CN115124973A

CN115124973A - Adhesive paste, method for using adhesive paste, and method for manufacturing semiconductor device

Info

Publication number: CN115124973A
Application number: CN202210298900.3A
Authority: CN
Inventors: 三浦迪; 宫胁学
Original assignee: Lintec Corp
Current assignee: Lintec Corp
Priority date: 2021-03-26
Filing date: 2022-03-25
Publication date: 2022-09-30
Also published as: KR20220134436A; TW202300622A; JP2022151346A

Abstract

The present invention is an adhesive paste comprising a thermosetting organopolysiloxane compound (A) and an organic Solvent (SL) having a boiling point of 100 ℃ or higher and lower than 254 ℃, wherein the adhesive paste is heated at 100 ℃ for 2 hours and then the mass reduction rate of the adhesive paste before and after heating is reduced _100℃2h Is 10% or more, and the mass reduction rate of the adhesive paste before and after heating the adhesive paste at 170 ℃ for 2 hours is defined as the mass reduction rate _170℃2h When it is, the mass is reducedRate of decrease _170℃2h Mass reduction rate _100℃2h Less than 14%. According to the present invention, there are provided an adhesive paste which is excellent in adhesiveness of a cured product obtained by heating at a low temperature and which can mount a semiconductor element satisfactorily even after a long period of time has elapsed after being applied to an object to be coated, a method for using the adhesive paste as an adhesive for a semiconductor element-fixing material, and a method for producing a semiconductor device.

Description

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

Technical Field

The present invention relates to an adhesive paste which is excellent in adhesiveness of a cured product obtained by heating at a low temperature and which can mount a semiconductor element satisfactorily even after being left for a long time after being applied to an object to be coated, a method for using the adhesive paste as an adhesive for a semiconductor element-fixing material, and a method for manufacturing a semiconductor device using the adhesive paste as an adhesive for a semiconductor element-fixing material.

Background

Conventionally, adhesive pastes have been improved in various ways depending on the application, and are widely used industrially as raw materials, adhesives, coating agents, and the like for optical parts and molded articles.

The adhesive paste is also attracting attention as a paste for a semiconductor element-fixing material such as an adhesive for a semiconductor element-fixing material.

Examples of the semiconductor element include a light emitting element such as a laser or a Light Emitting Diode (LED), an optical semiconductor element such as a light receiving element such as a solar cell, a sensor such as a transistor, a temperature sensor, or a pressure sensor, and an integrated circuit.

An adhesive paste for semiconductor elements for fixing semiconductor elements is generally applied to an object to be coated, for example, a substrate such as a lead frame, using an application device having a discharge tube (needle).

In the coating apparatus having such a discharge pipe, for example, the discharge pipe is vertically lowered to be close to the object to be coated, and after a predetermined amount of adhesive paste is discharged from the tip end portion thereof, the discharge pipe is raised to be away from the object to be coated, and the object to be coated is moved laterally. Then, this operation is repeated, whereby the adhesive paste for semiconductor elements is continuously applied to the object to be coated. Then, the semiconductor element is mounted (mounted) on the applied adhesive paste and bonded to the object to be coated.

Generally, after an adhesive paste is applied to an object to be coated, a semiconductor element is quickly mounted on the applied adhesive paste and adhered to the object to be coated.

However, in a production line or the like, there are cases where the semiconductor element is not mounted and the applied adhesive paste is left for a long time.

In this case, if the applied adhesive paste is left for a long time, the viscosity of the adhesive paste changes, and the semiconductor element may not be mounted in an ideal state.

In order to solve this problem, patent document 1 proposes an adhesive obtained by dissolving a specific polysilsesquioxane compound in a solvent containing a high boiling point organic solvent having a boiling point of 254 ℃ or higher and 300 ℃ or lower, and describes that even after 20 minutes or longer has elapsed after the adhesive is applied to a substrate, an optical element can be mounted satisfactorily and the adhesiveness is excellent, as in the case immediately after the application.

However, the optical parts and the sensor chip are susceptible to heat. Therefore, when the heat curing method is used as a method of curing the adhesive, it is preferable to cure the adhesive at as low a temperature as possible from the viewpoint of avoiding the influence of heat on the optical component and the sensor chip.

However, the adhesive described in patent document 1 requires a long-time heat treatment at a high temperature of 170 ℃ for 2 hours, and in the heat treatment at a low temperature (for example, 100 ℃ for 2 hours), a large amount of solvent remains, and there is a fear that a sufficient adhesive strength cannot be obtained. Further, when heated at a low temperature, the rate of increase in the concentration of components (active ingredients) other than the solvent in the adhesive is slow, and therefore, it is difficult to sufficiently heat-cure the adhesive, and a cured product having sufficient adhesive strength may not be obtained.

In addition, when acetone or the like having a very low boiling point is used as a solvent, the adhesive may be dried immediately after the adhesive is discharged, and thus the semiconductor element may not be mounted satisfactorily.

Therefore, there is a need for an adhesive paste which is excellent in adhesiveness of a cured product obtained by heating at a low temperature and which can mount a semiconductor element on the adhesive paste satisfactorily even when left for a long time after being applied to an object to be coated, as in the case immediately after application.

Documents of the prior art

Patent literature

Patent document 1: japanese patent laid-open publication No. 2018-168286.

Disclosure of Invention

Problems to be solved by the invention

The present invention has been made in view of the above circumstances, and an object thereof is to provide an adhesive paste which has excellent adhesiveness of a cured product obtained by heating at a low temperature and can mount a semiconductor element satisfactorily even after a long period of time has elapsed after being applied to an object to be coated, a method for using the adhesive paste as an adhesive for a semiconductor element-fixing material, and a method for manufacturing a semiconductor device using the adhesive paste as an adhesive for a semiconductor element-fixing material.

In the present invention, "low temperature" means "80 ℃ to 120 ℃.

Further, "excellent adhesion" means "high adhesion strength".

Means for solving the problems

The present inventors have conducted extensive studies to solve the above problems. As a result, the present inventors have found that an adhesive paste obtained by dissolving a thermosetting organopolysiloxane compound in a solvent containing an organic solvent having a boiling point of 100 ℃ or higher and lower than 254 ℃ and having a controlled mass loss rate is excellent in adhesiveness of a cured product obtained by heating the adhesive paste at low temperature because the solvent is efficiently volatilized, and that a semiconductor element can be mounted well even after a long period of time has elapsed after the adhesive paste is applied to an object to be coated, thereby completing the present invention.

Thus, the present invention provides the following adhesive pastes [1] to [10], a method for using the adhesive paste [11], and a method for producing a semiconductor device using the adhesive paste [12 ].

[1]A bonding paste comprising a thermosetting organopolysiloxane compound (A) and a solvent (S), the thermosetting organopolysiloxane compound (A) being dissolved in the solvent (S), wherein the solvent (S) comprises an organic Solvent (SL) having a boiling point of 100 ℃ or higher and lower than 254 ℃, and the bonding paste is heated at 100 ℃ for 2 hours, and the mass reduction rate of the bonding paste before and after heating is reduced _100℃2h Is 10% or more, and the mass reduction rate of the adhesive paste before and after heating at 170 ℃ for 2 hours is defined as the mass reduction rate _170℃2h Time, mass reduction rate _170℃2h Mass reduction rate _100℃2h Less than 14%.

[2] The adhesive paste according to [1], wherein the thermosetting organopolysiloxane compound (A) is a polysilsesquioxane compound.

[3] The adhesive paste according to [1] or [2], wherein the boiling point of the organic Solvent (SL) is 100 ℃ or higher and less than 200 ℃.

[4] The bonding paste according to [1] or [2], wherein the content of the organic Solvent (SL) is 10% by mass or more and 50% by mass or less with respect to the total mass of the bonding paste.

[5] The adhesive paste according to [1] or [2], wherein the solvent (S) contains an organic Solvent (SH) having a boiling point of 254 ℃ or higher and 300 ℃ or lower.

[6] The adhesive paste according to [1] or [2], which further comprises the following component (B),

(B) the components: a silane coupling agent.

[7] The adhesive paste according to [1] or [2], which further comprises the following component (C),

(C) the components: and (3) microparticles.

[8] The adhesive paste according to [1] or [2], wherein the solid content concentration is 50% by mass or more and 90% by mass or less.

[9] The adhesive paste according to [1] or [2], which contains substantially no noble metal catalyst.

[10] The adhesive paste according to [1] or [2], which is an adhesive for a semiconductor element-fixing material.

[11] A method of using the adhesive paste according to any one of [1] to [10] as an adhesive for a semiconductor element-fixing material.

[12] A method for producing a semiconductor device using the adhesive paste according to any one of [1] to [10] as an adhesive for semiconductor element-fixing material, the method comprising the steps (BI) and (BII),

step (BI): applying the adhesive paste to one or both of the adhesive surfaces of the semiconductor element and the supporting substrate, and pressing the adhesive surfaces;

step (BII): and (b) heating and curing the adhesive paste of the pressure-sensitive adhesive obtained in step (BI) to fix the semiconductor element on the support substrate.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there is provided an adhesive paste which combines adhesiveness of a cured product obtained by heating at a low temperature and chip mountability in which a semiconductor element can be mounted well even after a long period of time has elapsed after the cured product is coated on an object to be coated.

Further, according to the present invention, there are provided a method of using the adhesive paste as an adhesive for a semiconductor element-fixing material, and a method of manufacturing a semiconductor device using the adhesive paste as an adhesive for a semiconductor element-fixing material.

Detailed Description

The present invention is divided into 1) an adhesive paste, 2) a method for using the adhesive paste, and a method for manufacturing a semiconductor device using the adhesive paste, and the following description will be given in detail.

