JP2022151346A - Adhesive paste, application method of adhesive paste and production method of semiconductor device - Google Patents

Abstract

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

Description

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

Conventionally, adhesive pastes have been improved in various ways according to their uses, and have been widely used industrially as raw materials for optical parts and moldings, adhesives, coating agents, and the like.
Adhesive pastes are also attracting attention as pastes for semiconductor element fixing materials such as adhesives for semiconductor element fixing materials.

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

2. Description of the Related Art A semiconductor element adhesive paste for fixing a semiconductor element is usually applied to an object to be applied, such as a substrate such as a lead frame, using a coating device having a discharge pipe (needle).
In a coating apparatus having such a discharge pipe, for example, the discharge pipe descends vertically to approach the object to be coated, and after discharging a predetermined amount of adhesive paste from the tip of the discharge pipe, the discharge pipe rises to the object to be coated. As the object is separated from the object, the object to be coated moves laterally. By repeating this operation, the semiconductor element adhesive paste is continuously applied to the object to be applied. After that, a semiconductor element is mounted (mounted) on the applied adhesive paste and adhered to the object to be applied.

Usually, after the adhesive paste is applied to the object to be applied, the semiconductor element is mounted on the applied adhesive paste immediately and adhered to the object to be applied.
However, in a production line or the like, for some reason, the applied adhesive paste may be left as it is for a long time without mounting the semiconductor element.
In such a case, if the applied adhesive paste is left for a long time, the viscosity of the adhesive paste may change and the semiconductor element may not be mounted in a preferable state.
In order to solve this problem, Patent Document 1 discloses an adhesive obtained by dissolving a specific polysilsesquioxane compound in a solvent containing a high-boiling organic solvent having a boiling point of 254° C. or more and 300° C. or less. It is proposed that the adhesive is capable of mounting an optical element well even after 20 minutes or more from being applied to a substrate, just as immediately after application, and is also excellent in adhesiveness. It is

By the way, optical parts and sensor chips are easily affected by heat. Therefore, when the heat curing method is used as a method for curing the adhesive, it is preferable to cure the adhesive at a low temperature as much as possible from the viewpoint of avoiding the influence of heating on the optical parts and the sensor chip.
However, the adhesive described in Patent Document 1 requires heat treatment at a high temperature of 170° C. for 2 hours and for a long time. There was a concern that it would remain on the surface and a sufficient adhesive strength could not be obtained. In addition, when the adhesive is heated at a low temperature, the rate at which the concentration of the component (active ingredient) excluding the solvent in the adhesive increases is slow, so the adhesive is difficult to sufficiently heat cure, and a cured product having sufficient adhesive strength can be obtained. I was worried that it wouldn't work.
Further, when acetone or the like having a very low boiling point is used as a solvent, there is a concern that the adhesive dries immediately after being discharged, making it impossible to satisfactorily mount the semiconductor element.

Therefore, the cured product obtained by heating at a low temperature has excellent adhesiveness, and even if it is left for a long time after being applied to the object to be coated, the semiconductor element can be adhered in the same manner as immediately after application. There is a need for an adhesive paste that can be well mounted on the paste.

JP 2018-168286 A

The present invention has been made in view of such circumstances, and the cured product obtained by heating at a low temperature has excellent adhesiveness, and even after a long time has passed after being applied to the object, it can be used as a semiconductor. An adhesive paste capable of mounting an element well, a method of using this adhesive paste as an adhesive for a semiconductor element fixing material, and a method of manufacturing a semiconductor device using this adhesive paste as an adhesive for a semiconductor element fixing material. intended to provide
In the present invention, low temperature means 80.degree. C. to 120.degree.
Moreover, "excellent adhesiveness" means "high adhesive strength".

The inventors of the present invention have made intensive studies to solve the above problems. As a result, an adhesive paste obtained by dissolving a thermosetting organopolysiloxane compound in a solvent containing an organic solvent having a boiling point of 100° C. or more and less than 254° C. and having a controlled mass reduction rate was found to be obtained when heated at a low temperature. , Since the solvent evaporates efficiently, the resulting cured product has excellent adhesiveness, and it is possible to mount the semiconductor element satisfactorily even after a long time has passed since it was applied to the object to be coated. The inventors have found that and completed the present invention.

Thus, according to the present invention, the following adhesive pastes [1] to [10], a method of using the adhesive paste of [11], and a method of manufacturing a semiconductor device using the adhesive paste of [12] are provided.

[1] An adhesive paste containing a thermosetting organopolysiloxane compound (A) and a solvent (S), wherein the thermosetting organopolysiloxane compound (A) is dissolved in the solvent (S) , the solvent (S) contains an organic solvent (SL) having a boiling point of 100 ° C. or higher and lower than 254 ° C., and the mass of the adhesive paste before and after heating after heating the adhesive paste at 100 ° C. for 2 hours When the rate of decrease of _100° C. for 2 hours is 10% or more, and the rate of mass decrease of the adhesive paste before and after heating after heating the adhesive paste at 170° C. for 2 hours is the rate of mass decrease of _170° C. for 2 hours, Weight loss rate _{170°C 2h} - Adhesive paste whose mass loss rate _{100°C 2h} is 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 organic solvent (SL) has a boiling point of 100°C or higher and lower than 200°C.
[4] The adhesive paste according to any one of [1] to [3], wherein the content of the organic solvent (SL) is 10% by mass or more and 50% by mass or less with respect to the total mass of the adhesive paste.
[5] The adhesive paste according to any one of [1] to [4], wherein the solvent (S) contains an organic solvent (SH) having a boiling point of 254°C or higher and 300°C or lower.

