silver, platinum, chromium, titanium and these metals. alloys, metals such as stainless steel (SUS302, SUS304, SUS304L, SUS309, etc.); polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyether Synthetic resins such as ether ketone, polyethersulfone, polyphenylene sulfide, polyetherimide, polyimide, polyamide, acrylic resin, norbornene resin, cycloolefin resin, and glass epoxy resin;

The adhesive paste of the present invention is preferably filled in a syringe.
Since the syringe is filled with the adhesive paste, workability in the coating process is excellent.
The material of the syringe may be synthetic resin, metal, or glass, but preferably synthetic resin.
The capacity of the syringe is not particularly limited, and may be appropriately determined according to the amount of adhesive paste to be filled or applied.
Moreover, a commercial item can also be used as a syringe. 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 adhesive paste descends vertically to approach the support substrate, and after discharging a predetermined amount of the adhesive paste from the tip of the syringe, the syringe rises to support the support substrate. As the substrate is separated, the support substrate moves laterally. By repeating this operation, the adhesive paste is continuously applied to the support substrate. After that, a semiconductor element is mounted on the applied adhesive paste and pressure-bonded to the support substrate.

The amount of the adhesive paste to be applied is not particularly limited, and may be any amount that allows the semiconductor element to be adhered and the supporting substrate to be firmly adhered by curing. Usually, the amount is such that the thickness of the coating film of the adhesive paste is 0.5 μm or more and 5 μm or less, preferably 1 μm or more and 3 μm or less.

Then, the semiconductor element is fixed to the support substrate by heating and curing the adhesive paste of the obtained press-fit.
The heating temperature and heating time are as described in the section 1) Adhesive paste.

Moreover, the method of manufacturing the semiconductor device of the present invention may be a method further including the following step (BIII) and step (BIV).
Step (BIII): Connecting wires between the semiconductor element obtained in Step (BII) and the electrodes of the support substrate Step (BIV): In Step (BII), the support substrate is provided with A step of covering the fixed semiconductor element with a sealing resin and heating and curing the sealing resin.

In the step (BIII), the electrodes of the semiconductor element and the electrodes of the support substrate are connected by wires to electrically connect them.
Wires to be used include copper, aluminum, gold, alloys, and the like.

In the above step (BIV), the method of covering the semiconductor element fixed to the support substrate with the sealing resin and heating and curing the sealing resin is not particularly limited. For example, a method of injecting a sealing resin having fluidity into a support substrate and curing the sealing resin by heating to form a sealing resin layer; and heat-curing the sealing resin to form a sealing resin layer.

The heating temperature for curing the sealing resin is usually 80 to 190°C, preferably 100 to 170°C. The heating time for curing is usually 30 minutes to 10 hours, preferably 30 minutes to 5 hours, more preferably 30 minutes to 3 hours.

The sealing resin to be used is not particularly limited as long as it can seal the semiconductor element. Examples thereof include silicone-based resins, rubber-based resins, (meth)acrylic-based resins, polyolefin-based resins, polyester-based resins, and styrene-based thermoplastic resins, with silicone-based resins being preferred.

The semiconductor device obtained by the semiconductor device manufacturing method of the present invention has high adhesion reliability in which peeling at the interface between the cured adhesive paste and the cured sealing resin is reduced or prevented, and Moreover, the semiconductor element is fixed with high adhesive strength.

EXAMPLES The present invention will be described in more detail below with reference to examples. However, the present invention is by no means limited to the following examples.
Parts and % in each example are based on mass unless otherwise specified.

[Average molecular weight measurement]
The mass-average molecular weight (Mw) and number-average molecular weight (Mn) of the curable organopolysiloxane compound (A) obtained in Production Examples were converted to standard polystyrene values and measured using the following equipment and conditions.
Apparatus name: HLC-8220GPC, manufactured by Tosoh Corporation Column: TSKgelGMHXL, TSKgelGMHXL, and TSKgel2000HXL sequentially connected Solvent: Tetrahydrofuran Injection volume: 20 μl
Measurement temperature: 40°C
Flow rate: 1 ml/min Detector: Differential refractometer