1) Adhesive paste

The adhesive paste of the present invention comprises a thermosetting organopolysiloxane compound (A) and a solvent (S), and is an adhesive paste obtained by dissolving the thermosetting organopolysiloxane compound (A) in the solvent (S), wherein the solvent (S) comprises an organic Solvent (SL) having a boiling point of 100 ℃ or higher and lower than 254 ℃, and the adhesive paste is heated at 100 ℃ for 2 hours, and the mass reduction rate of the adhesive paste before and after heating is the mass reduction rate of the adhesive paste before and after heating _100℃2h Is 10% or more, and the mass reduction rate of the adhesive paste before and after heating at 170 ℃ for 2 hours is defined as the mass reduction rate _170℃2h Mass reduction rate _170℃2h Mass reduction rate _100℃2h Less than 14%.

In the present invention, the "adhesive paste" refers to a "viscous liquid at room temperature (23 ℃) and a substance having fluidity".

The adhesive paste of the present invention has the above-described properties, and therefore, has excellent workability in the coating step.

Here, "excellent in workability in the coating step" means "that the amount of the drawn yarn is small or the drawn yarn is immediately interrupted when the adhesive paste is discharged from the discharge pipe and then the discharge pipe is lifted up in the coating step, and that the resin is not splashed or the periphery is not contaminated by spreading of the droplets after coating".

The adhesive paste of the present invention has a mass reduction rate before and after heating the adhesive paste at 100 ℃ for 2 hours _100℃2h Is 10% or more, preferably 12% or more and less than 50%, more preferably 13% or more and less than 45%.

Through mass reduction rate _100℃2h When the temperature is not lower than the lower limit, a cured product obtained by heating at a low temperature has more excellent adhesiveness.

In addition, if the mass reduction rate _100℃2h When the content is not less than the upper limit, the content of an active ingredient exhibiting an adhesive function of a cured product obtained by heating at a low temperature is reduced, and thus high adhesive strength may not be exhibited.

Here, the "active ingredient" means "an ingredient other than the solvent (S) contained in the adhesive paste".

In addition, in the adhesive paste of the present invention, the mass reduction rate of the adhesive paste before and after heating the adhesive paste at 170 ℃ for 2 hours was defined as the mass reduction rate _170℃2h Time, mass reduction rate _170℃2h Mass reduction rate _100℃2h Less than 14%, preferably less than 12%, more preferably 1% or more and less than 10%.

By mass reduction rate _170℃2h Mass reduction rate _100℃2h When the amount of the solvent is less than the above upper limit, the solvent is effectively volatilized when the composition is heated at a low temperature, as in the case of heating at a high temperature, and thus the cured product obtained by heating at a low temperature is more excellent in adhesiveness.

Rate of mass reduction _100℃2h And rate of mass reduction _170℃2h The measurement can be carried out by the method described in examples.

[ thermosetting organopolysiloxane Compound (A) ]

The adhesive paste of the present invention contains a thermosetting organopolysiloxane compound (a) (hereinafter, sometimes referred to as "component (a)").

The adhesive paste of the present invention contains the component (a), and thus a cured product having excellent adhesiveness can be easily obtained by heating at a low temperature.

The thermosetting organopolysiloxane compound (A) of the present invention is a compound having carbon-silicon bonds and siloxane bonds (-Si-O-Si-) in the molecule.

Further, since the component (a) is a thermosetting compound, it preferably has at least one functional group selected from a functional group capable of undergoing a condensation reaction by heating and a functional group capable of undergoing a condensation reaction by hydrolysis.

The functional group is preferably at least one selected from the group consisting of a hydroxyl group and an alkoxy group, and more preferably a hydroxyl group and an alkoxy group having 1 to 10 carbon atoms.

The main chain structure of the thermosetting organopolysiloxane compound (a) is not limited, and may be any of linear, ladder, and cage.

For example, the structure represented by the following formula (a-1) can be cited as the linear main chain structure, the structure represented by the following formula (a-2) can be cited as the ladder-like main chain structure, and the structure represented by the following formula (a-3) can be cited as the cage-like main chain structure.

[ chemical formula 1]

[ chemical formula 2]

[ chemical formula 3]

In the formulae (a-1) to (a-3), Rx, Ry, Rz each independently represents a hydrogen atom or an organic group, and as the organic group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or an alkylsilyl group is preferable. The plurality of Rx of formula (a-1), the plurality of Ry of formula (a-2) and the plurality of Rz of formula (a-3) may be the same or different, respectively. However, 2 of Rx in the above formula (a-1) are not all hydrogen atoms.

Examples of the alkyl group of the unsubstituted or substituted alkyl group include alkyl groups having 1 to 10 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group.

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

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

Examples of the substituent for the alkyl group, the cycloalkyl group and the alkenyl group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a hydroxyl group, a mercapto group, an epoxy group, a glycidyl group, a (meth) acryloyloxy group, an unsubstituted or substituted aryl group such as a phenyl group, a 4-methylphenyl group and a 4-chlorophenyl group.

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

Examples of the substituent for the aryl group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, a nitro group, a cyano group, a hydroxyl group, a mercapto group, an epoxy group, a glycidyl group, a (meth) acryloyloxy group, an unsubstituted or substituted aryl group such as a phenyl group, a 4-methylphenyl group, and a 4-chlorophenyl group, and the like.

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

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

The thermosetting organopolysiloxane compound (a) can be obtained, for example, by a known production method in which a silane compound having a hydrolyzable functional group (alkoxy group, halogen atom, or the like) is polycondensed.

The silane compound to be used may be appropriately selected depending on the structure of the target thermosetting organopolysiloxane compound (a). Preferred specific examples include: bifunctional silane compounds such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane and diethyldiethoxysilane,

trifunctional silane compounds such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and phenyldiethoxymethoxysilane,

tetrafunctional silane compounds such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-t-butoxysilane, tetra-sec-butoxysilane, methoxytriethoxysilane, dimethoxydiethoxysilane, and trimethoxyethoxysilane.

The mass average molecular weight (Mw) of the thermosetting organopolysiloxane compound (a) is generally 800 or more and 30,000 or less, preferably 1,000 or more and 20,000 or less, more preferably 1,200 or more and 15,000 or less, and particularly preferably 3,000 or more and 10,000 or less. By using the thermosetting organopolysiloxane compound (a) having a mass average molecular weight (Mw) within the above range, an adhesive paste that provides a cured product more excellent in heat resistance and adhesiveness can be easily obtained.

The molecular weight distribution (Mw/Mn) of the thermosetting organopolysiloxane compound (a) is not particularly limited, and is usually 1.0 or more and 10.0 or less, preferably 1.1 or more and 6.0 or less. By using the thermosetting organopolysiloxane compound (a) having a molecular weight distribution (Mw/Mn) within the above range, an adhesive paste that provides a cured product more excellent in heat resistance and adhesiveness can be easily obtained.

The mass average molecular weight (Mw) and the number average molecular weight (Mn) can be determined as values converted to standard polystyrene by Gel Permeation Chromatography (GPC) using Tetrahydrofuran (THF) as a solvent, for example.

The thermosetting organopolysiloxane compound (a) of the present invention is preferably a polysilsesquioxane compound obtained by polycondensation of a trifunctional organosilane compound.

The adhesive paste of the present invention contains a polysilsesquioxane compound as the component (a), and thus can be easily heated at a low temperature to obtain a cured product having excellent adhesiveness.

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 a polysilsesquioxane compound having a repeating unit represented by the following formula (a-4) as the component (a), and thus can be easily heated at a low temperature to obtain a cured product having more excellent adhesiveness.

[ chemical formula 4]

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

Examples of the "unsubstituted alkyl group having 1 to 10 carbon atoms" include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, and n-decyl groups.

R ¹ The number of carbon atoms of the "unsubstituted alkyl group having 1 to 10 carbon atoms" is preferably 1 to 6, more preferably 1 to 3.

R ¹ The "alkyl group having 1 to 10 carbon atoms having a substituent" preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. The number of carbon atoms refers to the number of carbon atoms of the moiety (alkyl moiety) other than the substituent. Thus, at R ¹ In the case of "alkyl group having 1 to 10 carbon atoms with substituent group", R ¹ The number of carbon atoms of (2) may exceed 10.

Examples of the "alkyl group having 1 to 10 carbon atoms as a substituent" include the same groups as those shown as the "unsubstituted alkyl group having 1 to 10 carbon atoms".

Examples of the substituent of the "alkyl group having 1 to 10 carbon atoms and having a substituent" include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and the like, a cyano group, represented by the formula: groups represented by OG, and the like.

The number of atoms (excluding the number of hydrogen atoms) of the substituent(s) "alkyl group having 1 to 10 carbon atoms as a substituent(s)" is usually 1 to 30, preferably 1 to 20.

Here, G represents a protecting group for a hydroxyl group. The protecting group for a hydroxyl group is not particularly limited, and known protecting groups known as protecting groups for hydroxyl groups can be mentioned. Examples thereof include acyl systems, silyl systems such as trimethylsilyl, triethylsilyl, t-butyldimethylsilyl and t-butyldiphenylsilyl, acetal systems such as methoxymethyl, methoxyethoxymethyl, 1-ethoxyethyl, tetrahydropyran-2-yl and tetrahydrofuran-2-yl, alkoxycarbonyl systems such as t-butoxycarbonyl, and ether systems such as methyl, ethyl, t-butyl, octyl, allyl, triphenylmethyl, benzyl, p-methoxybenzyl, fluorenyl, trityl and benzhydryl.

Examples of the "unsubstituted aryl group having 6 to 12 carbon atoms" include phenyl, 1-naphthyl and 2-naphthyl groups.

R ¹ The "unsubstituted C6-12The number of carbon atoms of the aryl group "is preferably 6.

R ¹ The "aryl group having 6 to 12 carbon atoms having a substituent" preferably has 6 carbon atoms. The number of carbon atoms refers to the number of carbon atoms of the moiety other than the substituent (the moiety of the aryl group). Thus, at R ¹ In the case of "aryl group having 6 to 12 carbon atoms with substituent(s)", R ¹ There may be more than 12 carbon atoms.