[6] The adhesive paste according to any one of [1] to [5], further comprising the following component (B).
(B) component: silane coupling agent [7] The adhesive paste according to any one of [1] to [6], further comprising the following component (C).
(C) Component: fine particles [8] The adhesive paste according to any one of [1] to [7], having a solid content concentration of 50% by mass or more and 90% by mass or less.
[9] The adhesive paste according to any one of [1] to [8], which does not substantially contain a noble metal catalyst.
[10] The adhesive paste according to any one of [1] to [9], which is an adhesive for a semiconductor element fixing material.

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

According to the present invention, a chip mount that can satisfactorily mount a semiconductor element even after a long time has passed since the cured product obtained by heating at a low temperature has adhesiveness and is applied to the object to be coated. Adhesive pastes are provided that are compatible with the properties.
Further, according to the present invention, there are provided a method of using this adhesive paste as an adhesive for a semiconductor element fixing material, and a method of manufacturing a semiconductor device using this adhesive paste as an adhesive for a semiconductor element fixing material.

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

1) Adhesive Paste The adhesive paste of the present invention contains a thermosetting organopolysiloxane compound (A) and a solvent (S), and the thermosetting organopolysiloxane compound (A) is dissolved in the solvent (S). wherein the solvent (S) contains an organic solvent (SL) having a boiling point of 100° C. or more and less than 254° C., and after heating the adhesive paste at 100° C. for 2 hours, The mass reduction rate of the adhesive paste before and after heating at _100° C. for 2 hours is 10% or more, and the mass reduction rate of the adhesive paste before and after heating after heating the adhesive paste at 170° C. for 2 hours is referred to as the mass reduction rate. When the temperature is _170°C for 2 hours, the mass reduction rate of _{170°C for 2h} - the mass reduction rate of _{100°C for 2h} is less than 14%.

In the present invention, the adhesive paste refers to a viscous liquid in a fluid state.
Since the adhesive paste of the present invention has the properties described above, it is excellent in workability in the coating process.
Here, excellent workability in the coating process means that in the coating process, when the adhesive paste is discharged from the discharge pipe and then the discharge pipe is pulled up, the amount of stringing is small or is interrupted immediately, causing resin to splatter. , means that there is no contamination of the surroundings due to spread of droplets after application.

After heating the adhesive paste at 100° C. for 2 hours, the adhesive paste of the present invention has a mass reduction rate of _100° C. for 2 hours before and after heating of 10% or more, preferably 12% or more and less than 50%, more preferably. is 13% or more and less than 45%.
When the mass reduction rate of _{100° C.} for 2 hours is equal to or higher than the above lower limit, the cured product obtained by heating at a low temperature has excellent adhesiveness.
In addition, when the mass reduction rate of _{100° C.} for 2 hours is equal to or higher than the above upper limit, the amount of the active ingredient that exhibits the adhesive function of the cured product obtained by heating at a low temperature decreases, so there is a risk that high adhesive strength will not be exhibited. By being less than the upper limit, the fear can be reduced.
Here, the term "active ingredient" refers to a component other than the solvent (S) contained in the adhesive paste.

Further, the adhesive paste of the present invention has a mass reduction rate of ₁₇₀ ° C. for 2 hours when the mass reduction rate of the adhesive paste before and after heating after heating the adhesive paste at ₁₇₀ ° C. for 2 hours is 170° C. for 2 hours. - The mass reduction rate at _{100°C for 2h} is less than 14%, preferably less than 12%, more preferably 1% or more and less than 10%.
Since the mass reduction rate of _{170°C for 2h} - the mass reduction rate of _{100°C for 2h} is less than the above upper limit, when heated at a low temperature, the solvent evaporates efficiently in the same way as when heated at a high temperature, so that at a low temperature The cured product obtained by heating is superior in adhesiveness.
The mass reduction rate of _{100° C.} for 2 hours and the mass reduction rate of _{170° C.} for 2 hours can be measured 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)").
Since the adhesive paste of the present invention contains the component (A), a cured product having excellent adhesiveness can be easily obtained by heating at a low temperature.

The thermosetting organopolysiloxane compound (A) of the present invention is a compound having a carbon-silicon bond and a siloxane bond (--Si--O--Si--) in its molecule.
In addition, since component (A) is a thermosetting compound, at least one functional group selected from the group consisting of functional groups capable of condensation reaction by heating and functional groups capable of condensation reaction through hydrolysis It is preferred to have a group.
Such a functional group is preferably at least one selected from the group consisting of a hydroxyl group and an alkoxy group, more preferably a hydroxyl group and an alkoxy group having 1 to 10 carbon atoms.
The main chain structure of the thermosetting organopolysiloxane compound (A) is not particularly limited, and may be linear, ladder-like, or cage-like.
For example, the structure represented by the following formula (a-1) is used as the linear main chain structure, and the structure represented by the following formula (a-2) is used as the ladder-like main chain structure. Examples of the main chain structure include structures represented by the following formula (a-3).

In formulas (a-1) to (a-3), Rx, Ry, and Rz each independently represent a hydrogen atom or an organic group, and the organic group includes an unsubstituted or substituted alkyl group, an unsubstituted A substituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or an alkylsilyl group is preferred. The plurality of Rx in formula (a-1), the plurality of Ry in formula (a-2), and the plurality of Rz in formula (a-3) may be the same or different. However, both Rx in formula (a-1) are not hydrogen atoms.

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

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

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

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

The aryl group of unsubstituted or substituted aryl group includes, for example, aryl groups having 6 to 10 carbon atoms such as phenyl group, 1-naphthyl group and 2-naphthyl group.

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

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

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

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

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

The mass average molecular weight (Mw) of the thermosetting organopolysiloxane compound (A) is usually 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. , 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, it becomes easier to obtain an adhesive paste that gives a cured product with superior heat resistance and adhesiveness.

