JP2002194215A - Sealing material, method of sealing semiconductor or the like, process for producing semiconductor device, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealing material having high reliability because of low moisture absorbency, having high utility because of low viscosity and rapid curability, and excellent in high-frequency characteristics with low permittivity and low dielectric dissipation factor, a method for sealing electronic parts, an electric circuit, an electric contact point or a semiconductor, with high reliability, high utility and excellent high-frequency characteristics, a process for producing a semiconductor device, and a semiconductor device having high reliability, high utility and excellent high-frequency characteristics. SOLUTION: The sealing material contains as the essential constituents (A) an organic compound having at least two carbon-carbon double bonds reactive with an SiH group in the molecule, (B) a silicon compound having at least two SiH groups in the molecule, and (C) a hydrosilylation catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealant, and more particularly, to a sealant having low hygroscopicity and high reliability.
A sealant with low viscosity, low-temperature fast-curing, high practicality, low dielectric constant, low dielectric loss tangent, and excellent high-frequency characteristics, thereby sealing electronic components, electric circuits, electric contacts or semiconductors. The present invention relates to a method for sealing an electronic component, an electric circuit, a semiconductor, or the like or a method for manufacturing a semiconductor device, and a semiconductor device in which a semiconductor is sealed by the method.

[0002]

2. Description of the Related Art As a sealing agent, particularly a sealing agent for semiconductors, an epoxy resin composition containing a polyfunctional epoxy compound, a phenol novolak-based curing agent and an inorganic filler as main components has been widely used. In recent years, with the demand for miniaturization of semiconductor packages, liquid sealing agents such as TAB sealing and underfill sealing for flip-chip connection have been used. An epoxy resin composition mainly containing an epoxy compound, an acid anhydride-based curing agent, and an inorganic filler is widely used. The basic characteristics required of these sealants are heat resistance, adhesiveness, and the like that do not cause a component to fail due to heat history such as solder reflow.

However, in recent years, due to the increase in the density and size of semiconductors and the change in the mounting method of electronic components, there has been a stronger demand for resistance to moisture-absorbing cracks than ever before. In particular, in the case of a liquid sealant, it is an important problem because of the difficulty in lowering the hygroscopicity due to the use of an acid anhydride-based curing agent.

In general, the epoxy resin composition requires a high temperature and a long time for curing, and it is difficult to produce a semiconductor package or the like, and the production cycle becomes long. In order to facilitate manufacturing, shorten the cycle, and reduce manufacturing costs, low-temperature fast-curing properties are required. In liquid sealants, further improvement in fluidity due to enlargement of semiconductors is required. further,
In recent years, as the driving frequency of semiconductor circuits has become higher and the communication frequency has become higher, semiconductors and sealants for electric circuits have been required to have good high-frequency characteristics, that is, materials having a low dielectric constant and a low dielectric loss tangent. ing.

[0005] From the above problems, attempts have been made to improve epoxy resin compositions such as denaturation with a silicone resin, but they are not necessarily sufficiently solved due to problems such as hygroscopicity and dielectric properties inherently derived from epoxy resins. Has not been reached. Also, a sealant using a thermoplastic resin such as PPS has been proposed, but since it is a thermoplastic resin, there is a limit to lowering the viscosity, and it lacks versatility including a liquid sealing method. .

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a low moisture absorption, high reliability, low viscosity, fast curing property, high practicality, a low dielectric constant and a low dielectric loss tangent. The purpose of the present invention is to provide a sealant excellent in high frequency characteristics. Another object of the present invention is to provide a method for sealing an electronic component, an electric circuit, an electric contact, or a semiconductor having high reliability, high practicality, and high frequency characteristics, and a method for manufacturing a semiconductor device. Another object is to provide a semiconductor device having high reliability, high practicality, and high frequency characteristics.

[0007]

Means for Solving the Problems In order to solve the above problems, the present inventors have made intensive studies and found that an organic compound containing at least two carbon-carbon double bonds having a reactivity with a SiH group in one molecule. A compound and at least two S
The present inventors have found that the above problem can be solved by using a silicon compound containing an iH group as an essential component as a sealing agent, and have accomplished the present invention. That is, the present invention relates to (A) Si
An organic compound containing at least two carbon-carbon double bonds in one molecule reactive with an H group, (B) a silicon compound containing at least two SiH groups in one molecule, and (C) hydrosilyl It is a sealant containing a chemical conversion catalyst as an essential component. The present invention is also a method for sealing an electronic component, an electric circuit, an electric contact or a semiconductor, wherein the electronic component, the electric circuit, the electric contact or the semiconductor is sealed with the above-mentioned sealing agent. Furthermore, the present invention is also a method for manufacturing a semiconductor device, in which a semiconductor is sealed with the above sealing agent. Furthermore, the present invention is also a semiconductor device in which a semiconductor is sealed with the above-mentioned sealing agent. Hereinafter, the present invention will be described in detail.

First, the component (A) in the present invention will be described. The component (A) is an organic compound containing at least two carbon-carbon double bonds reactive with a SiH group in one molecule. Examples of such a compound include siloxane units (Si-organic block copolymers and polysiloxane-organic graft copolymers).
O-Si), but containing C,
Those consisting only of H, N, O, S and halogen are preferred. This is because those containing a siloxane unit have problems of gas permeability and repellency. N and / or S
In the case of containing, since the curability tends to be low,
More preferably, it is composed of only C, H, O and halogen. In the case of a substance containing halogen, a toxic substance may be generated during combustion.
It consists only of H and O.