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

(Production example 1)
In a 300 mL eggplant-shaped flask, 56.2 g (257.5 mmol) of 3,3,3-trifluoropropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 30. After charging 6 g (171.7 mmol), an aqueous solution of 0.2236 g of 35% hydrochloric acid (the amount of HCl is 2.146 mmol, 0.5 mol % with respect to the total amount of silane compounds) dissolved in 46.35 ml of distilled water was added. The mixture was added with stirring, and the whole volume was stirred at 30° C. for 2 hours, then heated to 70° C. and stirred for 20 hours.
While continuing to stir the content, a mixed solution of 0.1305 g of 28% aqueous ammonia (the amount of NH ₃ is 2.146 mmol) and 59.4 g of propyl acetate was added, and the mixture was stirred at 70° C. for 1 hour.
While continuing to stir the content, a mixed solution of 0.1305 g of 28% aqueous ammonia (the amount of NH ₃ is 2.146 mmol) and 5 g of propyl acetate was added, and the mixture was stirred at 70° C. for 2 hours.
After allowing the reaction solution to cool to room temperature (23° C.), 80 g of propyl acetate and 100 g of water were added to the solution for liquid separation to obtain an organic layer containing a reaction product. Drying treatment was performed by adding magnesium sulfate to the organic layer.
After the magnesium sulfate was removed by filtration, the organic layer was concentrated by an evaporator and the concentrate was vacuum-dried to obtain 60.0 g of curable organopolysiloxane compound (A1).
The curable organopolysiloxane compound (A1) had a mass average molecular weight (Mw) of 3,000 and a molecular weight distribution (Mw/Mn) of 1.52.
IR spectrum data of the curable organopolysiloxane compound (A1) are shown below.
Si—CH ₃ : 1272 cm ⁻¹ , 1409 cm ⁻¹ , Si—O: 1132 cm ⁻¹ , CF: 1213 cm ⁻¹

(Production example 2)
A 300 mL eggplant-shaped flask was charged with 17.0 g (77.7 mmol) of 3,3,3-trifluoropropyltrimethoxysilane and 32.33 g (181.3 mmol) of methyltriethoxysilane, followed by adding 14 parts of distilled water. An aqueous solution prepared by dissolving 0.0675 g of 35% hydrochloric acid (0.65 mmol of HCl, 0.25 mol % with respect to the total amount of silane compounds) in 0.0 ml was added with stirring, and the total volume was heated at 30° C. for 2 hours. Then, the temperature was raised to 70° C. and the mixture was stirred for 20 hours.
While continuing to stir the contents, a mixed solution of 0.0394 g of 28% aqueous ammonia (the amount of _NH3 is 0.65 mmol) and 46.1 g of propyl acetate was added to adjust the pH of the reaction solution to 6.9. , and stirred at 70° C. for 40 minutes.
After the reaction solution was allowed to cool to room temperature (23° C.), 50 g of propyl acetate and 100 g of water were added thereto for liquid separation treatment to obtain an organic layer containing a reaction product. Drying treatment was performed by adding magnesium sulfate to the organic layer.
After removing magnesium sulfate by filtration, the organic layer was concentrated with an evaporator and the concentrate was dried in vacuo to obtain 22.3 g of a curable organopolysiloxane compound (A2).
The curable organopolysiloxane compound (A2) had a mass average molecular weight (Mw) of 5,500 and a molecular weight distribution (Mw/Mn) of 3.40.
IR spectrum data of the curable organopolysiloxane compound (A2) are shown below.
Si—CH ₃ : 1272 cm ⁻¹ , 1409 cm ⁻¹ , Si—O: 1132 cm ⁻¹ , CF: 1213 cm ⁻¹

(Production example 3)
A 300 mL eggplant-shaped flask was charged with 5.24 g (24.0 mmol) of 3,3,3-trifluoropropyltrimethoxysilane and 38.5 g (216.0 mmol) of methyltriethoxysilane, followed by adding 12 parts of distilled water. An aqueous solution prepared by dissolving 0.0625 g of 35% hydrochloric acid (0.6 mmol of HCl, 0.25 mol % with respect to the total amount of silane compounds) in 96 ml was added with stirring, and the total volume was heated at 30°C for 2 hours. Then, the temperature was raised to 70° C. and the mixture was stirred for 20 hours.
While continuing to stir the content, a mixed solution of 0.073 g of 28% aqueous ammonia (the amount of NH ₃ is 1.2 mmol) and 40.4 g of propyl acetate was added, and the mixture was stirred at 70° C. for 40 minutes. .
After the reaction solution was allowed to cool to room temperature (23° C.), 50 g of propyl acetate and 100 g of water were added thereto for liquid separation treatment to obtain an organic layer containing a reaction product. Drying treatment was performed by adding magnesium sulfate to the organic layer.
After the magnesium sulfate was removed by filtration, the organic layer was concentrated by an evaporator and the concentrate was vacuum-dried to obtain 23.4 g of a curable organopolysiloxane compound (A3).
The curable organopolysiloxane compound (A3) had a mass average molecular weight (Mw) of 6,000 and a molecular weight distribution (Mw/Mn) of 3.80.
IR spectrum data of the curable organopolysiloxane compound (A3) are shown below.
Si—CH ₃ : 1272 cm ⁻¹ , 1409 cm ⁻¹ , Si—O: 1132 cm ⁻¹ , CF: 1213 cm ⁻¹