Although the molecular weight distribution (Mw/Mn) of the thermosetting organopolysiloxane compound (A) is not particularly limited, it is usually 1.0 or more and 10.0 or less, preferably 1.1 or more and 6.0 or less. By using a thermosetting organopolysiloxane compound (A) having a molecular weight distribution (Mw/Mn) within the above range, it becomes easier to obtain an adhesive paste that gives a cured product with superior heat resistance and adhesiveness.
The mass average molecular weight (Mw) and number average molecular weight (Mn) can be obtained as standard polystyrene conversion values 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 trifunctional organosilane compounding.
Since the adhesive paste of the present invention contains a polysilsesquioxane compound as the component (A), it becomes easier to obtain a cured product having excellent adhesiveness by heating at a low temperature.

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

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

The "unsubstituted alkyl group having 1 to 10 carbon atoms" includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n- pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group and the like.
The number of carbon atoms in the “unsubstituted alkyl group having 1 to 10 carbon atoms” represented by R ¹ is preferably 1 to 6, more preferably 1 to 3.

The number of carbon atoms in the “substituted alkyl group having 1 to 10 carbon atoms” represented by R ¹ is preferably 1 to 6, more preferably 1 to 3. The number of carbon atoms means the number of carbon atoms in the portion (alkyl group portion) excluding the substituents. Therefore, when R ¹ is a “substituted alkyl group having 1 to 10 carbon atoms”, the number of carbon atoms in R ¹ may exceed 10 in some cases.
Examples of the alkyl group of the "substituted alkyl group having 1 to 10 carbon atoms" include the same groups as the "unsubstituted alkyl group having 1 to 10 carbon atoms".

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

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

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

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

Among these, R ¹ is an unsubstituted alkyl group having 1 to 10 carbon atoms, a fluorine atom, from the viewpoint of easily obtaining a polysilsesquioxane compound with a stable structure and more stable performance as an adhesive paste. and an unsubstituted aryl group having 6 to 12 carbon atoms.
By using a polysilsesquioxane compound in which R ¹ is an unsubstituted alkyl group having 1 to 10 carbon atoms, it becomes easier to obtain an adhesive paste that gives a cured product with excellent heat resistance and adhesiveness.
By using a polysilsesquioxane compound in which R ¹ is an alkyl group having 1 to 10 carbon atoms and having a fluorine atom, it becomes easier to obtain an adhesive paste or a cured product having a low refractive index. It becomes easy to be suitably used for the desired optical semiconductor device.
As the alkyl group having 1 to 10 carbon atoms and having a fluorine atom, a group represented by the composition formula: C _m H _(2m−n+1) F _n (m is an integer of 1 to 10, n is 1 or more, (2m+1) are the following integers). Among these, a 3,3,3-trifluoropropyl group is preferred.
By using a polysilsesquioxane compound in which R ¹ is an unsubstituted aryl group having 6 to 12 carbon atoms, it becomes easy to obtain an adhesive paste or a cured product having a high refractive index, and a high refractive index is desired. It becomes easy to be suitably used for the optical semiconductor element which is used.

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

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

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

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

In formula (a-5), R ¹ has the same meaning as R ¹ in formula (a-4). * represents a Si atom, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and at least one of the three * is a Si atom. Examples of alkyl groups having 1 to 10 carbon atoms represented by * include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group and t-butyl group. A plurality of * may all be the same or different.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[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°C or higher and lower than 254°C.
Here, the boiling point refers to the boiling point at 1013 hPa (same in this specification)
The organic solvent (SL) is not particularly limited as long as it has a boiling point of 100° C. or more and less than 254° C. and can dissolve or disperse the components of the adhesive paste of the present invention.
The boiling point of the organic solvent (SL) is 100°C or higher and lower than 254°C, preferably 100°C or higher and lower than 200°C, more preferably 105°C or higher and lower than 185°C, and 110°C or higher and lower than 170°C. It is particularly preferred to have

Such an organic solvent (SL) evaporates efficiently when heated at a low temperature compared to a high boiling point organic solvent having a boiling point of 254° C. or more and 300° C. or less. Therefore, by containing an organic solvent (SL), an adhesive paste having a mass reduction rate of 10% or more at _{100°C for 2h} and a mass reduction rate of _{170°C for 2h} - _{100°C for 2h} is less than 14%. easier to obtain. In addition, such an organic solvent (SL) has a relatively slow volatilization rate compared to a low boiling point organic solvent having a boiling point of less than 100°C.
Therefore, when an adhesive paste containing an organic solvent (SL) is heated at a low temperature, a large amount of the solvent is efficiently volatilized without remaining, so that sufficient adhesive strength can be easily obtained. However, since the speed at which the concentration of the active ingredient in the adhesive paste increases is high, the adhesive paste is easily cured. Therefore, the obtained cured product has excellent adhesiveness, and the semiconductor element can be satisfactorily mounted even after a long period of time after application to the object.