The structure of the component (A) is a carbon-carbon which is bonded to the skeleton by a covalent bond (possibly through a divalent or higher valent substituent) to the skeleton and has reactivity with the SiH group. When represented separately from a group having a double bond (alkenyl group), the alkenyl group may be present anywhere in the molecule. The skeleton of the component (A), which is an organic compound, is not particularly limited, and an organic polymer skeleton or an organic monomer skeleton may be used.

Examples of the organic polymer skeleton include polyether type, polyester type, polyarylate type, polycarbonate type, saturated hydrocarbon type, polyacrylate type, polyamide type, phenol-formaldehyde type (phenol resin type), A polyimide skeleton can be used. Such a skeleton may be linear or branched. As the organic monomer skeleton, for example, phenol, bisphenol, benzene, aromatic hydrocarbons such as naphthalene, aliphatic hydrocarbons,
And mixtures thereof. The alkenyl group of the component (A) is not particularly limited as long as it has reactivity with a SiH group.

[0011]

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An alkenyl group represented by the formula (wherein R ¹ represents a hydrogen atom or a methyl group) is preferred from the viewpoint of reactivity. Also, from the availability of raw materials,

[0013]

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Is particularly preferred. The alkenyl group of the component (A) is represented by the following general formula (II)

[0015]

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An alkenyl group represented by the formula (wherein R ¹ represents a hydrogen atom or a methyl group) is preferable from the viewpoint that the cured product has high heat resistance. Also, from the availability of raw materials,

[0017]

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Is particularly preferred. The alkenyl group may be covalently bonded to the skeleton portion of the component (A) via a divalent or higher valent substituent. Such a divalent or higher valent substituent may be a substituent having 0 to 10 carbon atoms. Although there is no particular limitation, it is preferable that the element be composed of only C, H, N, O, S and halogen. Examples of these substituents include

[0019]

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[0020]

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And the like. Also, two or more of these divalent or more substituents may be connected by a covalent bond to form one divalent or more substituent. Examples of the group covalently bonded to the skeleton as described above include a vinyl group, an allyl group, a methallyl group, an acryl group, a methacryl group,
Hydroxy-3- (allyloxy) propyl, 2-allylphenyl, 3-allylphenyl, 4-allylphenyl, 2- (allyloxy) phenyl, 3- (allyloxy) phenyl, 4- (allyloxy) phenyl Group, 2- (allyloxy) ethyl group, 2,2-bis (allyloxymethyl) butyl group, 3-allyloxy-
2,2-bis (allyloxymethyl) propyl group,

[0022]

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And the like. As the component (A), a low-molecular-weight compound which is difficult to be divided into a skeleton portion and an alkenyl group as described above can also be used. Specific examples of these low-molecular weight compounds include aliphatic chain polyene compounds such as butadiene, isoprene, octadiene, and decadiene, cyclopentadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene,
Aliphatic cyclic polyene compounds such as norbornadiene,
Substituted aliphatic cyclic olefin compounds such as vinylcyclopentene and vinylcyclohexene are exemplified.

From the viewpoint that the heat resistance can be further improved, the component (A) contains a carbon-carbon double bond having a reactivity with a SiH group in an amount of 0.0 / g of the component (A).
Those containing at least 01 mol are preferable, and those containing at least 0.005 mol per 1 g are more preferable.
Those containing 0.008 mol or more are particularly preferred. Specific examples include butadiene, isoprene, vinylcyclohexene, cyclopentadiene, dicyclopentadiene, cyclohexadiene, decadien, diallyl phthalate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, and divinylbenzenes (purity of 50 to 100%). Of, preferably a purity of 8
0-100%), 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and their oligomers, 1,2-polybutadiene (1,2-polybutadiene having a 1,2 ratio of 10 to 100%, preferably 1,2 ratio 50-1
00%),

[0025]

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And the like. The number of carbon-carbon double bonds reactive with the SiH group of the component (A) may be at least two per molecule on average, but exceeds 2 from the viewpoint that heat resistance can be further improved. The number is more preferably three or more, and particularly preferably four or more. When the number of carbon-carbon double bonds having reactivity with the SiH group of the component (A) is 1 or less per molecule, when the reaction with the component (B) occurs, only a graft structure is formed and a crosslinked structure is formed. No.

As the component (A), those which have fluidity at a temperature of 100 ° C. or less are preferable in order to obtain uniform mixing with other components and good workability. Specifically, the viscosity at 23 ° C. is preferably 200 Pa · s or less, more preferably 50 Pa · s or less, and 20 Pa · s or less.
More preferably, it is Pa · s or less.

The molecular weight of the component (A) is not particularly limited, and any one can be suitably used. However, a low molecular weight one is preferably used from the viewpoint that fluidity is more easily developed. Specifically, those having a molecular weight of 50 to 100,000 are preferable, those having a molecular weight of 50 to 1,000 are more preferable,
Those having 50 to 500 are more preferable.

In order to further enhance the reactivity with the component (B), the component (A) is preferably an organic compound containing at least one vinyl group reactive with a SiH group in one molecule. More preferably, one vinyl group
It is preferable that the organic compound contains at least two organic compounds in the molecule.

In order to further increase the reactivity with the component (B), the component (A) may be an organic compound containing at least one allyl group reactive with a SiH group in one molecule. It is preferable that the organic compound has at least two allyl groups in one molecule. Further, specific examples of preferred component (A) include polybutadiene, vinylcyclohexene, cyclopentadiene, dicyclopentadiene, divinylbiphenyl, and bisphenol A diallyl ether because of their industrial availability.

Further, from the viewpoint of having good compatibility with the component (B), one or more compounds selected from organic compounds having a carbon-carbon double bond and a chain having SiH groups and / or Alternatively, a reaction product with a cyclic organopolysiloxane is also preferable. In this case, in order to further increase the compatibility of the reactant with the component (B), a product obtained by removing an unreacted organic compound having a carbon-carbon double bond from the reactant by devolatilization or the like can be used. .