(Production example 4)
After charging 71.37 g (400 mmol) of methyltriethoxysilane into a 300 ml eggplant-shaped flask, dissolve 0.10 g of 35% hydrochloric acid (0.25 mol % with respect to the total amount of silane compounds) in 21.6 ml of distilled water. The resulting aqueous solution was added with stirring, and the total volume was stirred at 30° C. for 2 hours, then heated to 70° C. and stirred for 5 hours.
0.12 g of 28% aqueous ammonia (0.5 mol % with respect to the total amount of the silane compound) was added thereto while stirring the entire volume, the temperature was raised to 70° C., and the mixture was further stirred for 3 hours.
Purified water was added to the reaction solution, the phases were separated, and this operation was repeated until the pH of the aqueous layer reached 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 (A4).
The curable organopolysiloxane compound (A4) had a mass average molecular weight (Mw) of 7,800 and a molecular weight distribution (Mw/Mn) of 4.52.
IR spectrum data of the curable organopolysiloxane compound (A4) 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 shown below.
[(A) component]
Curable organopolysiloxane compound (A1): Organopolysiloxane compound obtained in Production Example 1 Curable organopolysiloxane compound (A2): Organopolysiloxane compound obtained in Production Example 2 Curable organopolysiloxane compound (A3 ): Organopolysiloxane compound obtained in Production Example 3 Curable organopolysiloxane compound (A4): Organopolysiloxane compound obtained in Production Example 4

[Solvent (S)]
Diethylene glycol monobutyl ether acetate (BDGAC) (SL) (manufactured by Tokyo Chemical Industry Co., 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) Component]
Fine particles (B1): silica fine particles (manufactured by Nippon Aerosil Co., Ltd., product name “AEROSIL RX300”, average primary particle size: 7 nm, specific surface area: 210 m ² /g)
Microparticles (B2): Silicone microparticles (manufactured by Nikko Rica, product name “MSP-SN08”, average primary particle size: 0.8 μm, shape: spherical)
[(C) component]
Silane coupling agent (C1): 1,3,5-N-tris[3-(trimethoxysilyl)propyl]isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM-9659”)
Silane coupling agent (C2): 3-(trimethoxysilyl)propylsuccinic anhydride (manufactured by Shin-Etsu Chemical Co., Ltd., product name “X-12-967C”)

(Example 1)
Curable organopolysiloxane compound (A1) 100 parts, fine particles (B1) 10 parts, fine particles (B2) 10 parts, solvent (S) 35.5 parts, silane coupling agent (C1) 5 parts, silane coupling agent (C2) 1 part was added, and the entire content was thoroughly mixed and defoamed to obtain an adhesive paste 1 having a solid concentration of 78%.

(Examples 2 to 9, Comparative Examples 1 to 7)
Adhesive pastes 2 to 9 and 1r to 7r were obtained in the same manner as in Example 1, except that the types and blending ratios of the compounds (each component) were changed to those shown in Table 1 below.

The following tests were performed using the adhesive pastes 1 to 9 and 1r to 7r obtained in Examples and Comparative Examples. The results are shown in Table 2 below.

[Measurement of refractive index of adhesive paste]
The adhesive pastes obtained in Examples and Comparative Examples were discharged onto a horizontal surface, and the measurement surface of a pen refractometer (manufactured by ATAGO, PEN-RI) was pressed at 25° C. to measure the refractive index (nD).

[Storage modulus and loss tangent]
The adhesive pastes obtained in Examples and Comparative Examples were cured by heating at 80° C. for 20 hours and then cured by heating at 100° C. for 20 hours to prepare test pieces of length 20 mm×width 5 mm×thickness 1 mm. Next, the test piece was placed on a dynamic viscoelasticity measuring device (manufactured by Netsch Japan, product name: DMA 242E Artemis) (distance between chucks 10 mm), tensile mode, frequency 10 Hz, amplitude 5 μm, temperature increase rate 5 ° C. /min, the storage modulus in the temperature range of -65 to 30°C was measured, and the storage modulus and loss modulus at -60°C were extracted.
Also, the loss tangent tan δ (loss elastic modulus/storage elastic modulus) was calculated from the storage elastic modulus and the loss elastic modulus at -60°C.

