JP2001098248A - Adhesive composition and method for its preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition which is used for bonding electronic materials, such as for semiconductor mounting or for circuit boards, and is excellent in characteristics, such as heat resistance and permittivity, in addition to adhesive properties and to provide a method for preparing the same. SOLUTION: This adhesive composition contains, as essential ingredients, an organic compound having at least two carbon-carbon double bonds reactive with SiH groups per molecule and a silicon compound having at least two SiH groups per molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive, and more particularly, to an adhesive for semiconductor mounting, such as a rigid wiring board, a flexible printed wiring board, and a lead frame peripheral material, which has high adhesive strength even at high temperatures. The present invention relates to a heat-resistant adhesive to be used.

[0002]

2. Description of the Related Art In recent years, as electronic devices have become smaller and higher in performance, smaller, thinner, lighter, and higher-density packages have been required in the field of semiconductor mounting. In this semiconductor mounting technology, the development of a high-performance heat-resistant adhesive for joining components has been required.

[0003] For example, an adhesive tape is generally taped on a lead frame by a lead frame maker, then thermocompression-bonded to an IC chip by a semiconductor maker, and a temperature of about 250 ° C. while applying ultrasonic waves to the chip and the lead frame. Wire bonding at about 180 ° C to 20
Resin sealing is performed at a temperature of about 0 ° C. Then, it is mounted by solder reflow at a temperature of about 250 ° C. For this reason, the adhesive tape is required to have not only electrical properties but also comprehensive properties such as sufficient room temperature adhesive strength immediately after taping, adhesive strength to an IC chip, and soldering heat resistance.

[0004] Further, the adhesive for rigid circuit boards or flexible circuit boards does not deteriorate in properties of the adhesive due to a chemical treatment such as an acid or a base in a manufacturing process thereof, a heat treatment process such as heat lamination or soldering. Is required.

Further, with the recent increase in the speed of computers and the frequency of communications, these materials have been required to have a low dielectric constant and a low dielectric loss tangent.

As adhesives for conventional semiconductor mounting or circuit boards, acrylic, epoxy, rubber-phenol resin, thermoplastic polyimide and the like are generally and widely used.

[0007]

However, thermoplastic polyimide and epoxy adhesives have excellent heat resistance, chemical resistance, and dimensional stability, but lack adhesive strength and flexibility. In addition, the gas generated during curing contaminates the metal surface of the substrate, causing problems such as a decrease in adhesive strength and a crack in the package. Also, acrylic and rubber-phenolic resin adhesives have high ionic impurities, require high temperature and long time for heat curing, and have poor productivity, so they are said to satisfy the demand for high reliability adhesives. hard. Further, since these materials have a polar group, their dielectric constant and dielectric loss tangent generally have high values.

In order to improve these disadvantages, an adhesive composition using a silicon-based polymer has been proposed (JP-A-10-140127). However, this adhesive composition still has the problem that the adhesiveness at high temperatures is not sufficient, and no material has yet been found which can sufficiently satisfy the market requirements.

Accordingly, an object of the present invention is to provide an adhesive for electronic materials such as for semiconductor mounting or circuit boards, which has excellent properties such as heat resistance and dielectric constant in addition to adhesiveness, and an adhesive composition thereof. It is to provide a manufacturing method.

[0010]

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. Compound and at least two S atoms in one molecule
The inventors have found that the above problems can be solved by using an adhesive composition containing a silicon compound containing an iH group as an essential component, and have accomplished the present invention.

That is, the present invention relates to (A) an organic compound having an organic skeleton containing at least two carbon-carbon double bonds reactive with a SiH group in one molecule;
An adhesive composition comprising a silicon compound containing at least two SiH groups in one molecule and a hydrosilylation catalyst (C) as an essential component, wherein the component (A) is a carbon compound having a reactivity with a SiH group. -An organic compound containing at least 0.001 mol of carbon double bonds per 1 g of component (A),
An adhesive composition (Claim 1), wherein the component (A) is:
The following general formula (I)

[0012]

Embedded image (Wherein, R ¹ represents a group having 2 to 6 carbon atoms containing a carbon-carbon double bond reactive with a SiH group, or a hydrogen atom), and has a reactivity with a SiH group. An adhesive composition which is an organic compound containing at least two carbon-carbon double bonds in one molecule (Claim 2), wherein the component (B) is represented by the following general formula (II)

[0013]