Examples of the component (A) which is such a reactant include bisphenol A diallyl ether and 1,3,3
Reaction product of 5,7-tetramethylcyclotetrasiloxane, reaction product of vinylcyclohexene and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of divinylbenzene and 1,3,5,7-tetramethylcyclotetrasiloxane Reactants, dicyclopentadiene and 1,3,5,7
A reaction product of -tetramethylcyclotetrasiloxane; The various components (A) as described above can be used alone or as a mixture of two or more.

Next, the compound (B) having at least two SiH groups in one molecule will be described.
There is no particular limitation on the compound having a SiH group that can be used in the present invention. For example, International Publication WO 96/15194.
And at least two S in a molecule
Those having an iH group can be used. Of these,
In terms of availability, at least two SiHs per molecule
A chain and / or cyclic organopolysiloxane having a group is preferable, and from the viewpoint of good compatibility with the component (A), further, a compound represented by the following general formula (III):

[0034]

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(Wherein R ² represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10), and a cyclic group having at least two SiH groups in one molecule. Organopolysiloxanes are preferred. In general formula (III) the substituent R ² in the compound represented by, C, is preferably those composed of H and O, more preferably a hydrocarbon group.

The molecular weight of the component (B) is not particularly limited, and any one can be suitably used. However, a low molecular weight one is preferably used from the viewpoint of easier development of fluidity. Specifically, those having a molecular weight of 50 to 100,000 are preferable, those having a molecular weight of 50 to 1,000 are more preferable,
Those having 50 to 700 are more preferable.

From the viewpoint of having good compatibility with the component (A), as the component (B), a chain and / or cyclic hydrogen organopolysiloxane and a carbon-carbon double bond may be used. A reaction product with at least one compound selected from organic compounds having the same (hereinafter referred to as component (E)) (this reaction product still contains at least two SiH groups in one molecule even after the reaction. A reaction product of genpolysiloxane and an organic compound having a number of moles of carbon-carbon double bonds smaller than the number of moles of SiH groups contained in the hydrogenpolysiloxane is also preferable. In this case, in order to further increase the compatibility of the reactant with the component (A), an unreacted hydrogen polysiloxane or the like may be removed from the reactant by devolatilization or the like.

The component (E) is an organic compound containing at least one carbon-carbon double bond having reactivity with a SiH group in one molecule, and the same explanation as the component (A) can be used. . From the viewpoint that the compatibility of the component (B) with the component (A) can be increased, preferred specific examples of the component (E) include allyl ether of novolac phenol and diallyl ether of bisphenol A, and 2,2′-.
Diallyl bisphenol A, diallyl phthalate, bis (2-allyloxyethyl) ester of phthalic acid, styrene, α-methylstyrene, allyl-terminated polypropylene oxide, polyethylene oxide and the like.
The organic compound (E) can be used alone or in combination of two or more.

As the component (B), those having fluidity at a temperature of 100 ° C. or less are preferable in order to obtain a uniform mixture with other components and good workability. Specifically, the viscosity at 23 ° C. is preferably 200 Pa · s or less, more preferably 50 Pa · s or less, and 20 Pa · s or less.
More preferably, it is Pa · s or less.

Specific examples of the above component (B) include 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, polymethylhydro Gensiloxane,
A reaction product of 1,3,5,7-tetramethylcyclotetrasiloxane and bisphenol A diallyl ether,
Reaction product of 3,5,7-tetramethylcyclotetrasiloxane and vinylcyclohexene, reaction product of 1,3,5,7-tetramethylcyclotetrasiloxane and divinylbenzene, 1,3,5,7-tetramethylcyclotetra A reaction product of siloxane and dicyclopentadiene can be used. The various (B) components as described above can be used alone or in combination of two or more.