Specific examples of the organic solvent (SL) include diethylene glycol monobutyl ether acetate (boiling point 247° C.), dipropylene glycol-n-butyl ether (boiling point 229° C.), dipropylene glycol methyl ether acetate (boiling point 209° C.), and diethylene glycol butyl methyl ether. (boiling point 212°C), dipropylene glycol-n-propyl ether (boiling point 212°C), tripropylene glycol dimethyl ether (boiling point 215°C), triethylene glycol dimethyl ether (boiling point 216°C), diethylene glycol monoethyl ether acetate (boiling point 218°C) , diethylene glycol-n-butyl ether (boiling point 230° C.), ethylene glycol monophenyl ether (boiling point 245° C.),
Tripropylene glycol methyl ether (boiling point 242°C), propylene glycol phenyl ether (boiling point 243°C), triethylene glycol monomethyl ether (boiling point 249°C), benzyl alcohol (boiling point 204.9°C), phenethyl alcohol (boiling point 219-221°C) ), ethylene glycol monobutyl ether acetate (boiling point 192°C), ethylene glycol monoethyl ether (boiling point 134.8°C), ethylene glycol monomethyl ether (boiling point 124.5°C), propylene glycol monomethyl ether acetate (boiling point 146°C), cyclo Pentanone (boiling point 130°C), cyclohexanone (boiling point 157°C), cycloheptanone (boiling point 180°C), cyclooctanone (boiling point 195-197°C), cyclohexanol (boiling point 161°C), cyclohexadienone (boiling point 104- 104.5°C) and the like.
Among these, as the organic solvent (SL), diethylene glycol monoethyl ether acetate, ethylene glycol from the viewpoint of being able to further express the effect of using the organic solvent (SL) and from the viewpoint of easily mixing the active ingredient well. Monobutyl ether acetate and cyclohexanone are preferred, and ethylene glycol monobutyl ether acetate and cyclohexanone are more preferred.
The organic solvent (SL) may be used singly or in combination of two or more.

The content of the organic solvent (SL) in the adhesive paste of the present invention is preferably 10% by mass or more and 50% by mass or less, and 18% by mass or more and 45% by mass or less, relative to the total mass of the adhesive paste. is more preferable, and it is particularly preferable to be 20% by mass or more and 40% by mass or less.
By setting the content of the organic solvent (SL) to the total mass of the adhesive paste within the above range, the workability in the process of filling the adhesive paste into a syringe and the coating process is excellent, and the effect of using the organic solvent (SL) is further enhanced. can be expressed.
Here, excellent workability in the step of filling the syringe with the adhesive paste means that an appropriate amount can be filled into the syringe without air bubbles.

The adhesive paste of the present invention may contain solvents other than the organic solvent (SL).
As a solvent other than the organic solvent (SL), an organic solvent having a boiling point of 254° C. or more and 300° C. or less (hereinafter sometimes referred to as “organic solvent (SH)”) is preferable.
The organic solvent (SH) is not particularly limited as long as it has a boiling point of 254° C. or more and 300° C. or less and can dissolve or disperse the components of the adhesive paste of the present invention.
By using the organic solvent (SL) together with a solvent other than the organic solvent (SL), the temperature range for heating the adhesive paste to obtain a cured product can be adjusted more precisely. It is possible to reduce the influence of heating on parts and sensor chips.

Specific examples of the organic solvent (SH) include tripropylene glycol-n-butyl ether (boiling point 274° C.), 1,6-hexanediol diacrylate (boiling point 260° C.), diethylene glycol dibutyl ether (boiling point 256° C.), triethylene glycol butyl methyl ether (boiling point 261° C.), polyethylene glycol dimethyl ether (boiling point 264-294° C.), tetraethylene glycol dimethyl ether (boiling point 275° C.), polyethylene glycol monomethyl ether (boiling point 290-310° C.) and the like.
Among these, as the organic solvent (SH), tripropylene glycol-n-butyl ether, 1,6-hexanediol diol diol, from the viewpoint that the effect of using the organic solvent (SL) and the organic solvent (SH) in combination is more likely to be obtained. Acrylates are preferred.

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

The organic solvent (SL) accounts for preferably 60% by mass or more, more preferably 65% by mass or more, and particularly preferably 70% by mass or more, of the entire solvent (S).
By using the organic solvent (SL) in the entire 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 such an amount that the solid content concentration is preferably 50% by mass or more and 90% by mass or less, more preferably 70% by mass or more and 90% by mass or less.
When the solid content concentration is within this range, it is easy to mix the active ingredient well, the workability in the process of filling the adhesive paste into the syringe and the coating process is excellent, and the effect of using the organic solvent (SL) is more expressed. can do.
In addition, when performing die bonding, it is possible to suppress the formation of voids between the adhesive paste and the substrate or the like to which it is to be adhered, thereby increasing the reliability of the package.

[Other ingredients]
The adhesive paste of the present invention contains a thermosetting organopolysiloxane compound (A) and a solvent (S), and 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).
As the silane coupling agent, a silane coupling agent (B1) having a nitrogen atom in the molecule (hereinafter sometimes referred to as "component (B1)") or a silane coupling agent having an acid anhydride structure in the molecule. (B2) (hereinafter sometimes referred to as "(B2) component").

The adhesive paste containing the silane coupling agent (B1) has excellent workability in the coating process, and has excellent curability due to the condensation reaction with the component (A) when heated, and has excellent adhesiveness when heated at a low temperature. , to give a cured product that is more excellent in heat resistance and crack suppression properties of the cured product.
Here, the phrase “excellent crack suppression of the cured product” means that when the adhesive paste is heated to obtain a cured product, cracking of the cured product does not occur due to temperature changes.

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

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

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

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

Among these, the silane coupling agent (B1) is preferably an isocyanurate-based silane coupling agent and a urea-based silane coupling agent, since a cured product having higher adhesive strength can be easily obtained. In addition, those having 4 or more silicon-bonded alkoxy groups are preferred.
Having 4 or more silicon-bonded alkoxy groups means that the total number of alkoxy groups bonded to the same silicon atom and alkoxy groups bonded to different silicon atoms is 4 or more.

As the isocyanurate-based silane coupling agent having 4 or more silicon-bonded alkoxy groups, a compound represented by the following formula (b-3) is a urea-based silane cup having 4 or more silicon-bonded alkoxy groups. Ring agents include compounds represented by the following formula (b-4).