Embedded image (Wherein, R ² represents an organic group having 1 to 6 carbon atoms, and n represents 3 to
Represents the number 10. ), Which is a cyclic polyorganosiloxane containing at least two SiH groups in one molecule or a heat-resistant adhesive composition (Claim 4). Wherein the ratio of the number (X) of carbon-carbon double bonds reactive with the SiH groups of (A) to the number (Y) of SiH groups in the component (B) is Y / X ≧ 1.2. And a heat-resistant adhesive composition (Claim 5), wherein in addition to using the components (A) to (C) as essential components, a curing retarder (D) is further contained as an essential component. Or a heat-resistant adhesive composition (claim 6), wherein the cured product obtained by curing the adhesive composition has a Tg of 50 ° C. or more (claim 6). Item 3), wherein the adhesive composition or the heat-resistant adhesive composition is prepared in advance. Mixed, carbon reactive with a SiH group in the composition - carbon double bonds and Si
A method for producing an adhesive composition by reacting a part of H groups (claim 8).

Further, the adhesive composition is preferably a heat-resistant adhesive composition for electronic materials or a heat-resistant adhesive composition (claim 7).

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The component (A) in the present invention will be described. The component (A) is an organic compound having an organic skeleton containing at least two carbon-carbon double bonds reactive with a SiH group in one molecule. In the component (A), the structure in which the structure is bonded to the skeleton portion and the skeleton by a covalent bond (in some cases, via a divalent or higher valent substituent).
When the iH group and the group having a reactive carbon-carbon double bond (alkenyl group) are separately represented, the alkenyl group may be present anywhere in the molecule.

The skeleton of the component (A), which is an organic compound, may be a polysiloxane-based resin due to problems of gas permeability and repellency.
Siloxane units (Si-OS) such as organic block copolymers and polysiloxane-organic graft copolymers
not containing i) but as constituent elements C, H, N,
There is no particular limitation as long as the skeleton contains only O, S, and halogen, and an organic polymer skeleton or an organic monomer skeleton may be used. For example, as the organic polymer skeleton, polyether,
Polyester, polycarbonate, saturated hydrocarbon, polyacrylate, polyamide, and phenol-formaldehyde (phenol resin) skeletons can be used. Examples of the monomer skeleton include phenol-based, bisphenol-based, hydrocarbon-based, and mixtures thereof.

The alkenyl group of the component (A) is SiH
It is not particularly limited as long as it has reactivity with the group,
The following general formula (III)

[0019]

Embedded image (Wherein, R ³ represents a hydrogen atom or a methyl group). Also, from the availability of raw materials,

[0020]

Embedded image Is particularly preferred.

The alkenyl group may be covalently bonded to the skeleton of the component (A) via a divalent or higher valent substituent, and the divalent or higher valent substituent may be C, H, N, O,
There is no particular limitation as long as it is a substituent having 0 to 10 carbon atoms containing only S and halogen.

[0022]

Embedded image Is mentioned. 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 above skeleton include vinyl, allyl, methallyl, acryl, methacryl, 2-hydroxy-3- (allyloxy) propyl, and 2-allylphenyl. Group, 3-allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group,
-(Allyloxy) phenyl group, 2- (allyloxy)
Ethyl group, 2,2-bis (allyloxymethyl) butyl group, 3-allyloxy-2,2-bis (allyloxymethyl) propyl group,

[0024]

Embedded image Is mentioned.

From the viewpoint that the heat resistance can be further improved, the component (A) contains a carbon-carbon double bond reactive with a SiH group in an amount of 0.000 g per gram of the component (A).
What is necessary is just to contain 1 mol or more.
Those containing 0.005 mol or more per g are preferable, and those containing 0.008 mol or more are particularly preferable. Specific examples include butadiene, isoprene, cyclopentadiene, dicyclopentadiene, cyclohexadiene, decadien, diallyl phthalate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, and divinylbenzenes (purity of 50).
-100%, preferably 80-100% pure), 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and oligomers thereof,
1,2-polybutadiene (1, 2 ratio of 10 to 100%, preferably 1, 2 ratio of 50 to 100%),

[0026]

Embedded image And the like.

The component (A) is represented by the following general formula (I) from the viewpoint that heat resistance can be further improved and that it can be easily obtained industrially.

[0028]

Embedded image (Wherein, R ¹ represents a group having 2 to 6 carbon atoms containing a carbon-carbon double bond reactive with a SiH group, or a hydrogen atom), and has a reactivity with a SiH group. Organic compounds containing at least two carbon-carbon double bonds in one molecule are preferred. The substituent R ¹ in the compound represented by the general formula (I) is preferably an organic group composed of C, H, and O, and is preferably a hydrocarbon group having 2 to 6 carbon atoms. More preferred. As a specific example,

[0029]

Embedded image Is mentioned.