[Adhesion strength evaluation]
The adhesive paste obtained in Examples and Comparative Examples was applied to the mirror surface of a square silicon chip with a side length of 1 mm (area of 1 mm ² ), and the coated surface was an adherend [electroless silver-plated copper plate (silver The average roughness of the plated surface Ra: 0.025 μm)], and the pressure bonding was performed so that the thickness of the adhesive paste after pressure bonding was about 2 μm. After that, it was cured by heat treatment at 170° C. for 2 hours to obtain an adherend with a test piece. This adherend with the test piece is left on the measurement stage of a bond tester (Daige, series 4000) at 100 ° C. for 30 seconds, and is adhered at a speed of 200 μm / s from a position 100 μm above the adherend. Stress was applied in the horizontal direction (shearing direction) to the surface, and the adhesive strength (N/mm□) between the test piece and the adherend was measured at 100°C.

[Maintenance rate of total light transmittance]
The adhesive pastes obtained in Examples and Comparative Examples were cured by heating at 150° C. for 3 hours to prepare test pieces having a thickness of 1 mm.
Using a spectrophotometer (manufactured by SHIMADZU, product name: UV-VIS-NIR SPECTROPHOTOMETER UV-3600, using an integrating sphere), the total light transmittance T ₀ (%) at a wavelength of 450 nm was measured for the test piece. Furthermore, the test piece obtained by heating the test piece at 200° C. for 100 hours was measured for total light transmittance T ₁ (%) at a wavelength of 450 nm.
From the measured total light transmittance T ₀ and total light transmittance T ₁ , the total light transmittance maintenance rate of the cured product before and after the heat history (%) [(T ₁ (%) / T ₀ (%)) × 100] was calculated.

[Evaluation of peel resistance between cured product of adhesive paste and cured product of sealing resin]
Support substrate with molding frame (reflector) for LED package [manufactured by Enomoto, product name: 5050 D / G PKG LEADFRAME, inner depth of molding frame (that is, inner wall height): 0.85 mm], Examples and comparison The adhesive paste obtained in Example was applied in a diameter of 1.8 mm. Then, after curing by heat treatment at 150 ° C. for 3 hours, a silicone-based sealing resin (manufactured by Shin-Etsu Chemical Co., Ltd., product name "LPS-3419") is poured into the molding frame of the support substrate with a molding frame and molded. Filled up to the upper end face of the frame. This was heated at 120° C. for 1 hour and then at 150° C. for 1 hour to obtain a test piece.
Next, after exposing this test piece to an environment of 85 ° C. and 85% RH for 168 hours, IR reflow (reflow furnace: manufactured by Sagami Riko Co., Ltd., product Name: WL-15-20DNX type) was subjected to reflow treatment. After that, 500 cycles were carried out using a thermal cycle tester, with one cycle being a test of leaving at -60°C and +125°C for 30 minutes each. After that, the hardened sealing resin adhering to the inner wall of the molding frame of the support substrate with molding frame is cut off with a cutter, and a needle ("silk needle 5 defined in JIS S 3008" is attached to the cut part that has been cut off). No.”) is inserted from the upper end toward the direction of the cured adhesive paste to a depth of 0.5 mm ± 0.05 mm from the upper surface of the cured sealing resin, and the needle is rotated 80° (sealing resin The hardened product of (2) is caught and lifted) for 2 seconds to remove the hardened product of the encapsulating resin.
During the operation to remove the cured product of the sealing resin, cohesive failure occurs inside the cured product of the sealing resin (OK test piece), or at the interface between the cured product of the adhesive paste and the cured product of the sealing resin. It was tested whether it was peeled off (NG test piece). The same test was performed 100 times for each of the adhesive pastes obtained in Examples and Comparative Examples.
Of the 100 test pieces, the number of OK test pieces and the number of NG test pieces are used to calculate the rate of peeling (%) [(number of NG test pieces / total number of test pieces) × 100], and the following criteria evaluated with
A: The peeling occurrence rate was 15% or less.
B: The peeling occurrence rate was greater than 15% and 25% or less.
C: The rate of occurrence of peeling was greater than 25%.