Examples of the "aryl group having 6 to 12 carbon atoms as a substituent" include the same groups as those shown as the "unsubstituted aryl group having 6 to 12 carbon atoms".

Examples of the "aryl group having 6 to 12 carbon atoms and having a substituent" include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, and an isooctyl group, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, and an alkoxy group such as a methoxy group and an ethoxy group.

The number of the substituents (excluding the number of hydrogen atoms) of the "aryl group having 6 to 12 carbon atoms as a substituent" is usually 1 to 30, preferably 1 to 20.

Wherein, as R ¹ From the viewpoint of easily obtaining a polysilsesquioxane compound having a stable structure and more stable performance as an adhesive paste, at least one selected from the group consisting of an unsubstituted alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and an unsubstituted aryl group having 6 to 12 carbon atoms is preferable.

By using R ¹ Disclosed is an adhesive paste which is a polysilsesquioxane compound that is an unsubstituted alkyl group having 1-10 carbon atoms and which can easily provide a cured product having excellent heat resistance and adhesion.

By using R ¹ The polysilsesquioxane compound is a C1-10 alkyl group having a fluorine atom, can easily give an adhesive paste and a cured product having a low refractive index, and can be easily and suitably used for an optical semiconductor element requiring a low refractive index.

As having fluorineThe alkyl group having 1 to 10 carbon atoms includes those represented by the following compositional formula: c _m H _(2m-n+1) F _n A group (m is an integer of 1 to 10, n is an integer of 1 to 2m + 1). Among them, 3,3, 3-trifluoropropyl group is preferable.

By using R ¹ A polysilsesquioxane compound which is an unsubstituted aryl group having 6 to 12 carbon atoms, which can easily give an adhesive paste or a cured product having a high refractive index, and which can be suitably used for an optical semiconductor element requiring a high refractive index.

The content ratio of the repeating unit represented by the above formula (a-4) (i.e., the T site described below) in the polysilsesquioxane compound is usually 50 to 100mol%, more preferably 70 to 100mol%, still more preferably 90 to 100mol%, and particularly preferably 100mol% based on the total repeating units.

By using the polysilsesquioxane compound having the content ratio of the repeating unit (T site) represented by the above formula (a-4) as described above, an adhesive paste that easily exhibits properties of heat resistance, adhesiveness, and refractive index can be obtained.

For example, in the case where the assignment of NMR peaks and the integration of the area can be performed, the content ratio of the repeating unit (T site) represented by the above formula (a-4) in the polysilsesquioxane compound can be determined by ²⁹ Si-NMR and ¹ H-NMR.

Polysilsesquioxane compounds are soluble in various organic solvents such as ketone solvents such as acetone, aromatic hydrocarbon solvents such as benzene, sulfur-containing solvents such as dimethyl sulfoxide, ether solvents such as tetrahydrofuran, ester solvents such as ethyl acetate, halogen-containing solvents such as chloroform, and mixed solvents of two or more of these. Therefore, using these solvents, the solution state of the polysilsesquioxane compound can be determined ²⁹ Si-NMR。

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

[ chemical formula 5]

The polysilsesquioxane compound has a partial structure, generally referred to as a T site, in which 3 oxygen atoms are bonded to a silicon atom and 1 group other than oxygen atoms (R) is bonded, as shown in the formula (a-5) ¹ ) And (4) preparing the composition.

In the formula (a-5), R ¹ R in the above formula (a-4) ¹ The same meaning is used. Represents a Si atom, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and at least 1 of 3 atoms is a Si atom. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group. A plurality may be identical to or different from each other.

The polysilsesquioxane compound is a thermosetting compound, and is a compound that undergoes a condensation reaction by heating and/or a condensation reaction by hydrolysis. Therefore, in the formula (a-5) in which the polysilsesquioxane compound has a plurality of repeating units (T sites), at least 1 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom.

In the case where the polysilsesquioxane compound is soluble in the solvent for measurement, the measurement is carried out ²⁹ Si-NMR confirmed the presence of hydrogen atoms or alkyl groups having 1 to 10 carbon atoms in the formula (a-5) and whether or not the repeating units are 3 repeating units wherein all of the groups are Si atoms in the formula (a-5).

In addition, can be carried out ²⁹ In the case of assignment of peaks and integration of areas in Si-NMR, the total number of repeating units of 3 x all of which are Si atoms in the above formula (a-5) can be estimated with respect to the total number of repeating units (T sites) represented by the above formula (a-4) in the polysilsesquioxane compound.

From the viewpoint of easily obtaining an adhesive paste that provides a cured product having more excellent heat resistance, the total number of repeating units in which all of 3 x in the formula (a-5) are Si atoms is preferably 30 to 95mol%, and more preferably 40 to 90mol%, based on the total number of repeating units (T sites) represented by the formula (a-4) in the polysilsesquioxane compound.

Polysilsesquioxane compoundsThe compound may have one R ¹ (homopolymer) may have two or more R ¹ (copolymer).

When the polysilsesquioxane compound is a copolymer, the polysilsesquioxane compound may be any of a random copolymer, a block copolymer, a graft copolymer, an alternating copolymer, and the like, and a random copolymer is preferable from the viewpoint of ease of production and the like.

The polysilsesquioxane compound may have any structure of a ladder structure, a double layer (double decker) structure, a cage structure, a partially split cage structure, a cyclic structure, and a random structure.

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

The method for preparing the polysilsesquioxane compound is not particularly limited. The polysilsesquioxane compound may be prepared, for example, by polycondensation using at least one of the silane compounds (1) represented by the following formula (a-6).

[ chemical formula 6]

(in the formula, R ¹ Represents the same as R in the above formula (a-4) ¹ The same meaning is used. R ² Represents an alkyl group having 1 to 10 carbon atoms, X ¹ Represents a halogen atom, and p represents an integer of 0 to 3. Plural R ² And a plurality of X ¹ May be respectively the same or different from each other. )

As R ² Examples of the alkyl group having 1 to 10 carbon atoms include the same groups as those shown as the alkyl group having 1 to 10 carbon atoms in the formula (a-5).

As X ¹ Examples of the halogen atom of (b) include a chlorine atom and a bromine atom.

Specific examples of the silane compound (1) include:

alkyltrialkoxysilane compounds such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane and ethyltripropoxysilane,

alkylhaloalkoxysilane compounds such as methylchlorodimethoxysilane, methylchlorodiethoxysilane, methyldichlormethoxysilane, methylbromodimethoxysilane, ethylchlorodimethoxysilane, ethylchlorodiethoxysilane, ethyldichloromethoxysilane and ethylbromodimethoxysilane,

alkyltrihalosilane compounds such as methyltrichlorosilane, methyltrtribromosilane, ethyltrichlorosilane, ethyltribromosilane and the like,

substituted alkyltrialkoxysilane compounds such as 3,3, 3-trifluoropropyltrimethoxysilane, 3, 3-trifluoropropyltriethoxysilane, 2-cyanoethyltrimethoxysilane and 2-cyanoethyltriethoxysilane,

substituted alkylhaloalkoxysilane compounds such as 3,3, 3-trifluoropropylchlorodimethoxysilane, 3,3, 3-trifluoropropylchlorodiethoxysilane, 3,3, 3-trifluoropropyldichloromethoxysilane, 3, 3-trifluoropropyldichloroethoxysilane, 2-cyanoethylchlorodimethoxysilane, 2-cyanoethylchlorodiethoxysilane, 2-cyanoethyldichloromethoxysilane and 2-cyanoethyldichloroethoxysilane,

substituted alkyltrihalosilane compounds such as 3,3, 3-trifluoropropyltrichlorosilane and 2-cyanoethyltrichlorosilane,

phenyltrialkoxysilane compounds having a substituent or having no substituent such as phenyltrimethoxysilane and 4-methoxyphenyltrimethoxysilane,

phenyl halogenoalkoxysilane compounds having or not having a substituent such as phenylchlorodimethoxysilane, phenyldichloromethoxysilane, 4-methoxyphenylchlorodimethoxysilane, 4-methoxyphenyldichloromethoxysilane and the like,

and phenyl trihalosilane compounds having a substituent or having no substituent, such as phenyltrichlorosilane and 4-methoxyphenyltrichlorosilane.

These silane compounds (1) may be used singly or in combination of two or more.

The method for 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 at a predetermined temperature may be mentioned. More specifically, there may be mentioned: (a) a method in which a predetermined amount of an acid catalyst is added to the silane compound (1) and the mixture is stirred at a predetermined temperature; (b) a method in which a predetermined amount of a base catalyst is added to the silane compound (1) and the mixture is stirred at a predetermined temperature; (c) a method in which a predetermined amount of an acid catalyst is added to the silane compound (1), and the mixture is stirred at a predetermined temperature, and then an excess amount of a base catalyst is added to make the reaction system basic, and the mixture is stirred at a predetermined temperature. Among them, the method (a) or (c) is preferable because the objective polysilsesquioxane compound can be efficiently obtained.

The polycondensation catalyst used may be any of an acid catalyst and a base catalyst. In addition, two or more polycondensation catalysts may be used in combination, and preferably at least an acid catalyst is used.

Examples of the acid catalyst include inorganic acids such as phosphoric acid, hydrochloric acid, boric acid, sulfuric acid and nitric acid, and organic acids such as citric acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid. Among them, at least one selected from phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, citric acid, acetic acid and methanesulfonic acid is preferable.

Examples of the base catalyst include ammonia water, organic bases such as trimethylamine, triethylamine, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, pyridine, 1, 8-diazabicyclo [5.4.0] -7-undecene, aniline, picoline, 1, 4-diazabicyclo [2.2.2] octane and imidazole, organic salt hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, metal alkoxides such as sodium methoxide, sodium ethoxide, sodium tert-butoxide and potassium tert-butoxide, metal hydrides such as sodium hydride and calcium hydride, metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, metal carbonates such as sodium carbonate, potassium carbonate and magnesium carbonate, and metal bicarbonates such as sodium bicarbonate and potassium bicarbonate.