Examples of the combination of component (A) / component (B) include bisphenol A diallyl ether / 1,3,5,7-tetramethylcyclotetrasiloxane, bisphenol A diallyl ether / 1,
Reaction product of 3,5,7-tetramethylcyclotetrasiloxane and bisphenol A diallyl ether, bisphenol A diallyl ether / reaction product of 1,3,5,7-tetramethylcyclotetrasiloxane and vinylcyclohexene, bisphenol A diallyl ether / 1,3,3
Reaction product of 5,7-tetramethylcyclotetrasiloxane and divinylbenzene, bisphenol A diallyl ether / 1,3,5,7-tetramethylcyclotetrasiloxane and reaction product of dicyclopentadiene, 1,2-polybutadiene / 1, 3,5,7-tetramethylcyclotetrasiloxane, 1,2-polybutadiene / 1,3,5,7
A reaction product of tetramethylcyclotetrasiloxane and bisphenol A diallyl ether, a reaction product of 1,2-polybutadiene / 1,3,5,7-tetramethylcyclotetrasiloxane and vinylcyclohexene, 1,2-polybutadiene / 1,3 Reaction product of 1,5,7-tetramethylcyclotetrasiloxane and divinylbenzene, reaction product of 1,2-polybutadiene / 1,3,5,7-tetramethylcyclotetrasiloxane and dicyclopentadiene, bisphenol A diallyl ether and 1 Mixture of 1,2-polybutadiene / 1,3,5,7-tetramethylcyclotetrasiloxane, bisphenol A diallyl ether and 1,
Mixture of 2-polybutadiene / 1,3,5,7-tetramethylcyclotetrasiloxane and reaction product of bisphenol A diallyl ether, mixture of bisphenol A diallyl ether and 1,2-polybutadiene / 1,3,5,5
Reaction product of 7-tetramethylcyclotetrasiloxane and vinylcyclohexene, mixture of bisphenol A diallyl ether and 1,2-polybutadiene / 1,3,5,7
Reaction product of tetramethylcyclotetrasiloxane and divinylbenzene, mixture of bisphenol A diallyl ether and 1,2-polybutadiene / 1,3,5,7-reaction product of tetramethylcyclotetrasiloxane and dicyclopentadiene, 2,2 '-Diallylbisphenol A diallyl ether / 1,3,5,7-tetramethylcyclotetrasiloxane, 2,2'-diallylbisphenol A diallyl ether / 1,3,5,7-tetramethylcyclotetrasiloxane and bisphenol A diallyl A reactant of ether, a reactant of 2,2'-diallylbisphenol A diallyl ether / 1,3,5,7-tetramethylcyclotetrasiloxane and vinylcyclohexene,
Reaction product of 2,2'-diallylbisphenol A diallyl ether / 1,3,5,7-tetramethylcyclotetrasiloxane and divinylbenzene, 2,2'-diallylbisphenol A diallyl ether / 1,3,5,7- Reaction product of tetramethylcyclotetrasiloxane and dicyclopentadiene, reaction product of divinylbenzene and 1,3,5,7-tetramethylcyclotetrasiloxane / 1,3,3
Reaction product of 5,7-tetramethylcyclotetrasiloxane and bisphenol A diallyl ether, reaction product of divinylbenzene and 1,3,5,7-tetramethylcyclotetrasiloxane / 1,3,5,7-tetramethylcyclotetra Reaction product of siloxane and vinylcyclohexene, reaction product of divinylbenzene and 1,3,5,7-tetramethylcyclotetrasiloxane / reaction product of 1,3,5,7-tetramethylcyclotetrasiloxane and divinylbenzene, divinylbenzene And the reaction product of 1,3,5,7-tetramethylcyclotetrasiloxane / the reaction product of 1,3,5,7-tetramethylcyclotetrasiloxane and dicyclopentadiene. Examples and their various mixtures / (B)
Various combinations of those listed as specific examples of the components and various mixtures thereof can be given.

The mixing ratio of component (A) and component (B) as described above is not particularly limited as long as the required strength is not lost, but in general, carbon having reactivity with the SiH group in component (A) is used. -The ratio of the number of carbon double bonds (X) to the number of SiH groups (Y) in the component (B) is 2 ≧ Y / X ≧ 0.
It is preferably 5. Y / X> 2 or 0.5
If> Y / X, sufficient curability cannot be obtained, sufficient strength may not be obtained, and heat resistance may be low. Further, from the viewpoint that the adhesion to the non-adhered body can be improved, it is preferable that Y / X> 1 and Y / X ≧ 1.2.
Is more preferable.

Next, the hydrosilylation catalyst as the component (C) will be described. The hydrosilylation catalyst is not particularly limited as long as it has the catalytic activity of the hydrosilylation reaction, and examples thereof include a simple substance of platinum, alumina, silica, carbon black and the like on which solid platinum is supported, chloroplatinic acid, platinum chloride Complexes of acids with alcohols, aldehydes, ketones, etc., platinum-olefin complexes (for example, Pt
_{(CH 2 = CH 2) 2} (PPh 3) 2, Pt (CH 2 =
CH ₂ ) ₂ Cl ₂ ), a platinum-vinylsiloxane complex (for example, Pt (ViMe ₂ SiOSiMe ₂ Vi) _n , P
t [(MeViSiO) ₄ ] _m ), a platinum-phosphine complex (for example, Pt (PPh ₃ ) ₄ , Pt (PB
u ₃ ) ₄ ), a platinum-phosphite complex (for example, Pt
[P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ )
(In the formula, Me is a methyl group, Bu is a butyl group, Vi is a vinyl group, Ph is a phenyl group, and n and m are integers.), Dicarbonyldichloroplatinum, Karstedt's catalyst, Ashby (Ash
by) US Patents 3,159,601 and 31,596
No. 62, as well as the platinum-hydrocarbon complex described in Lamoreaux.
Platinum alcoholate catalysts described in U.S. Pat. No. 2,209,72. In addition, Modic
Platinum chloride-olefin complexes described in U.S. Pat. No. 3,516,946 are also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , and RhAl ₂ O
₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlC
l ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiC
l _4, and the like. Among these, chloroplatinic acid, a platinum-olefin complex, a platinum-vinylsiloxane complex and the like are preferable from the viewpoint of catalytic activity. These catalysts may be used alone or in combination of two or more.

The amount of the hydrosilylation catalyst to be added is not particularly limited. However, in order to have sufficient curability and keep the cost of the sealing agent relatively low, 1 mol of the SiH group in the component (B) is used. The range is preferably from 10 ^-1 to 10 ^-8 mol, more preferably from 10 ^-2 to 10 ^-6 mol. Further, a co-catalyst can be used in combination with the above-mentioned catalyst, and examples thereof include a phosphorus-based compound such as triphenylphosphine, a 1,2-diester-based compound such as dimethyl maleate, and 2-hydroxy-2-methyl-1. -Acetylene alcohol-based compounds such as butyne, sulfur-based compounds such as simple sulfur, and amine-based compounds such as triethylamine. The addition amount of the co-catalyst is not particularly limited, the catalyst 1 ^mol, preferably 10-2 to ² mols, more preferably from ¹⁰ -1 to 10 mol.

Further, a curing retarder can be used for the purpose of improving the storage stability of the sealant of the present invention or for adjusting the reactivity of the hydrosilylation reaction in the production process. Examples of the curing retarder include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin-based compound, and an organic peroxide. These may be used in combination. Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, ene-yne compounds, and maleic esters. Examples of the organic phosphorus compound include triorganophosphines, diorganophosphines, organophosphones, and triorganophosphites. Examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, thiazole,
Benzothiazole, benzothiazole disulfide and the like are exemplified. Examples of the nitrogen-containing compound include ammonia, primary and secondary alkylamines such as tetramethylethylenediamine, arylamines, urea, and hydrazine. Examples of the tin compound include stannous halide dihydrate, stannous carboxylate, and the like. Organic peroxides include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide,
Examples are t-butyl perbenzoate and the like.