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

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

Specific examples of the compound represented by formula (b-4) include N,N'-bis(3-trimethoxysilylpropyl)urea, N,N'-bis(3-triethoxysilylpropyl)urea, N , N'-bis(3-tripropoxysilylpropyl)urea, N,N'-bis(3-tributoxysilylpropyl)urea, N,N'-bis(2-trimethoxysilylethyl)urea, etc. N'-bis[(tri(C1-C6)alkoxysilyl)(C1-C10)alkyl]urea;
N,N'-bis(3-dimethoxymethylsilylpropyl)urea, N,N'-bis(3-dimethoxyethylsilylpropyl)urea, N,N'-bis(3-diethoxymethylsilylpropyl)urea, etc. N,N'-bis[(di(C1-C6)alkoxy(C1-C6)alkylsilyl(C1-C10)alkyl)urea;
N,N'-bis(3-dimethoxyphenylsilylpropyl)urea, N,N'-bis[(di(C1-6) such as N,N'-bis(3-diethoxyphenylsilylpropyl)urea alkoxy (6 to 20 carbon atoms) arylsilyl (1 to 10 carbon atoms) alkyl) urea;
The silane coupling agents (B1) can be used singly or in combination of two or more.

Among these, the silane coupling agent (B1) includes 1,3,5-N-tris(3-trimethoxysilylpropyl) isocyanurate, 1,3,5-N-tris(3-triethoxysilylpropyl) ) isocyanurate (the above two are hereinafter referred to as “isocyanurate compounds”), N,N′-bis(3-trimethoxysilylpropyl)urea, N,N′-bis(3-triethoxysilylpropyl)urea (The above two are hereinafter referred to as "urea compounds"), and a combination of the isocyanurate compound and the urea compound is preferably used.

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

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

The adhesive paste containing the silane coupling agent (B2) is excellent in workability in the coating step and gives a cured product with excellent adhesiveness and heat resistance when heated at a low temperature.

Silane coupling agents (B2) include 2-(trimethoxysilyl)ethyl succinic anhydride, 2-(triethoxysilyl)ethyl succinic anhydride, 3-(trimethoxysilyl)propyl succinic anhydride, 3-(tri tri(1-6C)alkoxysilyl(2-8C)alkyl succinic anhydrides, such as ethoxysilyl)propyl succinic anhydride;
di(C1-C6)alkoxymethylsilyl(C2-C8)alkyl succinic anhydrides such as 2-(dimethoxymethylsilyl)ethyl succinic anhydride;
(1-6 carbon atoms) alkoxydimethylsilyl (2-8 carbon atoms) alkyl succinic anhydrides, such as 2-(methoxydimethylsilyl)ethyl succinic anhydride;

trihalogenosilyl (2-8 carbon atoms) alkyl succinic anhydrides such as 2-(trichlorosilyl)ethyl succinic anhydride and 2-(tribromosilyl)ethyl succinic anhydride;
dihalogenomethylsilyl (2-8 carbon atoms) alkyl succinic anhydride, such as 2-(dichloromethylsilyl)ethyl succinic anhydride;
2-(chlorodimethylsilyl)ethyl succinic anhydride, halogenodimethylsilyl (2-8 carbon atoms) alkyl succinic anhydride;
Silane coupling agents (B2) can be used singly or in combination of two or more.

Among them, the silane coupling agent (B2) is preferably tri(C 1-6) alkoxysilyl (C 2-8) alkyl succinic anhydride, 3-(trimethoxysilyl) propyl succinic anhydride or 3-(Triethoxysilyl)propyl succinic anhydride is particularly preferred.

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

(2) Microparticles (C)
The adhesive paste of the present invention may contain fine particles as the component (C).
The fine particles include fine particles (C1) having an average primary particle diameter of 5 nm or more and 40 nm or less (hereinafter sometimes referred to as "component (C1)") or fine particles (C2) having an average primary particle diameter of more than 0.04 μm and not more than 8 μm. (hereinafter sometimes referred to as "(C2) component").

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

The specific surface area of the fine particles (C1) is preferably 10 m ² /g or more and 500 m ² /g or less, more preferably 20 m ² /g or more and 300 m ² /g or less. When the specific surface area is within the above range, it becomes easier to obtain an adhesive paste with better workability in the coating process.
The specific surface area can be determined by the BET multipoint method.

The shape of the fine particles (C1) may be spherical, chain-like, needle-like, plate-like, flake-like, rod-like, fiber-like, and the like, but is preferably spherical. The term "spherical" as used herein means a true sphere, as well as a substantially spherical shape including spheroids, oval shapes, confetti-like shapes, polyhedral shapes that can be approximated to spheres such as cocoon-like spheres.

The constituent components of fine particles (C1) are not particularly limited, and include metals, metal oxides, minerals, metal carbonates, metal sulfates, metal hydroxides, metal silicates, inorganic components, organic components, silicone, and the like. mentioned.
Further, the fine particles (C1) to be used may have a modified surface.

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

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

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

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

Silicone means an artificial polymer compound having a main skeleton formed by siloxane bonds. Examples include dimethylpolysiloxane, diphenylpolysiloxane, and methylphenylpolysiloxane.

Fine particles (C1) can be used singly or in combination of two or more.
Among these, in the present invention, silica, metal oxides, and minerals are preferable, and silica is more preferable, because an adhesive paste having excellent transparency can be easily obtained.

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

When the adhesive paste of the present invention contains fine particles (C1) [component (C1)], the content of component (C1) is not particularly limited, but the amount is determined by the mass ratio of component (A) to component (C1). [Component (A): Component (C1)], 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, more preferably 100:0.8 to 100:30.
By using the component (C1) within the above range, the effect of adding the component (C1) can be further exhibited.