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

When a solvent is used in the polycondensation, the solvent to be used may be appropriately selected depending on the kind of the silane compound (1) and the like. Examples thereof include water, aromatic hydrocarbons such as benzene, toluene and xylene, esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate and methyl propionate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol. These solvents may be used singly or in combination of two or more. In the case of the method (c), after the polycondensation reaction is carried out in an aqueous system in the presence of an acid catalyst, an organic solvent and an excess amount of a base catalyst (ammonia water or the like) are added to the reaction solution, and the polycondensation reaction can be further carried out under an alkaline condition.

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

The temperature at which the silane compound (1) is polycondensed is usually in the range of 0 ℃ to the boiling point of the solvent used, and preferably in the range of 20 ℃ to 100 ℃. If the reaction temperature is too low, the polycondensation reaction may not be sufficiently performed. On the other hand, if the reaction temperature is too high, it is difficult to suppress gelation. The reaction is usually completed within 30 minutes to 30 hours.

Depending on the kind of monomer used, it may be difficult to increase the molecular weight. For example R ¹ Monomer which is an alkyl group having a fluorine atom has a reactivity ratio R ¹ Monomers which are normal alkyl groups tend to be poor. In this case, by reducing the amount of the catalyst and conducting the reaction under mild conditions for a long period of time, the polysilsesquioxane compound of the target molecular weight is easily obtained.

After the reaction is completed, the objective polysilsesquioxane compound can be obtained by adding an aqueous alkaline solution such as sodium hydrogencarbonate to the reaction solution for neutralization in the case of using an acid catalyst, adding an acid such as hydrochloric acid to the reaction solution for neutralization in the case of using an alkaline catalyst, and removing the salt generated at this time by filtration, washing with water, or the like.

In the preparation of the polysilsesquioxane compound by the above-mentioned method, at OR of the silane compound (1) ² Or X ¹ In the case of (b), a part in which hydrolysis, condensation reaction, and the like do not occur remains in the polysilsesquioxane compound.

When the component (a) is, for example, a polysilsesquioxane compound obtained by a polycondensation reaction of a silane compound (1), curing proceeds by a condensation reaction including a reaction with a silane coupling agent described below, and therefore the adhesive paste of the present invention is different from a general heat-curable silicone adhesive that is cured by an addition reaction in the presence of a noble metal catalyst such as a platinum catalyst.

Therefore, the adhesive paste containing the polysilsesquioxane compound of the present invention contains substantially no noble metal catalyst or contains a small amount of noble metal catalyst.

Here, "the precious metal catalyst is not substantially contained or the content of the precious metal catalyst is small" means "the content of the precious metal catalyst is, for example, less than 1 mass ppm in terms of the mass of the catalytic metal element relative to the amount of the active component in the adhesive paste, except that the component that can be interpreted as the precious metal catalyst is not intentionally added".

From the viewpoints of stable production in view of mixing variation and the like, storage stability, and the fact that the noble metal catalyst is expensive, it is preferable that the binder paste contains substantially no noble metal catalyst or contains a small amount of noble metal catalyst.

[ solvent (S) ]

The adhesive paste of the present invention is obtained by dissolving the thermosetting organopolysiloxane compound (a) in a solvent (S) containing an organic Solvent (SL) having a boiling point of 100 ℃ or higher and lower than 254 ℃.

Here, "boiling point" means "boiling point at 1013 hPa" (the same in the present specification).

The organic Solvent (SL) is not particularly limited as long as it has a boiling point of 100 ℃ or higher and lower than 254 ℃ and can dissolve or disperse the components of the adhesive paste of the present invention.

The boiling point of the organic Solvent (SL) is 100 ℃ or higher and lower than 254 ℃, preferably 100 ℃ or higher and lower than 200 ℃, more preferably 105 ℃ or higher and lower than 185 ℃, and particularly preferably 110 ℃ or higher and lower than 170 ℃.

Such an organic Solvent (SL) is more effective in volatilizing the solvent when heated at a low temperature than a high boiling point organic solvent having a boiling point of 254 ℃ to 300 ℃. Therefore, by containing the organic Solvent (SL), the mass reduction rate is easily obtained _100℃2h Is 10% or more and has a mass reduction rate of _170℃2h Mass reduction rate _100℃2h Less than 14% of binding paste. In addition, such an organic Solvent (SL) has a lower volatilization rate than a low boiling point organic solvent having a boiling point lower than 100 ℃.

Therefore, when the adhesive paste containing the organic Solvent (SL) is heated at low temperature, a large amount of the solvent is efficiently volatilized without remaining, and thus sufficient adhesive strength is easily obtained, and even when heated at low temperature, the concentration of the active ingredient in the adhesive paste is increased at a high rate, and thus curing is easily performed. Therefore, the obtained cured product has excellent adhesiveness, and the semiconductor element can be mounted well even after a long time has elapsed after the cured product is applied to an object to be coated.

Specific examples of the organic Solvent (SL) include diethylene glycol monobutyl ether acetate (boiling point: 247 ℃ C.), dipropylene glycol n-butyl ether (boiling point: 229 ℃ C.), dipropylene glycol methyl ether acetate (boiling point: 209 ℃ C.), diethylene glycol butyl methyl ether (boiling point: 212 ℃ C.), dipropylene glycol n-propyl ether (boiling point: 212 ℃ C.), tripropylene glycol dimethyl ether (boiling point: 215 ℃ C.), triethylene glycol dimethyl ether (boiling point: 216 ℃ C.), diethylene glycol monoethyl ether acetate (boiling point: 218 ℃ C.), diethylene glycol n-butyl ether (boiling point: 230 ℃ C.), ethylene glycol monophenyl ether (boiling point: 245 ℃ C.), 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.), benzyl alcohol (boiling point: 219 to 221 ℃ C.), ethylene glycol monobutyl ether acetate (boiling point: 192 ℃ C.), and triethylene glycol monobutyl ether acetate (boiling point: 249 ℃ C.) Ethylene glycol monoethyl ether (boiling point: 134.8 ℃), ethylene glycol monomethyl ether (boiling point: 124.5 ℃), propylene glycol monomethyl ether acetate (boiling point: 146 ℃), cyclopentanone (boiling point: 130 ℃), cyclohexanone (boiling point: 157 ℃), cycloheptanone (boiling point: 180 ℃), cyclooctanone (boiling point: 195 to 197 ℃), cyclohexanol (boiling point: 161 ℃), cyclohexadienone (boiling point: 104 to 104.5 ℃) and the like.

Among these, as the organic Solvent (SL), diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, and cyclohexanone are preferable, and ethylene glycol monobutyl ether acetate and cyclohexanone are more preferable, from the viewpoint of further exhibiting the effect of using the organic Solvent (SL) and from the viewpoint of easily and favorably mixing the active ingredients.

The organic Solvent (SL) may be used singly or in combination of two or more.

In the adhesive paste of the present invention, the content of the organic Solvent (SL) is preferably 10 mass% or more and 50 mass% or less, more preferably 18 mass% or more and 45 mass% or less, and particularly preferably 20 mass% or more and 40 mass% or less, with respect to the total mass of the adhesive paste.

By setting the content of the organic Solvent (SL) in the above range with respect to the total mass of the adhesive paste, the workability in the process of filling the adhesive paste into a syringe and the coating process is excellent, and the effect of using the organic Solvent (SL) can be further exhibited.

Here, "excellent in workability in the step of filling the adhesive paste into the syringe" means "that an appropriate amount of adhesive paste can be filled into the syringe without air bubbles".

The adhesive paste of the present invention may contain a solvent other than the organic Solvent (SL).

The solvent other than the organic Solvent (SL) is preferably an organic solvent having a boiling point of 254 ℃ or higher and 300 ℃ or lower (hereinafter, sometimes referred to as "organic Solvent (SH)").

The organic Solvent (SH) is not particularly limited as long as it has a boiling point of 254 ℃ to 300 ℃ and can dissolve or disperse the components of the adhesive paste of the present invention.

By using the organic Solvent (SL) and a solvent other than the organic Solvent (SL) in combination, the temperature range of the cured product obtained by heating the adhesive paste can be adjusted more precisely, and therefore the influence of heating on the optical component or the sensor chip which is easily affected by heat can be reduced.

Specific examples of the organic Solvent (SH) include tripropylene glycol n-butyl ether (boiling point: 274 ℃), 1, 6-hexanediol diacrylate (boiling point: 260 ℃), diethylene glycol dibutyl ether (boiling point: 256 ℃), triethylene glycol butyl methyl ether (boiling point: 261 ℃), polyethylene glycol dimethyl ether (boiling point: 264 to 294 ℃), tetraethylene glycol dimethyl ether (boiling point: 275 ℃), and polyethylene glycol monomethyl ether (boiling point: 290 to 310 ℃).

Among them, tripropylene glycol n-butyl ether and 1, 6-hexanediol diacrylate are preferable as the organic Solvent (SH) from the viewpoint of more easily obtaining the effect of using the organic Solvent (SL) and the organic Solvent (SH) in combination.

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

The organic Solvent (SL) is preferably 60 mass% or more, more preferably 65 mass% or more, and particularly preferably 70 mass% or more of the entire solvent (S).

By using the organic Solvent (SL) in the whole solvent (S) within the above range, the effect of using the organic Solvent (SL) can be further exhibited.

The adhesive paste of the present invention preferably contains the solvent (S) in an amount such that the solid content concentration is preferably 50 mass% or more and 90 mass% or less, more preferably 70 mass% or more and 90 mass% or less.

Since the solid content concentration is within this range, the effective component can be easily mixed well, and the workability in the step of filling the adhesive paste into a syringe and the coating step is excellent, and the effect of using the organic Solvent (SL) can be further exhibited.

In addition, when die bonding is performed, generation of voids (voids) between the adhesive paste and the substrate or the like to be bonded can be suppressed, and reliability of the package can be improved.