Among these curing retarders, benzothiazole, thiazole, dimethylmalate and 3-hydroxy-3-methyl-1-butyne are preferred from the viewpoint of good retarding activity and good raw material availability. Alkylamines such as tetramethylethylenediamine are preferred from the viewpoint of good delay activity at high temperatures. These curing retarders can be used alone or in combination. The amount of the curing retarder to be added is 10 ^-1 to 1 mol of the hydrosilylation catalyst used.
10 ³ mols, more preferably from 1 to 50
Range of moles.

The sealant of the present invention may optionally contain an inorganic filler. The addition of the inorganic filler is effective in reducing the coefficient of linear expansion and increasing the strength of the material. Examples of the inorganic filler include silica such as fused silica, crystalline silica, ultrafine amorphous silica, hydrophobic ultrafine silica, and spherical silica, alumina, aluminum hydroxide, talc, and barium sulfate. Among these, silicas are preferred from the viewpoint that they hardly inhibit the curing reaction and the effect of reducing the linear expansion coefficient is large, and spherical silica is more preferred from the viewpoint that the viscosity when added is low. It is preferable that these inorganic fillers have low radiation properties. The addition amount of the inorganic filler is not particularly limited, but from the viewpoint that the effect of reducing the linear expansion coefficient is high and the fluidity of the sealant is good, 50 to 8 of the total sealant is used.
It is preferably 0% by weight.

Further, various resins can be added for the purpose of modifying the properties of the sealant of the present invention. Examples of the resin include a polycarbonate resin, a polyether sulfone resin, a polyarylate resin, an epoxy resin, a cyanate resin, a phenol resin, an acrylic resin, a polyimide resin, a polyvinyl acetal resin, a urethane resin, and a polyester resin silicone resin. It is not limited. Various elastomers can be added as the resin.

The sealant of the present invention may be composed of only the above-mentioned components, but may also contain a solvent for the purpose of lowering the viscosity. Solvents that can be used are not particularly limited, and specific examples include hydrocarbon solvents such as benzene, toluene, hexane, and heptane; ether solvents such as tetrahydrofuran, 1,4-dioxane, and diethyl ether; and acetone. , Ketone solvents such as methyl ethyl ketone, chloroform, methylene chloride,
A halogen-based solvent such as 1,2-dichloroethane can be suitably used. The solvent can be used as a mixed solvent of two or more kinds. As the solvent, toluene, tetrahydrofuran and chloroform are preferred. The amount of the solvent used is 0 to 10 with respect to 1 g of the reactive (A) component used.
It is preferably used in the range of mL, more preferably in the range of 0.5 to 5 mL, and particularly preferably in the range of 1 to 3 mL. If the amount used is small, it is difficult to obtain the effect of using a solvent such as lowering the viscosity, and if the amount used is large, the solvent tends to remain in the material, easily causing problems such as thermal cracks, and also in terms of cost. It is disadvantageous and reduces the industrial use value.

A coupling agent can be added to the sealant of the present invention for the purpose of imparting adhesiveness. As the coupling agent, for example, an epoxy group, a methacryl group, an acryl group, an isocyanate group, an isocyanurate group, a vinyl group, a carbamate group, SiH
A silane coupling agent having at least one functional group selected from the group consisting of groups and a silicon-bonded alkoxy group can be used. Among the above functional groups, an epoxy group, a methacryl group, and an acryl group are particularly preferable in the molecule from the viewpoint of curability and adhesiveness. Specifically, examples of the organosilicon compound having an epoxy functional group and a silicon-bonded alkoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2- (3,4-epoxy). Cyclohexyl) ethyltrimethoxysilane, 2-
(3,4-epoxycyclohexyl) ethyltriethoxysilane. Examples of the organosilicon compound having a methacryl group or an acrylic group and a silicon-bonded alkoxy group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxy. Roxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane. Of these, a silane coupling agent having an epoxy functional group and a silicon-bonded alkoxy group is preferably used from the viewpoint that the curability is not particularly hindered and the adhesion-imparting effect is high. Specifically, 3-glycidoxypropyltrimethoxysilane is particularly preferably used. These coupling agents may be used alone or in combination of two or more.

The sealant of the present invention further includes an antioxidant, a radical inhibitor, an ultraviolet absorber, an adhesion improver, a flame retardant, a surfactant, a storage stability improver, an ozone deterioration inhibitor, a light stabilizer. Agents, thickeners, plasticizers, antioxidants, heat stabilizers, conductivity-imparting agents, antistatic agents, radiation blocking agents, nucleating agents,
Phosphorus peroxide decomposers, lubricants, pigments, metal deactivators,
A physical property modifier and the like can be added within a range that does not impair the purpose and effect of the present invention.

As the sealant of the present invention, various combinations can be used as described above. From the viewpoint of good heat resistance, the Tg (viscoelasticity) of the cured product obtained by curing the sealant is used. (Tan δ peak temperature) 50 ° C
It is preferable that the temperature is at least 100 ° C., more preferably at least 100 ° C., and particularly preferable is at least 150 ° C.

The sealant of the present invention preferably has fluidity at a temperature of 100 ° C. or lower in order to obtain good workability. Specifically, the viscosity at 23 ° C. is 10
It is preferably at most 00 Pa · s, more preferably at most 500 Pa · s, even more preferably at most 100 Pa · s.