An adhesive paste containing the fine particles (C2) gives a cured product with excellent adhesiveness and heat resistance when heated at a low temperature.
Since this effect is more likely to be obtained, the average primary particle size 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, still more preferably more than 1 μm and 4 μm or less.

The average primary particle diameter of the fine particles (C2) is measured by a laser scattering method using a laser diffraction/scattering particle size distribution analyzer (for example, product name “LA-920” manufactured by Horiba, Ltd.). is obtained by doing

The shape of the fine particles (C2) may be the same as those exemplified as the shape of the fine particles (C1), but a spherical shape is preferred.
Further, as the constituent component of the fine particles (C2), the same components as those exemplified as the constituent components of the fine particles (C1) can be mentioned.
Fine particles (C2) can be used singly or in combination of two or more.
Among these, from the viewpoint that it is relatively easy to mix as an adhesive paste, and from the fact that it is easy to obtain a cured product with excellent adhesiveness and heat resistance, it consists of a metal oxide, silica, and silicone whose surface is coated with silicone. At least one fine particle selected from the group is preferable, and silica and silicone are more preferable.

When the adhesive paste of the present invention contains fine particles (C2) [component (C2)], the content of component (C2) is not particularly limited, but the amount is determined by the mass ratio of component (A) to component (C2). [Component (A): Component (C2)], preferably 100:0.1 to 100:40, more preferably 100:0.2 to 100:30, more preferably 100:0.3 to 100:20 , more preferably 100:0.5 to 100:15, and particularly preferably 100:0.8 to 100:12.
By using the component (C2) within the above range, the effect of adding the component (C2) can be further exhibited.

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

Antioxidants are added to prevent oxidative deterioration during heating. Antioxidants include phosphorus antioxidants, phenolic antioxidants, sulfur antioxidants, and the like.

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

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

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

A light stabilizer is added for the purpose of improving the light resistance of the resulting adhesive paste.
Light stabilizers include, for example, poly[{6-(1,1,3,3,-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6 ,6-tetramethyl-4-piperidine)imino}hexamethylene {(2,2,6,6-tetramethyl-4-piperidine)imino}] and other hindered amines.
These light stabilizers can be used singly or in combination of two or more.
The total amount of component (D) used is generally 20% by mass or less relative to component (A).

The adhesive paste of the present invention can be produced, for example, by a production method comprising the following steps (AI) and (AII).
Step (AI): Polycondensation of at least one compound represented by the above formula (a-6) in the presence of a polycondensation catalyst to obtain a polysilsesquioxane compound Step (AII): Step (AI) ) is dissolved in a solvent (S) containing an organic solvent (SL) having a boiling point of 100° C. or more and less than 254° C. to obtain a solution containing the polysilsesquioxane compound. process

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

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

In the present invention, a cured product can be obtained by heating the adhesive paste to volatilize the solvent (S) and cure the adhesive paste.
The heating temperature for curing is usually 80°C to 180°C, preferably 80°C to 120°C. The heating time for curing is usually 30 minutes to 10 hours, preferably 30 minutes to 5 hours, more preferably 30 minutes to 3 hours.

A cured product obtained by curing the adhesive paste of the present invention has excellent adhesiveness.
For example, it can be confirmed as follows that the cured product obtained by curing the adhesive paste of the present invention has excellent adhesiveness. That is, the adhesive paste of the present invention is applied to the mirror surface of a square silicon chip with a side length of 1 mm (area is 1 mm ² ), and the coated surface is placed on a silver-plated copper plate and crimped (adhesive paste after crimping). thickness: about 2 μm) and cured by heat treatment at 100° C. for 2 hours. This is left on the measurement stage of a bond tester at 23 ° C. for 30 seconds, and stress is applied in the horizontal direction (shear direction) to the adhesive surface at a speed of 200 μm / s from a position 100 μm above the adherend, The adhesive strength (N/mm□) between the test piece and the adherend is measured.

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

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

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

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

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

The adhesive paste of the present invention is preferably filled in a syringe.
Since the syringe is filled with the adhesive paste, workability in the coating process is excellent.
The material of the syringe may be synthetic resin, metal or glass, but synthetic resin is preferred.
The capacity of the syringe is not particularly limited, and may be appropriately determined according to the amount of adhesive paste to be filled or applied.
Moreover, as a syringe, a commercial item can also be used. Commercially available products include, for example, SS-01T series (manufactured by TERUMO) and PSY series (manufactured by Musashi Engineering).

In the manufacturing method of the semiconductor device of the present invention, the syringe filled with the adhesive paste descends vertically to approach the support substrate, and after discharging a predetermined amount of the adhesive paste from the tip of the syringe, the syringe rises to support the support substrate. As the substrate is separated, the support substrate moves laterally. By repeating this operation, the adhesive paste is continuously applied to the support substrate. After that, a semiconductor element is mounted on the applied adhesive paste and pressure-bonded to the support substrate.