[ other ingredients ]

The adhesive paste of the present invention contains the thermosetting organopolysiloxane compound (a) and the solvent (S), but may contain the following components.

(1) Silane coupling agent (B)

The adhesive paste of the present invention may contain a silane coupling agent as the component (B).

Examples of the silane coupling agent include a silane coupling agent (B1) (hereinafter, sometimes referred to as a "(B1) component") having a nitrogen atom in the molecule, and a silane coupling agent (B2) (hereinafter, sometimes referred to as a "(B2) component") having an acid anhydride structure in the molecule.

An adhesive paste containing the silane coupling agent (B1) is excellent in workability in a coating step, excellent in curability obtained by condensation reaction together with the component (a) during heating, and provides a cured product having excellent adhesiveness, heat resistance and crack-inhibiting property of the cured product when heated at low temperature.

Here, "more excellent in crack suppression of the cured product" means "that cracking of the cured product does not occur with a change in temperature when the adhesive paste is heated to obtain the cured product.

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

[ chemical formula 7]

In the above formula, R ^a Represents an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, or the like. Plural R ^a May be the same or different from each other.

R ^b And (b) represents an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, or the like, or an aryl group having a substituent or no substituent such as a phenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, a 1-naphthyl group, or the like.

R ^c Represents an organic group having 1 to 10 carbon atoms and having a nitrogen atom. In addition, R ^c And may also be bonded to groups containing other silicon atoms.

As R ^c Specific examples of the organic group having 1 to 10 carbon atoms include N-2- (aminoethyl) -3-aminopropyl, N- (1, 3-dimethyl-butylene) aminopropyl, 3-ureidopropyl, N-phenyl-aminopropyl and the like.

In the compound represented by the above formula (b-1) or (b-2), R is ^c The compound in the case of an organic group bonded to a group containing another silicon atom includes a compound bonded to another silicon atom via an isocyanurate skeleton to form an isocyanurate-based silane coupling agent and a compound bonded to another silicon atom via a urea skeleton to form a urea-based silane coupling agent.

Among them, the silane coupling agent (B1) is preferably an isocyanurate-based silane coupling agent or a urea-based silane coupling agent, and more preferably a compound having 4 or more alkoxy groups bonded to a silicon atom in the molecule, in view of easy obtainment of a cured product having a higher adhesive strength.

The alkoxy group having 4 or more bonded to a silicon atom means that the total number of the alkoxy groups bonded to the same silicon atom and the alkoxy groups bonded to different silicon atoms is 4 or more.

Examples of the isocyanurate-based silane coupling agent having 4 or more alkoxy groups bonded to a silicon atom include compounds represented by the following formula (b-3), and examples of the urea-based silane coupling agent having 4 or more alkoxy groups bonded to a silicon atom include compounds represented by the following formula (b-4).

[ chemical formula 8]

In the formula, R ^a Represents the same as R in the above formulae (b-1) and (b-2) ^a The same meaning is used. t1 to t5 each independently represent an integer of 1 to 10, preferably an integer of 1 to 6, and particularly preferably 3.

Specific examples of the compound represented by the formula (b-3) include:

1,3, 5-N-tris [ (tri (C1-C6) alkoxy) silyl (C1-C10) alkyl ] isocyanurate such as 1,3, 5-N-tris (3-trimethoxysilylpropyl) isocyanurate, 1,3, 5-N-tris (3-triisopropoxysilylpropyl) isocyanurate, 1,3, 5-N-tris (3-tributoxysilylpropyl) isocyanurate or the like,

1,3, 5-N-tris (3-dimethoxymethylsilylpropyl) isocyanurate, 1,3, 5-N-tris (3-dimethoxyethylsilylpropyl) isocyanurate, 1,3, 5-N-tris (3-dimethoxyisopropylsilylpropyl) 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-N-propylsilylpropyl) isocyanurate, 1,3, 5-N-tris (3-diethoxyphenylsilylpropyl) isocyanurate, 1,3, 5-N-tris (3-diisopropoxymethylsilylpropyl) isocyanurate, 1,3, 5-N-tris (3-diisopropoxyethylsilylpropyl) isocyanurate, 1,3, 5-N-tris (3-diisopropoxyesopropylsilylpropyl) isocyanurate, 1,3, 5-N-tris (3-diisopropoxyen-propylsilylpropyl) isocyanurate, 1,3, 5-N-tris (3-diisopropoxyphenylsilylpropyl) isocyanurate, 1,3, 5-N-tris (3-dibutoxymethylsilylpropyl) isocyanurate, 1,3, 5-N-tris (3-dibutoxyethylsilylpropyl) isocyanurate, 1,3, 5-N-tris [ (di (alkoxy having 1 to 6 carbon atoms) and silyl (alkyl having 1 to 10 carbon atoms) ] isocyanurates such as 1,3, 5-N-tris (3-dibutoxy-N-propylsilylpropyl) isocyanurate, 1,3, 5-N-tris (3-dibutoxyphenylsilylpropyl) isocyanurate and the like.

Specific examples of the compound represented by the formula (b-4) include N, N '-bis [ (tri (C1-C6) alkoxysilyl) (C1-C10) alkyl ] ureas such as N, N' -bis (3-trimethoxysilylpropyl) urea, N '-bis (3-triethoxysilylpropyl) urea, N' -bis (3-tripropoxysilylpropyl) urea, N '-bis (3-tributoxysilylpropyl) urea, and N, N' -bis (2-trimethoxysilylethyl) urea,

n, N '-bis [ (di (C1-6) alkoxy (C1-6) alkylsilyl (C1-10) alkyl) urea such as N, N' -bis (3-dimethoxymethylsilylpropyl) urea, N '-bis (3-dimethoxyethylsilylpropyl) urea, and N, N' -bis (3-diethoxymethylsilylpropyl) urea,

n, N ' -bis [ (di (C1-C6) alkoxy (C6-C20) arylsilyl (C1-C10) alkyl) urea such as N, N ' -bis (3-dimethoxyphenylsilylpropyl) urea or N, N ' -bis (3-diethoxyphenylsilylpropyl) urea.

The silane coupling agent (B1) may be used singly or in combination of two or more.

Among them, as the silane coupling agent (B1), 1,3, 5-N-tris (3-trimethoxysilylpropyl) isocyanurate, 1,3, 5-N-tris (3-triethoxysilylpropyl) isocyanurate (hereinafter, the above 2 species are referred to as "isocyanurate compound"), N '-bis (3-trimethoxysilylpropyl) urea, N' -bis (3-triethoxysilylpropyl) urea (hereinafter, the above 2 species are referred to as "urea compound"), and a combination of the above isocyanurate compound and urea compound are preferably used.

When the isocyanurate compound and the urea compound are used in combination, the ratio of the isocyanurate compound to the urea compound is preferably 100:1 to 100:200, and more preferably 100:10 to 100:110, in terms of the mass ratio of the isocyanurate compound to the urea compound. By using the isocyanurate compound and the urea compound in combination at such a ratio, an adhesive paste which provides a cured product having higher adhesive strength and more excellent heat resistance can be obtained.

When the adhesive paste of the present invention contains the silane coupling agent (B1) [ (B1) component ], (B1) component content is not particularly limited, and the amount thereof is: the amount of the component (A) to the component (B1) is preferably 100:0.1 to 100:90, more preferably 100:0.5 to 100:70, still more preferably 100:1 to 100:55, still more preferably 100:3 to 100:45, and further preferably 100:5 to 100:35 in terms of the mass ratio of the component (A) to the component (B1) [ (component (A): (B1) ].

By using the (B1) component within the above range, the effect of adding the (B1) component can be further exhibited.

The adhesive paste containing the silane coupling agent (B2) is excellent in workability in the coating step, and provides a cured product having more excellent adhesiveness and heat resistance when heated at low temperatures.

Examples of the silane coupling agent (B2) include:

tri (C1-C6) alkoxysilyl (C2-C8) alkylsuccinic anhydrides such as 2- (trimethoxysilyl) ethylsuccinic anhydride, 2- (triethoxysilyl) ethylsuccinic anhydride, 3- (trimethoxysilyl) propylsuccinic anhydride and 3- (triethoxysilyl) propylsuccinic anhydride,

di (C1-C6) alkoxymethylsilyl (C2-C8) alkylsuccinic anhydride such as 2- (dimethoxymethylsilyl) ethylsuccinic anhydride,

(C1-C6) alkoxydimethylsilyl (C2-C8) alkylsuccinic anhydride such as 2- (methoxydimethylsilyl) ethylsuccinic anhydride,

trihalosilyl (C2-C8) alkyl succinic anhydrides such as 2- (trichlorosilyl) ethylsuccinic anhydride and 2- (tribromosilyl) ethylsuccinic anhydride,

dihalomethylsilyl (C2-C8) alkylsuccinic anhydride such as 2- (dichloromethylsilyl) ethylsuccinic anhydride,

and halogenated dimethylsilyl (C2-C8) alkyl succinic anhydrides such as 2- (chlorodimethylsilyl) ethyl succinic anhydride.

The silane coupling agent (B2) may be used singly or in combination of two or more.

Among them, the silane coupling agent (B2) is preferably a tri (c 1-c 6) alkoxysilyl (c 2-c 8) alkyl succinic anhydride, and particularly preferably 3- (trimethoxysilyl) propylsuccinic anhydride or 3- (triethoxysilyl) propylsuccinic anhydride.

When the adhesive paste of the present invention contains the silane coupling agent (B2) [ (B2) component ], the content of the (B2) component is not particularly limited, and the amount thereof is preferably 100:0.01 to 100:40, more preferably 100:0.01 to 100:30, and still more preferably 100:0.1 to 100:10, in terms of the mass ratio of the (a) component to the (B2) component [ (a) (B2) component ].

By using the (B2) component within the above range, the effect of adding the (B2) component can be further exhibited.

(2) Microparticle (C)

The adhesive paste of the present invention may contain fine particles as the component (C).