Various electronic parts, electric circuits, electric contacts, or semiconductors can be sealed using the sealing agent of the present invention. There are no particular restrictions on the various electronic components, electrical circuits, electrical contacts or semiconductors to be sealed here,
The electronic components include, for example, automotive electrical components such as ignition coils, flyback transformers, capacitors, and the like. Various substrates can be used as the electric circuit. Examples of the electrical contact include a connection point between a board and a cable, a connection point between a cable and a cable or a connection point between boards, a connection point between a board and an element, a connection point between a cable and an element, and the like. Semiconductors include transistors, light-emitting diodes,
Diodes, memory, logic circuits, etc.
C and LSI.

Specifically, capacitors, transistors,
Potting, dipping, transfer mold sealing of diodes, light emitting diodes, ICs, LSIs, etc., potting sealing of ICs, LSIs such as COB, COF, TAB, underfills such as flip chips, IC packages such as BGA, CSP Sealing (underfill) at the time of mounting can be exemplified.

The sealant of the present invention is mixed in advance, cured by reacting a carbon-carbon double bond having a reactivity with a SiH group in the sealant and part or all of the SiH group, and then cured and sealed. Can be stopped. Various methods can be used as the mixing method, but a method of mixing the component (A) with the component (C) and the component (B) is preferable. When the method of mixing the component (C) with the mixture of the component (A) and the component (B), it is difficult to control the reaction. When the method of mixing the component (A) with the mixture of the component (B) with the component (B) is used, the component (B) has a reactivity with moisture in the presence of the component (C), so that it is stored. It may be transformed into

In the case of curing by reacting the sealing agent, the necessary amounts of each of the components (A), (B) and (C) may be mixed and reacted at a time. And reacting only a part of the functional groups in the encapsulant by controlling the reaction conditions and utilizing the difference in the reactivity of the substituents after mixing. Stage), and then a process such as molding is performed to further cure. According to these methods, viscosity adjustment at the time of molding becomes easy.

The above mixture or B-staged product can be stored at room temperature or low temperature without substantially proceeding the curing reaction (so-called one-pack).
Therefore, a storage stability improver can be added as needed. As the storage stability improver, a curing retarder can be used, and preferred examples and preferred amounts of the curing retarder are as described above.

As a curing method, the reaction can be carried out simply by mixing, or the reaction can be carried out by heating. From the viewpoint that the reaction is fast and a material having high heat resistance is generally easily obtained, a method of performing the reaction by heating is preferable.

The reaction temperature can be variously set, for example, a temperature of 30 to 300 ° C. can be applied, and a temperature of 100 to 250 ° C.
Is more preferable, and 150 to 200C is further preferable.
When the reaction temperature is low, the reaction time for causing a sufficient reaction is prolonged, and when the reaction temperature is high, molding tends to be difficult. The reaction may be performed at a constant temperature, but the temperature may be changed in multiple stages or continuously as needed. The reaction time can also be set variously. The pressure during the reaction can be variously set as required, and the reaction can be performed at normal pressure, high pressure, or reduced pressure.

Various methods can be used for sealing, including a method used for a conventional sealing agent. For example, it can be sealed by potting, dipping, or screen printing, or can be sealed by molding such as transfer molding. Alternatively, sealing can be performed by a method (underfill) of dispensing into a gap after dispensing.

Various processes can be performed as necessary during molding. For example, a treatment for removing bubbles by centrifuging, depressurizing, or the like can be applied to the sealing agent or a partially reacted sealing agent to suppress voids generated during molding. A semiconductor device can be manufactured by sealing a semiconductor by the method described above using the sealing agent of the present invention.

[0064]

EXAMPLES Examples and comparative examples of the present invention will be shown below, but the present invention is not limited by the following. (Synthesis Example 1) A stirrer and a condenser were set in a 1 L three-necked flask. In this flask, add bisphenol A1
14 g, potassium carbonate 145 g, allyl bromide 14
0 g and acetone (250 mL) were added, and the mixture was stirred at 60 ° C. for 12 hours. The supernatant was taken, washed with an aqueous sodium hydroxide solution using a separating funnel, and then washed with water. After the oil layer was dried over sodium sulfate, the solvent was distilled off using an evaporator, and 126 g of a pale yellow liquid was obtained. ¹ H-
NMR revealed that bisphenol A was diallyl ether in which the OH group of bisphenol A was allyl etherified. The yield was 82% and the purity was 95% or more. The viscosity of this compound was 0.05 Pa · s.

(Synthesis Example 2) A stirrer and a condenser were set in a 1 L three-necked flask. In this flask, bisphenol A diallyl ether 500 synthesized in Synthesis Example 1 was added.
g was added and stirred at 200 ° C. for 4 hours to obtain a pale yellow liquid. ¹ H-NMR revealed that the allyl group of bisphenol A diallyl ether was 2,2′-diallyl bisphenol A, which was rearranged. A stirrer and a condenser were set in a 1 L three-necked flask. In this flask, 154 g of 2,2'-diallylbisphenol A synthesized here, 145 g of potassium carbonate, 140 g of allyl bromide, and 250 mL of acetone were added and stirred at 60 ° C for 12 hours. The supernatant was taken, washed with an aqueous sodium hydroxide solution using a separating funnel, and then washed with water. After the oil layer was dried over sodium sulfate, the solvent was distilled off using an evaporator, and 170 g of a pale yellow liquid was obtained. ¹
By H-NMR, it was found that the 2,2'-diallylbisphenol A diallyl ether was an allyl etherified 2,2'-diallylbisphenol A OH group. The viscosity of this compound was 19.5 Pa · s.