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

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

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

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

[Average molecular weight measurement]
The mass-average molecular weight (Mw) and number-average molecular weight (Mn) of the thermosetting organopolysiloxane compound (A) obtained in Production Examples were converted to standard polystyrene values and measured using the following equipment and conditions.
Apparatus name: HLC-8220GPC, manufactured by Tosoh Corporation Column: TSKgelGMHXL, TSKgelGMHXL, and TSKgel2000HXL sequentially connected Solvent: Tetrahydrofuran Injection volume: 80 μl
Measurement temperature: 40°C
Flow rate: 1 ml/min Detector: Differential refractometer

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

(Production example 1)
After charging 71.37 g (400 mmol) of methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) in a 300 ml eggplant-shaped flask, 0.10 g of 35% hydrochloric acid (with respect to the total amount of silane compounds) was added to 21.6 ml of distilled water. 0.25 mol%) was added with stirring, the whole volume was stirred at 30°C for 2 hours, then heated to 70°C and stirred for 5 hours. 140 g of propyl was added.
0.12 g of 28% aqueous ammonia (0.5 mol % with respect to the total amount of the silane compound) was added thereto while stirring the entire volume, the temperature was raised to 70° C., and the mixture was further stirred for 3 hours.
Purified water was added to the reaction solution, the phases were separated, and this operation was repeated until the pH of the aqueous layer reached 7.0.
The organic layer was concentrated by an evaporator, and the concentrate was vacuum-dried to obtain 55.7 g of thermosetting organopolysiloxane compound (A1).
The thermosetting organopolysiloxane compound (A1) had a mass average molecular weight (Mw) of 7,800 and a molecular weight distribution (Mw/Mn) of 4.52.
IR spectrum data of the thermosetting organopolysiloxane compound (A1) are shown below.
Si—CH ₃ : 1272 cm ⁻¹ , 1409 cm ⁻¹ , Si—O: 1132 cm ⁻¹

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

(Production example 3)
After charging 28.91 g (145.8 mmol) of phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) in a 300 ml eggplant-shaped flask, 0.0376 g of 35% hydrochloric acid (total amount of silane compound) was added to 7.874 ml of distilled water. 0.25 mol%) was added with stirring, and the total volume was stirred at 30°C for 2 hours, then heated to 70°C and stirred for 5 hours, and then the reaction solution was returned to room temperature (23°C). , 50 g of propyl acetate and 100 g of water were added to perform liquid separation treatment to obtain an organic layer containing a reaction product. Drying treatment was performed by adding magnesium sulfate to this organic layer.
After removing the magnesium sulfate by filtration, the organic layer was concentrated by an evaporator and the concentrate was vacuum-dried to obtain 17.0 g of a thermosetting organopolysiloxane compound (A3).
The thermosetting organopolysiloxane compound (A3) had a mass average molecular weight (Mw) of 1,100 and a molecular weight distribution (Mw/Mn) of 1.2.
IR spectrum data of the thermosetting organopolysiloxane compound (A3) are shown below.
Si—C ₆ H ₅ : 698 cm ⁻¹ , Si—O: 1132 cm ⁻¹

The compounds used in Examples and Comparative Examples are shown below.
[(A) component]
Thermosetting organopolysiloxane compound (A1): Organopolysiloxane compound obtained in Production Example 1 Thermosetting organopolysiloxane compound (A2): Organopolysiloxane compound obtained in Production Example 2 Thermosetting organopolysiloxane Compound (A3): Organopolysiloxane compound obtained in Production Example 3

[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 Dow Chemical Company (boiling point 274° C.)
(3) Other 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 (manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM-9659”)
Silane coupling agent (B2): 3-(trimethoxysilyl)propylsuccinic anhydride (manufactured by Shin-Etsu Chemical Co., Ltd., product name “X-12-967C”)
[(C) component]
Fine particles (C1): silica fine particles (manufactured by Nippon Aerosil Co., Ltd., product name “AEROSIL RX300”, average primary particle size: 7 nm, specific surface area: 210 m ² /g)
Microparticles (C2): Silicone microparticles (manufactured by Nikko Rica, product name “MSP-SN08”, average primary particle size: 0.8 μm, shape: spherical)

(Example 1)
28 parts of EDGAC (SL), 10 parts of silane coupling agent (B1), and 3 parts of silane coupling agent (B2) are added to 100 parts of thermosetting organopolysiloxane compound (A1), and the entire volume is thoroughly mixed, By defoaming, an adhesive paste 1 having a solid 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 types and blending ratios of the compounds (each component) were changed to those shown in Table 1 below.
In Examples 9 and 10, fine particles (C1) and fine particles (C2) were added before adding cyclohexanone (SL), silane coupling agent (B1) and silane coupling agent (B2).

The following tests were performed using the adhesive pastes 1 to 13 and 1r to 4r obtained in Examples and Comparative Examples. Table 2 shows the results.

[Measurement of mass reduction rate]
15 mg of the adhesive paste obtained in Examples and Comparative Examples was put into a differential thermal/thermogravimetric simultaneous measurement device (manufactured by Shimadzu Corporation, product name “DTG-60”), and the measurement start temperature was 40 ° C. and the temperature increase rate was 10 ° C./ minutes at 100 ° C. for 2 hours, the mass of the adhesive paste before and after heating is measured, and the mass reduction rate before and after heating is _{100 ° C. 2 h} (%) [{[(mass of adhesive paste before heating) - (100 The mass of the adhesive paste after heating at ° C. for 2 hours)]/(the mass of the adhesive paste before heating)}×100] was calculated.
In addition, except that the heating conditions were changed to 170 ° C. for 2 hours, the mass loss rate of the adhesive paste before and after heating was _{170 ° C. 2 h (} %) [{ [(mass of adhesive paste before heating)−(mass of adhesive paste after heating at 170° C. for 2 hours)]/(mass of adhesive paste before heating)}×100] was calculated.
Further, from the measured mass loss rate, mass loss rate _{170°C 2h} - mass loss rate _{100°C 2h} (%) was calculated.

[Chip mountability evaluation]
The adhesive pastes obtained in Examples and Comparative Examples were discharged onto an electroless silver-plated copper plate (average roughness Ra of the silver-plated surface: 0.025 μm) so that the diameter was 0.5 mm, and tested under a standard environment (temperature : 23°C ± 1°C, relative humidity: 50 ± 5%). After 5 minutes, a square silicon chip with a side length of 1 mm (area of 1 mm ² ) was mounted, and the tilt of the chip was observed. was evaluated as "bad".