Examples of the fine particles include fine particles (C1) (hereinafter, sometimes referred to as "C1 component") having an average primary particle diameter of 5nm or more and 40nm or less, and fine particles (C2) (hereinafter, sometimes referred to as "C2 component") having an average primary particle diameter of more than 0.04 μm and 8 μm or less.

The adhesive paste containing the fine particles (C1) is excellent in workability in the coating step, and provides a cured product having more excellent adhesiveness and heat resistance when heated at low temperatures.

In view of easier achievement of this effect, the average primary particle diameter of the fine particles (C1) is preferably 5nm or more and 30nm or less, more preferably 5nm or more and 20nm or less.

The average primary particle diameter of the fine particles (C1) can be determined by observing the shape of the fine particles using a transmission electron microscope.

Microparticles (C)1) Is preferably 10m ² 500m above/g ² A ratio of 20m or less per gram ² More than 300 m/g ² The ratio of the carbon atoms to the carbon atoms is less than g. When the specific surface area is within the above range, an adhesive paste having more excellent workability in the coating step can be easily obtained.

The specific surface area can be determined by the multipoint BET method.

The shape of the fine particles (C1) may be any of spherical, chain, needle, plate, sheet, rod, fiber, etc., and is preferably spherical. Here, "spherical" means "substantially spherical" including a polyhedron shape that can be approximated to a sphere, such as a spheroid, an ovoid, a candy-shaped, and a cocoon-shaped, in addition to a regular sphere.

The constituent component of the fine particles (C1) is not particularly limited, and examples thereof include metals, metal oxides, minerals, metal carbonates, metal sulfates, metal hydroxides, metal silicates, inorganic components, organic components, and silicones.

In addition, the microparticles (C1) used may be surface-modified microparticles.

The metal means an element belonging to group 1 (excluding H), group 2 to group 11, group 12 (excluding Hg), group 13 (excluding B), group 14 (excluding C and Si), group 15 (excluding N, P, As and Sb) or group 16 (excluding O, S, Se, Te and Po) of the periodic table.

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

Examples of the mineral include smectite (smectite), bentonite, and the like.

Examples of the smectite include montmorillonite, beidellite, hectorite, saponite, stevensite, nontronite, and sauconite.

Examples of the metal carbonate include calcium carbonate, magnesium carbonate, and the like; examples of the metal sulfate include calcium sulfate, barium sulfate, and the like; examples of the metal hydroxide include aluminum hydroxide; examples of the metal silicate include aluminum silicate, calcium silicate, and magnesium silicate.

Examples of the inorganic component include silica and the like. Examples of the silica include dry silica, wet silica, and surface-modified silica (surface-modified silica).

Examples of the organic component include acrylic polymers.

Silicone refers to an artificial polymer compound having a main skeleton based on siloxane bonds. Examples thereof include dimethylpolysiloxane, diphenylpolysiloxane, and methylphenylpolysiloxane.

The fine particles (C1) may 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, in view of easy availability of a bonding paste having excellent transparency.

Among the silicas, surface-modified silicas are preferable, and hydrophobic surface-modified silicas are more preferable, from the viewpoint of easier mixing as an adhesive paste and from the viewpoint of easier availability of an adhesive paste having more excellent workability in the coating step.

Examples of the hydrophobic surface-modified silica include silica having a surface to which 1 to 20 carbon atom alkylsilyl group such as 1 to 20 trialkylsilyl group having 1 to 20 three carbon atoms, e.g., trimethylsilyl group, dimethylsilyl group, etc., and 1 to 20 carbon atom alkylsilyl group such as octylsilyl group, etc., are bonded, and silica having a surface treated with silicone oil, etc.

The hydrophobic surface-modified silica can be obtained by surface-modifying silica particles with a silane coupling agent having a trialkylsilyl group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or the like, or by treating silica particles with silicone oil.

In the case where the adhesive paste of the present invention contains fine particles (C1) [ (C1) component ], the content of the (C1) component is not particularly limited, and the amount thereof is: the mass ratio of the component (A) to the component (C1) [ (the component (C1) ], is preferably 100:0.1 to 100:90, more preferably 100:0.2 to 100:60, more preferably 100:0.3 to 100:50, more preferably 100:0.5 to 100:40, and more preferably 100:0.8 to 100: 30.

By using the (C1) component within the above range, the effect of adding the (C1) component can be further exhibited.

The adhesive paste containing the fine particles (C2) provides a cured product having more excellent adhesiveness and heat resistance when heated at low temperatures.

In view of more easily obtaining this effect, the average primary particle diameter of the fine particles (C2) is preferably more than 0.06 μm and 7 μm or less, more preferably more than 0.3 μm and 6 μm or less, and still more preferably more than 1 μm and 4 μm or less.

The average primary particle diameter of the fine particles (C2) can be determined by measuring the particle size distribution by a laser light scattering method using a laser light diffraction-scattering particle size distribution measuring apparatus (e.g., product name "LA-920" manufactured by horiba ltd.).

The shape of the fine particles (C2) is the same as that exemplified as the shape of the fine particles (C1), and is preferably spherical.

The constituent component of the fine particles (C2) is the same as the constituent component exemplified for the fine particles (C1).

The fine particles (C2) may be used singly or in combination of two or more.

Among them, from the viewpoint of easier mixing as an adhesive paste and from the viewpoint of easy obtaining of a cured product excellent in adhesiveness and heat resistance, at least one kind of fine particles selected from the group consisting of metal oxides, silica and silicone whose surfaces are covered with silicone is preferable, and silica and silicone are more preferable.

In the case where the adhesive paste of the present invention contains fine particles (C2) [ (C2) component ], the content of the (C2) component is not particularly limited, and the amount thereof is: the amount of the component (A) to the component (C2) is preferably 100:0.1 to 100:40, more preferably 100:0.2 to 100:30, still more preferably 100:0.3 to 100:20, further preferably 100:0.5 to 100:15, particularly preferably 100:0.8 to 100:12 in terms of the mass ratio of the component (A) to the component (C2) [ (component (A): (C2) ].

By using the (C2) component within the above range, the effect of adding the (C2) component can be further exhibited.

(3) Other additional ingredients

The adhesive paste of the present invention may contain components [ (D) component ] other than the above components (a) to (C) within a range not to impair the object of the present invention.

Examples of the component (D) include antioxidants, ultraviolet absorbers, and light stabilizers.

The antioxidant is added to prevent oxidative deterioration during heating. Examples of the antioxidant include a phosphorus antioxidant, a phenol antioxidant, and a sulfur antioxidant.

Examples of the phosphorus-based antioxidant include phosphites, oxaphosphaphenanthrene oxides, and the like.

Examples of the phenol-based antioxidant include monophenols, bisphenols, and polymeric phenols.

Examples of the sulfur-based antioxidant include dilauryl 3,3 ' -thiodipropionate, dimyristyl 3,3 ' -thiodipropionate, and distearyl 3,3 ' -thiodipropionate.

These antioxidants may be used singly or in combination of two or more. The amount of the antioxidant used is usually 10% by mass or less based on the component (a).

The ultraviolet absorber is added to improve the light resistance of the resulting adhesive paste.

Examples of the ultraviolet absorber include salicylic acids, benzophenones, benzotriazoles, and hindered amines.

These ultraviolet absorbers may be used singly or in combination of two or more.

The amount of the ultraviolet absorber used is usually 10% by mass or less based on the component (A).

The light stabilizer is added to improve the light resistance of the adhesive paste obtained.

Examples of the light stabilizer include hindered amines such as poly [ {6- (1,1,3, 3-tetramethylbutyl) amino-1, 3, 5-triazine-2, 4-diyl } { (2,2,6, 6-tetramethyl-4-piperidine) imino } hexamethylene { (2,2,6, 6-tetramethyl-4-piperidine) imino } ].

These light stabilizers may be used singly or in combination of two or more.

(D) The total amount of the component (A) used is usually 20% by mass or less based on the component (A).

The adhesive paste of the present invention can be produced, for example, by a production method having the following steps (AI) and (AII).

Step (AI): a step of obtaining a polysilsesquioxane compound by polycondensation using at least one of the compounds represented by the above formula (a-6) in the presence of a polycondensation catalyst;

step (AII): and (b) a step of dissolving the polysilsesquioxane compound obtained in the step (AI) in a solvent (S) containing an organic Solvent (SL) having a boiling point of 100 ℃ or higher and lower than 254 ℃ to obtain a solution containing the polysilsesquioxane compound.

The polysilsesquioxane compound obtained by polycondensation in the step (AI) using at least one of the compounds represented by the above formula (a-6) in the presence of a polycondensation catalyst may be obtained by the same method as the method exemplified in the item 1) adhesive paste. Examples of the organic Solvent (SL) and the solvent (S) used in the step (AII) include those similar to those exemplified as the organic Solvent (SL) and the solvent (S) in the item of the adhesive paste 1).

In the step (AII), as a method of dissolving the polysilsesquioxane compound in the solvent (S) containing the organic Solvent (SL), for example, a method of mixing and defoaming the polysilsesquioxane compound and, if necessary, the components (B) to (D) described above with the solvent (S) to dissolve the polysilsesquioxane compound is exemplified.

The mixing method and the 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 having the above steps (AI) and (AII), the adhesive paste of the present invention can be produced efficiently and easily.

In the present invention, the adhesive paste is heated to volatilize the solvent (S) and cure the adhesive paste, thereby obtaining a cured product.

The heating temperature during curing is usually 80 ℃ to 180 ℃, and preferably 80 ℃ to 120 ℃. The heating time during curing is usually 30 minutes to 10 hours, preferably 30 minutes to 5 hours, and more preferably 30 minutes to 3 hours.

The cured product obtained by curing the adhesive paste of the present invention has excellent adhesiveness.