(Synthesis Example 3) A stirrer and a condenser were set in a 1 L three-necked flask. 100 g of 2,2'-diallylbisphenol A diallyl ether synthesized in Synthesis Example 2 was placed in this flask, and heated and stirred at 200 ° C. for 4 hours to obtain a pale yellow liquid. ^{According to 1} H-NMR, 2,
It was found that 2,2,2 ', 2'-tetraallylbisphenol A in which the allyl group of 2'-diallylbisphenol A diallyl ether was rearranged. The viscosity of this compound was less than 10 Pa · s.

(Synthesis Example 4) A stirrer, a condenser, and a dropping funnel were set in a 1 L four-necked flask. In this flask, 150 g of toluene, 15.6 μL of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum),
500 g of 1,3,5,7-tetramethylcyclotetrasiloxane was added, and the mixture was heated to 70 ° C. and stirred in an oil bath. 64 g of bisphenol A diallyl ether produced in Synthesis Example 1 was diluted with 40 g of toluene and added dropwise from a dropping funnel. After stirring at the same temperature for 60 minutes, the mixture was allowed to cool, and 4.74 mg of benzothiazole was added. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a slightly viscous liquid. ^{According to 1} H-NMR, this was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with bisphenol A diallyl ether (referred to as a partial reactant A)
It turned out to be. The viscosity of this compound is 0.7 Pa
-It was s.

(Synthesis Example 5) A magnetic stirrer and a cooling tube were set in a 100 mL eggplant-shaped flask. In this flask, 25 g of 1,3-dioxolane, 2.5 g of triallyl isocyanurate, 19 g of 1,3,5,7-tetramethylcyclotetrasiloxane, 45.4 μL of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) ,
Was added and the mixture was heated and stirred at 80 ° C. for 3 hours in an oil bath. The mixture was allowed to cool, and 250 mg of benzothiazole was added.
Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a viscous liquid (referred to as partial reactant B). The viscosity of this compound is 1
It was less than Pa · s.

Example 1 15.4 g of bisphenol A diallyl ether synthesized in Synthesis Example 1, 1, 3, 5, 7
-Tetramethylcyclotetrasiloxane (viscosity of 0.1
6.0 g, xylene solution of platinum vinyl siloxane complex (containing 3 wt% as platinum) 2.65 μL
Were mixed to form a sealant of the present invention. The viscosity of this sealant was very low at 1.2 Pa · s when the viscosity was measured.
This sealant was placed in a metal can covered with a polyimide film and left at room temperature. After about 10 minutes, the reaction was exothermic and cured. Further, by curing at 150 ° C. for 2 hours in an oven, the composition was sufficiently cured, and showed low-temperature rapid curing property. The water absorption of the obtained sample was measured. The measurement was performed by determining the weight change after immersing the sample in pure water at 23 ° C./24 hours or 100 ° C./1 hour. The obtained water absorption (23 ° C./24 hours) was 0.04%, and the water absorption (10
(0 ° C./1 hour) was as low as 0.2%. Further, the dielectric properties of the obtained sample were measured. The obtained values showed a good dielectric property of a dielectric constant of 2.7 and a dielectric loss tangent of 0.01. The heat resistance of the obtained sample was measured. According to the viscoelasticity measurement, the peak temperature of tan δ was 80 ° C.
Met.

Example 2 1,2-polybutadiene (Nippon Soda, B-1000, viscosity less than 20 Pa · s)
0 g, 1,3,5,7-tetramethylcyclotetrasiloxane, 6.0 g, and 52.9 μL of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) were used as a sealant of the present invention. The viscosity of this sealant was very low at 3.3 Pa · s when measured for viscosity. This sealant was placed in a metal can covered with a polyimide film and cured in an oven at 150 ° C. for 2 hours to sufficiently cure and exhibit low-temperature rapid curing. The water absorption and the dielectric properties of the sample obtained in the same manner as in Example 1 were measured. The obtained water absorption (23 ° C./24 hours) is 0.04
%, The water absorption (100 ° C./1 hour) was a low value of 0.2%, and the dielectric constant was 2.4, and the dielectric loss tangent was 0.003, showing good dielectric properties. The heat resistance of the obtained sample was measured. The measurement was performed by viscoelasticity measurement. In the measurement up to 400 ° C., neither a decrease in the elastic modulus nor a peak of tan δ was observed, indicating high heat resistance.

(Example 3) 2,2 'synthesized in Synthesis Example 2
-9.7 g of diallyl bisphenol A diallyl ether
And 6.0 g of 1,3,5,7-tetramethylcyclotetrasiloxane and 2.65 μL of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) to obtain a sealant of the present invention. . The viscosity of this sealant is 20P
a · s or less. This sealant was placed in a metal can covered with a polyimide film and cured in an oven at 150 ° C. for 2 hours to sufficiently cure and exhibit low-temperature rapid curing. The water absorption of the sample obtained in the same manner as in Example 1 was measured. The obtained water absorption (100 ° C./1 hour) was a low value of 0.2%. The heat resistance of the obtained sample was measured. According to the viscoelasticity measurement,
The peak temperature of tan δ was 105 ° C.

(Examples 4 to 12) As shown in Table 1, component (A), component (B) and component (C) were mixed to obtain a sealant of the present invention. Reactants A and B contain the platinum vinyl siloxane complex as component (C) of the present invention.) The viscosity of the sealant was as shown in each table. In the table, the viscosities of the above-mentioned vinylbenzene, divinylbiphenyl, 4-vinylcyclohexene, triallyl isocyanurate and trivinylcyclohexane were all less than 0.1 Pa · s.