[Adhesion strength evaluation]
The adhesive paste obtained in Examples and Comparative Examples was applied to the mirror surface of a square silicon chip with a side length of 1 mm (area of 1 mm ² ), and under standard environment (temperature: 23 ° C. ± 1 ° C., relative humidity) : 50±5%). 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)], and the thickness of the adhesive paste after pressure bonding was about 2 μm. crimped to. After that, it was cured by heat treatment at 100° C. for 2 hours to obtain an adherend with a test piece. The adherend with this test piece is left on the measurement stage of a bond tester (manufactured by Daisy, series 4000) for 30 seconds at 23 ° C., and adhered at a speed of 200 µm / s from a position 100 µm above the adherend. A stress was applied in the horizontal direction (shear direction) to the surface, and the adhesive strength (N/mm□) between the test piece and the adherend was measured at 23°C.

Tables 1 and 2 reveal the following.
The adhesive pastes 1 to 13 of Examples 1 to 13 are excellent in adhesive strength of cured products obtained by curing the adhesive pastes, and are also excellent in chip mountability.
In particular, when a solvent with a lower boiling point is contained as the organic solvent (SL), the adhesive strength of the cured product obtained by curing the adhesive paste is superior (Examples 1 to 3).
Even when a mixed solvent of an organic solvent (SL) and an organic solvent (SH) is used as the solvent (S), it is possible to obtain an adhesive paste having excellent adhesive strength of the cured product and excellent chip mountability. Yes (Examples 4-6).
An adhesive paste having a high solid content concentration is superior in adhesive strength of a cured product obtained by curing the adhesive paste (Examples 4 and 7, Examples 3 and 8).
The adhesive paste to which the fine particles (C) are added has good adhesion even though the content of the components (A) and (B) is relatively small compared to the adhesive paste to which the fine particles (C) are not added. Gives cured products with strength (Examples 9 and 10).
Even when the type of the thermosetting organopolysiloxane compound (A) (type of polysilsesquioxane compound side chain) is changed, the adhesive strength of the cured product obtained by curing the adhesive paste is excellent (implementation Examples 11-13).

On the other hand, since the adhesive paste 1r of Comparative Example 1 contains only a high boiling point organic solvent (SH) as the solvent (S), the mass reduction rate at _{100° C.} for 2 hours is small, and a large amount of solvent remains. The adhesive paste cannot be cured sufficiently, and 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, resulting in poor chip mountability.
In the adhesive paste 3r of Comparative Example 3, the content of the organic solvent (SL) is small relative to the total mass of the adhesive paste and the entire solvent (S), so the mass reduction rate at _{100 ° C. 2h} is small, and the adhesive paste is sufficiently It cannot be cured and does not develop sufficient adhesive strength.
Although the adhesive paste 4r of Comparative Example 4 satisfies the mass reduction rate of _{100° C.} for 2 hours, the content of the organic solvent (SH) in the solvent (S) is large. A relatively large amount of organic solvent (SH) remains in the adhesive paste, and the adhesive paste cannot be sufficiently cured, resulting in insufficient adhesive strength.

Claims (12)

An adhesive paste containing a thermosetting organopolysiloxane compound (A) and a solvent (S), wherein the thermosetting organopolysiloxane compound (A) is dissolved in the solvent (S),
The solvent (S) contains an organic solvent (SL) having a boiling point of 100° C. or more and less than 254° C.,
After heating the adhesive paste at 100° C. for 2 hours, the mass reduction rate _100° C. for 2 hours of the adhesive paste before and after heating is 10% or more, and
After heating the adhesive paste at 170 ° C. for 2 hours, when the mass loss rate of the adhesive paste before and after heating is _{170 ° C. 2 h} , the mass loss rate _{170 ° C. 2 h} - mass loss rate _{100 ° C. 2 h} is Adhesive pastes that are less than 14%. The adhesive paste according to claim 1, wherein the thermosetting organopolysiloxane compound (A) is a polysilsesquioxane compound. The adhesive paste according to claim 1 or 2, wherein the organic solvent (SL) has a boiling point of 100°C or higher and lower than 200°C. The adhesive paste according to any one of claims 1 to 3, wherein the content of the organic solvent (SL) is 10% by mass or more and 50% by mass or less with respect to the total mass of the adhesive paste. The adhesive paste according to any one of claims 1 to 4, wherein the solvent (S) contains an organic solvent (SH) having a boiling point of 254°C or higher and 300°C or lower. The adhesive paste according to any one of claims 1 to 5, further comprising the following component (B).
(B) component: silane coupling agent The adhesive paste according to any one of claims 1 to 6, further comprising the following component (C).
(C) component: fine particles The adhesive paste according to any one of claims 1 to 7, which has a solid content concentration of 50% by mass or more and 90% by mass or less. The adhesive paste according to any one of claims 1 to 8, which is substantially free of noble metal catalysts. The adhesive paste according to any one of claims 1 to 9, which is an adhesive for a semiconductor element fixing material. A method of using the adhesive paste according to any one of claims 1 to 10 as an adhesive for a semiconductor element fixing material. A method for manufacturing a semiconductor device using the adhesive paste according to any one of claims 1 to 10 as an adhesive for a semiconductor element fixing material, comprising the following steps (BI) and (BII). Method.
Step (BI): Applying the adhesive paste to the bonding surface of one or both of the semiconductor element and the support substrate, and press-bonding Step (BII): Heating and curing the adhesive paste of the crimped product obtained in Step (BI) and fixing the semiconductor element to the support substrate