The cured product obtained by curing the adhesive paste of the present invention has excellent adhesiveness, which can be confirmed, for example, as follows. I.e. a square with a length of 1mm on one side (area of 1 mm) ² ) The adhesive paste of the present invention was applied to the mirror surface of the silicon chip, and the applied surface was placed on a silver-plated copper plate and pressed (thickness of the adhesive paste after pressing: about 2 μm) was heated at 100 c for 2 hours to cure it. The sheet was left on the measuring table of an adhesion tester at 23 ℃ for 30 seconds, and the adhesive surface was stressed at a speed of 200 μm/s in the horizontal direction (shear direction) from a position 100 μm high from the adherend to measure the adhesive strength (N/mm □) between the test piece and the adherend.

The adhesive strength of a cured product obtained by curing the adhesive paste of the present invention is preferably 7N/mm □ or more, more preferably 10N/mm □ or more, still more preferably 14N/mm □ or more, and particularly preferably 15N/mm □ or more at 23 ℃.

In the present specification, "1 mm □" means "1 mm square", that is, "1 mm × 1mm (square having a side length of 1 mm)".

The adhesive paste of the present invention can be suitably used as an adhesive for a semiconductor element-fixing material because of the above-mentioned characteristics.

2) Method of using adhesive paste and method of manufacturing semiconductor device using adhesive paste

The method for producing a semiconductor device using the adhesive paste of the present invention as an adhesive for optical element-fixing materials is a method having the following step (BI) and step (BII).

Step (BI): a step of applying an adhesive paste to one or both of the adhesive surfaces of the semiconductor element and the supporting substrate and pressing the adhesive surfaces;

step (BII): and (b) heating and curing the adhesive paste of the pressure-sensitive adhesive product obtained in the step (BI) to fix the semiconductor element on the support substrate.

Examples of the semiconductor element include a light emitting element such as a laser or a Light Emitting Diode (LED), an optical semiconductor element such as a light receiving element such as a solar cell, a sensor such as a transistor or a temperature sensor or a pressure sensor, and an integrated circuit. Among them, optical semiconductor elements are preferred from the viewpoint of easily and more suitably exhibiting the effects of the use of the adhesive paste of the present invention.

Examples of the material for the supporting substrate for bonding the semiconductor element include glasses such as soda-lime glass and heat-resistant hard glass, ceramics, sapphire, metals such as iron, copper, aluminum, gold, silver, platinum, chromium, titanium, and alloys of these metals, stainless steel (SUS302, SUS304L, SUS309, and the like), synthetic resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyether ether ketone, polyether sulfone, polyphenylene sulfide, polyether imide, polyimide, polyamide, acrylic resin, norbornene-based resin, cycloolefin resin, and glass epoxy resin.

The adhesive paste of the present invention is preferably filled into a syringe.

By filling the adhesive paste into a syringe, the workability in the coating step is excellent.

The material of the syringe may be any of synthetic resin, metal, and glass, and is preferably synthetic resin.

The volume of the syringe is not particularly limited, and may be appropriately determined depending on the amount of the adhesive paste to be filled or applied.

Further, a commercially available syringe may be used. Examples of commercially available products include SS-01T series (TERUMO Co., Ltd.), PSY series (Musashi Engineering, Inc.) and the like.

In the method for manufacturing a semiconductor device of the present invention, the syringe filled with the adhesive paste is vertically lowered to be close to the support substrate, and after a predetermined amount of the adhesive paste is discharged from the tip of the syringe, the syringe is raised to be separated from the support substrate, and the support substrate is moved laterally. Then, by repeating this operation, the adhesive paste is continuously applied on the support substrate. Then, a semiconductor element is mounted on the coated adhesive paste and is press-bonded to the support substrate.

The amount of the adhesive paste to be applied is not particularly limited as long as the adhesive paste can firmly bond the semiconductor element to be bonded and the supporting substrate by curing. The thickness of the coating film of the adhesive paste is usually 0.5 μm or more and 5 μm or less, preferably 1 μm or more and 3 μm or less.

Subsequently, the obtained adhesive paste of the pressure-sensitive adhesive is cured by heating, whereby the semiconductor element is fixed to the supporting substrate.

The heating temperature and heating time are as described in the item 1) for binding paste.

In the semiconductor device obtained by the method for manufacturing a semiconductor device of the present invention, the semiconductor element is favorably mounted on the adhesive paste, and 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 not limited to the following examples.

The parts and% in each example are on a mass basis unless otherwise specified.

[ average molecular weight measurement ]

The mass average molecular weight (Mw) and the number average molecular weight (Mn) of the thermosetting organopolysiloxane compound (a) obtained in the preparation example were standard polystyrene conversion values, and were measured by the following apparatus and conditions.

Device name: HLC-8220GPC, manufactured by TOSOH CORPORATION;

column: sequentially connecting TSKgel GMHXL, TSKgel GMHXL and TSKgel 2000 HXL;

solvent: tetrahydrofuran;

injection amount: 80 μ l;

measuring temperature: 40 ℃;

flow rate: 1 ml/min;

a detector: a differential refractometer.

[ measurement of IR Spectrum ]

The IR Spectrum of the thermosetting organopolysiloxane compound (A) obtained in preparation example was measured using a Fourier transform infrared spectrophotometer (Perkin Elmer, Inc., Spectrum 100).

Preparation example 1

71.37g (400mmol) of methyltriethoxysilane (manufactured by shin-Etsu chemical Co., Ltd.) was charged into a 300ml eggplant-shaped flask, an aqueous solution obtained by dissolving 0.10g of 35% hydrochloric acid (0.25 mol% based on the total amount of silane compounds) in 21.6ml of distilled water was added thereto with stirring, the whole contents were stirred at 30 ℃ for 2 hours, then, the temperature was raised to 70 ℃ and the mixture was stirred for 5 hours, the reaction mixture was returned to room temperature (23 ℃) and 140g of propyl acetate was added thereto.

While the entire contents were stirred, 0.12g of 28% aqueous ammonia (0.5 mol% based on the total amount of silane compounds) was added thereto, and the mixture was further stirred at 70 ℃ for 3 hours.

Purified water was added to the reaction solution, and the reaction solution was separated, followed by repeating this operation until the pH of the aqueous layer reached 7.0.

The organic layer was concentrated with an evaporator, and the concentrate was vacuum-dried, whereby 55.7g of a thermosetting organopolysiloxane compound (A1) was obtained.

The thermosetting organopolysiloxane compound (A1) had a mass average molecular weight (Mw) of 7,800 and a molecular weight distribution (Mw/Mn) of 4.52.

Further, the IR spectrum data of the thermosetting organopolysiloxane compound (a1) is shown below.

Si-CH ₃ ：1272cm ^-1 、1409cm ^-1 ，Si-O：1132cm ^-1 。

(preparation example 2)

A300 mL eggplant-shaped flask was charged with 17.0g (77.7mmol) of 3,3, 3-trifluoropropyltrimethoxysilane (manufactured by shin-Etsu chemical Co., Ltd.) and 32.33g (181.3mmol) of methyltriethoxysilane, and an aqueous solution prepared by dissolving 0.0675g of 35% hydrochloric acid (0.65 mmol of HCl and 0.25mol% based on the total amount of silane compounds) in 14.0mL of distilled water was added thereto under stirring, and the whole was stirred at 30 ℃ for 2 hours, and then heated to 70 ℃ for 20 hours.

While the contents were stirred further, 0.0394g of 28% aqueous ammonia (NH) was added thereto ₃ In an amount of 0.65mmol) and 46.1g of propyl acetate, the reaction solution was stirred at 70 ℃ for 40 minutes in such a state that the pH of the reaction solution was 6.9.

After the reaction mixture was cooled to room temperature (23 ℃), 50g of propyl acetate and 100g of water were added thereto to conduct a liquid separation treatment, thereby obtaining an organic layer containing the reaction product. Magnesium sulfate was added to the organic layer to carry out drying treatment.

After magnesium sulfate was removed by filtration, the organic layer was concentrated by an evaporator, and the concentrate was dried in vacuo, whereby 22.3g of a thermosetting organopolysiloxane compound (A2) was obtained.

The thermosetting organopolysiloxane compound (A2) had a mass average molecular weight (Mw) of 5,500 and a molecular weight distribution (Mw/Mn) of 3.40.

Further, the IR spectrum data of the thermosetting organopolysiloxane compound (a2) is shown below.

Si-CH ₃ ：1272cm ^-1 、1409cm ^-1 ，Si-O：1132cm ^-1 ，C-F：1213cm ^-1 。

Preparation example 3

A300 ml eggplant-shaped flask was charged with 28.91g (145.8mmol) of phenyltrimethoxysilane (manufactured by shin-Etsu chemical Co., Ltd.), an aqueous solution prepared by dissolving 0.0376g of 35% hydrochloric acid (0.25 mol% based on the total amount of silane compounds) in 7.874ml of distilled water was added with stirring, the whole contents were stirred at 30 ℃ for 2 hours, then the temperature was raised to 70 ℃ and stirred for 5 hours, the reaction solution was returned to room temperature (23 ℃) and 50g of propyl acetate and 100g of water were added to carry out liquid separation treatment, and an organic layer containing the reaction product was obtained. Magnesium sulfate was added to the organic layer to carry out drying treatment.

After magnesium sulfate was removed by filtration, the organic layer was concentrated by an evaporator, and the concentrate was dried in vacuo, whereby 17.0g of a thermosetting organopolysiloxane compound (a3) was obtained.

The thermosetting organopolysiloxane compound (A3) had a mass average molecular weight (Mw) of 1,100 and a molecular weight distribution (Mw/Mn) of 1.2.

Further, the IR spectrum data of the thermosetting organopolysiloxane compound (a3) is shown below.

Si-C ₆ H ₅ ：698cm ^-1 ，Si-O：1132cm ^-1 。

The compounds used in examples and comparative examples are shown below.

[ (A) component ]

Thermosetting organopolysiloxane compound (a 1): the organopolysiloxane compound obtained in preparation example 1,

thermosetting organopolysiloxane compound (a 2): the organopolysiloxane compound obtained in preparation example 2,

thermosetting organopolysiloxane compound (a 3): the organopolysiloxane compound obtained in preparation example 3.