[0073]

[Table 1]

These sealants were placed in a metal can covered with a polyimide film and cured in an oven at 200 ° C. for 2 hours to sufficiently cure to give a transparent and uniform cured product. The heat resistance of the obtained sample was measured. The measurement was performed by viscoelasticity measurement. In the case of Example 4, no decrease in elastic modulus and no peak of tan δ were observed in the measurement up to 400 ° C., indicating high heat resistance. In the case of Example 5, tan
The peak temperature of δ was 110 ° C. In the case of Example 7,
The peak temperature of tan δ was 150 ° C.

(Comparative Example 1) Bisphenol A type epoxy resin (oiled shell epoxy, Epikote 828)
0 g, an acid anhydride type curing agent (oiled shell epoxy, Epicure YH306) 12.0 g, and a curing accelerator (oiled shell epoxy, Epicure 3010) 1.0 g were mixed to form a sealant. This sealant was placed in a metal can covered with a polyimide film and cured in an oven at 150 ° C. for 12 hours. The water absorption of the sample obtained in the same manner as in Example 1 was measured. The obtained water absorption (23 ° C./24 hours) is 0.7%, and the water absorption (100 ° C./1 hour) is 3.7.
%.

Example 13 6.2 g of bisphenol A diallyl ether synthesized in Synthesis Example 1, 5.2 g of the partially reacted product A synthesized in Synthesis Example 4, spherical silica (Nippon Chemical,
11.4 g of SILSTAR MF-10) was mixed and devolatilized under vacuum for 2 hours as a sealant of the present invention. (As shown in Synthesis Example 1, partial reactant A contains a platinum vinyl siloxane complex as component (C) of the present invention.) The viscosity of this sealant was 5 Pa · s when measured. . Adhesion of epoxy FRP and aluminum substrate using this sealant, J
Shear adhesion was measured according to ISK6850. The value obtained was 5.2 MPa for the epoxy FRP adherend,
It was 3.8 MPa with respect to the aluminum adherend, indicating a sufficient adhesive strength.

(Examples 14 to 21) 15.4 g of bisphenol A diallyl ether synthesized in Synthesis Example 1, 13.1 g of the partially reacted product A synthesized in Synthesis Example 4, and the additives shown in Table 2 were mixed. The sealing agent of the present invention was used. (As shown in the synthesis example, the partial reactant A contains the platinum vinyl siloxane complex as the component (C) of the present invention.) This sealing agent is applied on a glass substrate, and is placed in an oven for 200 hours. ° C
/ 2 hours to sufficiently cure to give a transparent and uniform coating film. The adhesion of the obtained coating film was measured according to JIS K540.
According to 0, evaluation was made by the crosscut tape method.

[0078]

[Table 2]

From the above, it can be seen that additives such as a coupling agent and a filler can be added to the sealant of the present invention, and the adhesion and other physical properties can be improved by these additions.

(Examples 22 to 24) Bisphenol A diallyl ether synthesized in Synthesis Example 1 and partial reactant A synthesized in Synthesis Example 4 were mixed as shown in Table 3 to obtain a sealant of the present invention. (As shown in the synthesis example, partial reactant A
Contains a platinum vinyl siloxane complex as the component (C) of the present invention. ) This sealant was applied on a glass substrate and a copper substrate, and was sufficiently cured by curing in an oven at 200 ° C for 2 hours to give a transparent and uniform coating film.
The adhesiveness of the obtained coating film was evaluated by a grid tape method according to JIS K5400.

[0081]

[Table 3]

As described above, the sealant of the present invention can be cured even when the ratio of the carbon-carbon double bond to the SiH group in the sealant is changed, whereby the adhesion and other physical properties can be improved. You can see that there is.

[0083]

The sealant of the present invention has low hygroscopicity, low viscosity,
Shows low-temperature fast curing, low dielectric constant, and low dielectric loss tangent. Further, the sealant of the present invention has sufficient adhesiveness, and can effectively seal electronic components, electric circuits, semiconductors, and the like with the sealant of the present invention, and has high reliability. In addition, a semiconductor device having high high-frequency characteristics can be manufactured.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H017 AA04 AB16 AC19 AD06 AE05 4J002 CP04X GQ05 4M109 AA01 CA04 CA07 CA12 CA21 CA26 EA20 EC01 EC05 EC20

Claims (11)

[Claims] (A) a carbon having a reactivity with a SiH group;
Organic compounds containing at least two carbon double bonds in one molecule, (B) a silicon compound containing at least two SiH groups in one molecule, and (C) a hydrosilylation catalyst as essential components. A sealant characterized by the above-mentioned. 2. The component (A) has a carbon-carbon double bond reactive with a SiH group in an amount of 0.1 g / g of the component (A).
The sealant according to claim 1, wherein the sealant is contained in an amount of 001 mol or more. 3. The composition according to claim 1, wherein the component (A) is C,
The sealant according to claim 1, comprising only H, O, and halogen. 4. The method according to claim 1, wherein the component (A) is an organic compound containing at least one vinyl group reactive with a SiH group in one molecule. The sealant according to item. 5. The molecular weight of the component (B) is from 50 to 700.
The sealant according to any one of claims 1 to 4, wherein 6. A viscosity at 23 ° C. of 1000 Pa · s
The sealant according to any one of claims 1 to 5, wherein the sealant is liquid at 23 ° C. 7. The sealant according to claim 6, which is used for sealing a semiconductor. 8. An electronic component, an electric circuit, an electric contact, wherein an electronic component, an electric circuit, an electric contact or a semiconductor is sealed with the encapsulant according to any one of claims 1 to 6. Or a semiconductor sealing method. 9. A method for sealing a semiconductor, comprising sealing the semiconductor with the sealing agent according to claim 7. 10. A method for manufacturing a semiconductor device, comprising: sealing a semiconductor with the sealing agent according to claim 1. Description: 11. A semiconductor device in which a semiconductor is sealed by the sealant according to claim 1.