[Wire bonding evaluation]
The adhesive pastes obtained in Examples and Comparative Examples were each applied to the mirror surface of a square silicon chip (#2000 grinding, 50 μm thick) having a side length of 1 mm (area of 1 mm ² ), and the coated surface was covered. The adhesive paste was press-bonded onto an object [electroless silver-plated copper plate (silver-plated surface average roughness Ra: 0.025 µm)] so that the thickness of the adhesive paste after press-bonding was about 2 µm. Then, it was cured by heat treatment at 170° C. for 2 hours to obtain an adherend with a test piece. After that, using a wire bonder [manufactured by Shinkawa; UTC-2000 Super (φ25 μm, Cu wire)] at 150° C. for 0.01 second, a load of 25 gf, an ultrasonic output of 30 PLS, and four wires between the silicon chip and the copper plate. After bonding, "presence or absence of peeling of the test piece (hardened adhesive paste) from the electroless silver-plated copper plate" was observed. The same observation was repeated for 20 chips for each of the adhesive pastes obtained in Examples and Comparative Examples.
When 0 chips out of 20 chips were peeled off, the peeling was evaluated as "absent", and in other cases, the peeling was evaluated as "yes".

Tables 1 and 2 reveal the following.
The adhesive pastes 1 to 9 of Examples 1 to 9 have a low storage elastic modulus of less than 2900 MPa at -60 ° C. of the cured product obtained by heat curing, and the cured product obtained by heating at a high temperature has adhesiveness. It is excellent. Therefore, even after the cured product obtained by heating the adhesive pastes 1 to 9 undergoes temperature changes (repeated process of high and low temperatures) in the usage environment of the semiconductor package, the interface with the cured product of the sealing resin It has high adhesion reliability capable of reducing or preventing peeling in the wire bonding process, and can prevent peeling of the semiconductor element in the wire bonding process.
Further, the adhesive paste containing, as the component (A), a curable organopolysiloxane compound (A1) having a high proportion of repeating units having an alkyl group having a fluorine atom is a curable organopolysiloxane having a low proportion of the repeating units. Compared to the adhesive paste containing the compound (A2), the cured product obtained by heat curing has a lower storage elastic modulus at −60° C. and a cured product with a higher loss tangent tan δ can be obtained (Example 1 and 2). On the other hand, in the adhesive paste containing the curable organopolysiloxane compound (A1) having a large proportion of repeating units having an alkyl group having a fluorine atom, the proportion of the repeating units is higher than that of the curable organopolysiloxane compound (A2). Compared to adhesive pastes containing even less curable organopolysiloxane compound (A3), a cured product with a lower storage elastic modulus at -60 ° C. can be obtained, but the cured product obtained by heating at a high temperature The bond strength is lower (Example 6 and Comparative Example 5).
That is, as the component (A), by adjusting the proportion of repeating units having an alkyl group having a fluorine atom and the molecular weight of the alkyl group having a fluorine atom, the storage elastic modulus and adhesive strength at -60 ° C. are taken into consideration. , an optimal adhesive paste can be obtained.
An adhesive paste with a lower content of component (B) with respect to the total mass of the adhesive paste and the total mass of the solid content of the adhesive paste can provide a cured product with a lower storage elastic modulus at −60° C. (Example 3-5).
An adhesive paste with a low content of component (C1) has a significantly lower storage modulus at −60° C. of a cured product obtained by heat curing compared to an adhesive paste with a high content of component (C1). and the loss tangent tan δ can be significantly increased (Examples 1 and 6).
An adhesive paste with a lower content of component (C) relative to the total solid mass of the adhesive paste has a lower storage elastic modulus at −60° C. and a cured product with a higher loss tangent tan δ. (Examples 7-9).