[ solvent (S) ]

(1) Organic Solvent (SL)

Diethylene glycol monoethyl ether acetate (EDGAC): manufactured by Tokyo chemical industry Co., Ltd. (boiling point: 218 ℃ C.),

ethylene glycol monobutyl ether acetate (BMGAC): manufactured by Tokyo chemical industry Co., Ltd. (boiling point: 192 ℃ C.),

cyclohexanone: manufactured by Tokyo chemical industry Co., Ltd. (boiling point: 157 ℃ C.).

(2) Organic Solvent (SH)

Tripropylene glycol n-butyl ether (TPnB): manufactured by The Dow Chemical Company (boiling point 274 ℃ C.).

(3) Others (C)

Acetone: manufactured by Tokyo chemical industry Co., Ltd. (boiling point 56 ℃ C.).

[ (B) component ]

Silane coupling agent (B1): 1,3, 5-N-tris [3- (trimethoxysilyl) propyl ] isocyanurate (product name "KBM-9659" manufactured by shin-Etsu chemical Co., Ltd.),

silane coupling agent (B2): 3- (trimethoxysilyl) propylsuccinic anhydride (product name "X-12-967C" from shin-Etsu chemical Co., Ltd.).

[ (C) ingredient ]

Fine particles (C1): silica fine particles (NIPPON AEROSIL CO., manufactured by LTD., product name "AEROSIL RX 300", average primary particle diameter: 7nm, specific surface area: 210 m) ² /g)，

Fine particles (C2): silicone microparticles (product name "MSP-SN 08" manufactured by NIKKO RICA CORPORATION, average primary particle diameter: 0.8 μm, spherical shape).

(example 1)

To 100 parts of the thermosetting organopolysiloxane compound (a1), 28 parts of edgac (sl), 10 parts of silane coupling agent (B1), and 3 parts of silane coupling agent (B2) were added, and the entire contents were thoroughly mixed and deaerated, whereby adhesive paste 1 having a solid content concentration of 80% was obtained.

(examples 2 to 13, comparative examples 1 to 4)

Adhesive pastes 2 to 13 and 1r to 4r were obtained in the same manner as in example 1, except that the kinds and mixing ratios of the compounds (components) were changed to those shown in table 1 below.

In examples 9 and 10, the microparticles (C1) and microparticles (C2) were added before adding cyclohexanone (SL), the silane coupling agent (B1), and the silane coupling agent (B2).

Using the adhesive pastes 1 to 13 and 1r to 4r obtained in examples and comparative examples, the following tests were carried out, respectively. The results are shown in table 2.

[ measurement of the Mass reduction Rate ]

15mg of the adhesive pastes obtained in examples and comparative examples were charged into a differential thermal-thermogravimetric simultaneous measuring apparatus (product name "DTG-60" manufactured by Shimadzu corporation), heated at 100 ℃ for 2 hours at a measurement start temperature of 40 ℃ and a temperature rise rate of 10 ℃/min, the masses of the adhesive pastes before and after heating were measured, and the mass reduction rate before and after heating was calculated _100℃2h (%) [ { [ (Mass of adhesive paste before heating) - (Mass of adhesive paste after heating at 100 ℃ for 2 hours)]/(quality of bonding paste before heating) } × 100]。

In addition, the heating condition was changed to 170 ℃ for 2 hours, and the mass reduction rate was adjusted _100℃2h (%) measurement method was performed in the same manner, and the mass reduction rate of the adhesive paste before and after heating was calculated _170℃2h (%) [ { [ (Mass of cementitious paste before heating) - (Mass of cementitious paste after heating at 170 ℃ for 2 hours)]/(quality of bonding paste before heating) } × 100]。

Further, the mass reduction rate is calculated from the measured mass reduction rate _170℃2h Mass reduction rate _100℃2h (%)。

[ evaluation of chip mountability ]

The adhesive pastes obtained in examples and comparative examples were discharged onto an electroless silver-plated copper plate (average roughness Ra of silver-plated surface: 0.025 μm) to a diameter of 0.5mm, and allowed to stand under a standard environment (temperature: 23 ℃ C. + -1 ℃ C., relative humidity: 50. + -. 5%). After 5 minutes, a square having a side length of 1mm (area of 1 mm) was mounted ² ) The silicon chip of (2) was evaluated as "good" when the chip could be mounted without tilting by observing the tilt of the chip, and as "bad" when a problem such as chip tilt occurred.

[ evaluation of adhesive Strength ]

A square 1mm long on one side (1 mm area) ² ) The adhesive pastes obtained in examples and comparative examples were applied to the mirror surface of the silicon chip of (1), and the coating was dried under a standard atmosphere (temperature: 23 ℃ ± 1 ℃, relative humidity: 50 ± 5%) and standing. After 5 minutes, the coated surface was placed on an adherend [ electroless silver-plated copper plate (average roughness Ra of silver-plated surface: 0.025 μm)]The press-bonding is performed so that the thickness of the adhesive paste after press-bonding becomes about 2 μm. Then, the resultant was cured by heat treatment at 100 ℃ for 2 hours to obtain an adherend with a test piece. The adherend with the test piece was placed on a measuring table of a 23 ℃ adhesion tester (4000 series, manufactured by DAGE) for 30 seconds, and stress was applied to the adhesive surface in the horizontal direction (shear direction) at a speed of 200 μm/s from a position 100 μm high from the adherend to measure the adhesive strength (N/mm □) between the test piece and the adherend at 23 ℃.

[ Table 1]

[ Table 2]

The following is clear from tables 1 and 2.

In the adhesive pastes 1 to 13 of examples 1 to 13, cured products obtained by curing the adhesive pastes were excellent in adhesive strength and chip mountability.

In particular, when a solvent having a lower boiling point is contained as the organic Solvent (SL), the adhesive strength of the cured product obtained by curing the adhesive paste is more excellent (examples 1 to 3).

Even when a mixed solvent of an organic Solvent (SL) and an organic Solvent (SH) is used as the solvent (S), an adhesive paste having excellent adhesive strength of a cured product and excellent chip mountability can be obtained (examples 4 to 6).

The adhesive paste having a high solid content concentration is excellent in adhesive strength of a cured product obtained by curing the adhesive paste (examples 4 and 7, and examples 3 and 8).

The adhesive paste containing the fine particles (C) can provide cured products having a good adhesive strength, although the content ratio of the component (a) to the component (B) is relatively small, as compared with the adhesive paste containing no fine particles (C) (examples 9 and 10).

Even when the type of the thermosetting organopolysiloxane compound (a) (the type of the side chain of the polysilsesquioxane compound) was changed, the adhesive strength of the cured product obtained by curing the adhesive paste was excellent (examples 11 to 13).

On the other hand, since the adhesive paste 1r of comparative example 1 contains only the high-boiling organic Solvent (SH) as the solvent (S), the mass reduction rate is high _100℃2h Small, large amounts of solvent remain, and the adhesive paste is not sufficiently cured, and thus sufficient adhesive strength is not exhibited.

Since the adhesive paste 2r of comparative example 2 contains only an organic solvent having a very low boiling point as the solvent (S), the adhesive paste dries immediately after application, and the chip mountability is poor.

In the adhesive paste 3r of comparative example 3, the content of the organic Solvent (SL) was small relative to the total mass of the adhesive paste and the solvent (S) as a whole, and therefore the mass reduction rate was low _100℃2h Small, the adhesive paste could not be sufficiently cured, and the adhesive strength was insufficient.

The adhesive paste 4r of comparative example 4 satisfied the mass reduction rate _100℃2h However, since the content of the organic Solvent (SH) in the solvent (S) is large, a large amount of the organic Solvent (SH) remains in the cured product during heating at 100 ℃.

Claims

1. A bonding paste comprising a thermosetting organopolysiloxane compound (A) and a solvent (S), the thermosetting organopolysiloxane compound (A) being dissolved in the solvent (S),

the solvent (S) contains an organic Solvent (SL) having a boiling point of 100 ℃ or higher and lower than 254 ℃,

the mass reduction rate of the adhesive paste before and after heating the adhesive paste at 100 ℃ for 2 hours _100℃2h Is more than 10%, and

the mass reduction rate of the adhesive paste before and after heating at 170 ℃ for 2 hours was defined as the mass reduction rate _170℃2h Time, mass reduction rate _170℃2h Mass reduction rate _100℃2h Less than 14%.

2. The binding paste according to claim 1, wherein the thermosetting organopolysiloxane compound (a) is a polysilsesquioxane compound.

3. A binding paste according to claim 1 or 2, wherein the organic Solvent (SL) has a boiling point of more than 100 ℃ and less than 200 ℃.

4. Binding paste according to claim 1 or 2, wherein the content of organic Solvent (SL) is 10% by mass or more and 50% by mass or less with respect to the total mass of the binding paste.

5. The binding paste according to claim 1 or 2, wherein the solvent (S) contains an organic Solvent (SH) having a boiling point of 254 ℃ or higher and 300 ℃ or lower.

6. A bonding paste according to claim 1 or 2, further comprising the following component (B),

(B) the components: a silane coupling agent.

7. A bonding paste according to claim 1 or 2, further comprising the following component (C),

(C) the components: and (4) micro-particles.

8. The bonding paste according to claim 1 or 2, wherein the solid content concentration is 50% by mass or more and 90% by mass or less.

9. A bonding paste according to claim 1 or 2, which is substantially free of precious metal catalyst.

10. The adhesive paste according to claim 1 or 2, which is an adhesive for a semiconductor element-fixing material.

11. A method of using the adhesive paste according to any one of claims 1 to 10 as an adhesive for semiconductor element-fixing materials.

12. A method for producing a semiconductor device using the adhesive paste according to any one of claims 1 to 10 as an adhesive for semiconductor element-fixing materials, the method comprising the steps (BI) and (BII),