On the other hand, since the adhesive paste 1r of Comparative Example 1 contains a large amount of the component (C) relative to the total solid content of the adhesive paste, the cured product has a storage modulus of 2900 MPa or more at −60° C., and the loss tangent tan δ becomes less than 0.11. Therefore, when this cured product is used, peeling is often observed at the interface between the sealing resin and the cured product, resulting in poor adhesion reliability in the semiconductor package.
In addition, since the adhesive paste 2r of Comparative Example 2 has a very large content ratio of the (B1) component and the (C) component with respect to the total mass of the solid content of the adhesive paste, the storage elastic modulus of the cured product at -60 ° C. is 2900 MPa. As described above, the loss tangent tan δ is less than 0.11. Therefore, when this cured product is used, peeling is often observed at the interface between the sealing resin and the cured product, resulting in poor adhesion reliability in the semiconductor package.
Since the adhesive paste 3r of Comparative Example 3 contains a large amount of the component (B1) with respect to the total mass of the adhesive paste and the total mass of the solid content of the adhesive paste, the cured product has a storage elastic modulus of 2900 MPa or more at −60° C. . Therefore, when this cured product is used, peeling is often observed at the interface between the sealing resin and the cured product, resulting in poor adhesion reliability in the semiconductor package.
Since the adhesive paste 4r of Comparative Example 4 has a relatively large content ratio of the component (C) with respect to the total solid content of the adhesive paste, the storage elastic modulus of the cured product at -60 ° C. is 2900 MPa or more, and the loss tangent tan δ becomes less than 0.11. Therefore, when this cured product is used, peeling is often observed at the interface between the sealing resin and the cured product, resulting in poor adhesion reliability in the semiconductor package.

The adhesive paste 6r of Comparative Example 6 did not contain the component (C), and was cured by heating at 80°C for 20 hours and then at 100°C for 20 hours. ° C.), it was not possible to prepare a test piece for storage modulus measurement because the hardness did not reach a level that could be handled without deformation. Moreover, since the components (B) and (C) were not contained, the cured product obtained by heating the adhesive paste at a high temperature does not exhibit sufficient adhesive strength. Therefore, when this cured product was used, peeling of the semiconductor element was observed in the wire bonding process, and peeling occurred at the interface between the cured adhesive paste and the bottom surface of the support substrate with the molding frame. I couldn't.
The adhesive paste 7r of Comparative Example 7 has a low content of the component (C), and after curing the adhesive paste by heating at 80° C. for 20 hours, the cured product obtained by further heating and curing at 100° C. for 20 hours is room temperature ( 23° C.), it was not possible to prepare a test piece for measuring the storage elastic modulus because the hardness was not such that it could be handled without deformation. Moreover, since the component (B) was not contained and the content of the component (C) was low, the cured product obtained by heating the adhesive paste at a high temperature did not exhibit sufficient adhesive strength. Therefore, when this cured product was used, peeling of the semiconductor element was observed in the wire bonding process, and peeling occurred at the interface between the cured adhesive paste and the bottom surface of the support substrate with the molding frame. I couldn't.

Claims

An adhesive paste containing a curable organopolysiloxane compound (A),
After curing the adhesive paste by heating at 80° C. for 20 hours, the cured product obtained by further heating and curing at 100° C. for 20 hours has a storage modulus of less than 2900 MPa at −60° C. An adhesive paste having an adhesive strength of 5 N/mm square or more at 100° C. between a cured product obtained by heating and curing at 100° C. for 2 hours and a silver-plated copper plate.
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, which further contains a solvent (S) and has a solid content concentration of 70% by mass or more and less than 100% by mass.
The adhesive paste according to any one of claims 1 to 3, further comprising 5% by mass or more and less than 30% by mass of the following component (B) with respect to the total mass of the solid content of the adhesive paste.
(B) component: fine particles with an average primary particle size of 8 μm or less
The adhesive paste according to any one of claims 1 to 4, further comprising 2% by mass or more and less than 19% by mass of the following component (C) with respect to the total mass of the solid content of the adhesive paste.
(C) component: silane coupling agent
The adhesive paste according to any one of claims 1 to 5, which contains substantially no noble metal catalyst.
Claims 1 to 6, wherein the cured product obtained by heating and curing the adhesive paste at 80°C for 20 hours and then further heating and curing at 100°C for 20 hours has a loss tangent tan δ at -60°C of 0.11 or more. The adhesive paste according to any one of 1.
The adhesive paste according to any one of claims 1 to 7, which is an adhesive for semiconductor element fixing materials.
A method of using the adhesive paste according to any one of claims 1 to 8 as an adhesive for a semiconductor element fixing material.
A method for manufacturing a semiconductor device using the adhesive paste according to any one of claims 1 to 8 as an adhesive for a semiconductor element fixing material, comprising the following steps (BI) and (BII). Method.
Step (BI): Applying the adhesive paste to the bonding surface of one or both of the semiconductor element and the support substrate, and press-bonding Step (BII): Heating and curing the adhesive paste of the crimped product obtained in Step (BI) and fixing the semiconductor element to the support substrate