The number of carbon-carbon double bonds reactive with the SiH group of component (A) may be at least two per molecule on average, but from the viewpoint that heat resistance can be further improved, It is preferably more than 2, more preferably 3 or more, and particularly preferably 4 or more. When the number of carbon-carbon double bonds reactive with the SiH group of the component (A) is one or less per molecule,
Even if it reacts with the component (B), it only forms a graft structure and does not form a crosslinked structure.

As the component (A), those having fluidity at a temperature of 100 ° C. or less are preferable in order to obtain uniform mixing with other components and good workability, and may be linear or branched. Although the molecular weight is not particularly limited, it is 100
Any of ~ 100,000 can be suitably used. When the molecular weight is 100,000 or more, the raw material generally has a high viscosity and is inferior in workability, and the effect of crosslinking by the reaction between the alkenyl group and the SiH group is hardly exhibited.

Next, the compound having a SiH group as the component (B) will be described. The compound having a SiH group that can be used in the present invention is not particularly limited. For example, compounds described in International Publication WO 96/15194 having at least two SiH groups in one molecule can be used.

Of these, from the viewpoint of availability, a chain and / or cyclic polyorganosiloxane having at least two SiH groups in one molecule is preferable, and has good compatibility with the component (A). From the viewpoint, the following general formula (II)

[0034]

Embedded image (Wherein, R ² represents an organic group having 1 to 6 carbon atoms, and n represents 3 to
Represents the number 10. )), A cyclic polyorganosiloxane having at least two SiH groups in one molecule is preferable. In addition, the substituent R ² in the compound represented by the general formula (II) is preferably composed of C, H, and O, and more preferably a hydrocarbon group.

From the viewpoint of having good compatibility with the component (A), at least two S
a chain having, in its molecule, a skeleton introduced from at least one compound selected from organic compounds having an iH group and having a carbon-carbon double bond (hereinafter referred to as (E));
And / or cyclic polyorganosiloxanes are also preferred.

As the organic compound having a carbon-carbon double bond as the component (E), those having the same description as the component (A) can be used, but the compatibility of the component (B) with the component (A) is high. From the viewpoint that the component (E) can be used, preferred examples of the component (E) include allyl ether of novolac phenol and diallyl ether of bisphenol A,
Examples include 2′-diallylbisphenol A, diallyl phthalate, bis (2-allyloxyethyl) ester of phthalic acid, styrene, α-methylstyrene, allyl-terminated polypropylene oxide and polyethylene oxide. The organic compound (E) can be used alone or in combination of two or more.

The above-mentioned various components (B) can be used alone or in combination of two or more.

The mixing ratio of the above components (A) and (B) is not particularly limited as long as the performance as an adhesive is not lost. The ratio of the number of carbon-carbon double bonds (X) to the number of SiH groups (Y) in the component (B) is 2 ≧ Y /
It is preferable that X ≧ 0.5. When Y / X> 2 or 0.5> Y / X, sufficient curability cannot be obtained,
Heat resistance can be low.

Further, it is preferable that Y / X ≧ 1.2 from the viewpoint that the adhesion to the non-adhered body can be improved.

Next, the hydrosilylation catalyst which is the component (C)
Will be described. Hydrosilylation catalysts include
There is no particular limitation as long as it has catalytic activity for the rosilylation reaction
However, for example, simple substance of platinum, alumina, silica, carbon
Solid platinum supported on a carrier such as black, chloride
Platinic acid, chloroplatinic acid and alcohol, aldehyde, ketone
And platinum-olefin complexes (eg, Pt
(CH_Two= CH_Two)_Two(PPh_Three)_Two, Pt (CH_Two= C
H_Two)_TwoCl_Two), Platinum-vinylsiloxane complex (eg,
If Pt (ViMe_TwoSiOSiMe_TwoVi)_n, Pt
[(MeViSiO)_Four]_m), Platinum-phosphine complex
(For example, Pt (PPh_Three)_Four, Pt (PBu_Three)_Four),White
Gold-phosphite complex (for example, Pt [P (OP
h)_Three]_Four, Pt [P (OBu) _Three]_Four(Where Me is the
Butyl, Bu is butyl, Vi is vinyl, Ph is Fe
And n and m represent an integer. ), Dicarboni
Rudichloroplatinum, Karstedt
Catalysts are also disclosed in Ashby U.S. Pat.
Described in 159601 and 3159662
Platinum-hydrocarbon composite, as well as Lamorrow (La
Moreaux) U.S. Pat. No. 3,220,972.
And the platinum alcoholate catalysts described therein. Sa
No. 3,516, Modic.
No. 946, a platinum chloride-olefin complex described in
Coalescing is also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , RhAl ₂ O ₃ ,
RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdC
_{l 2 · 2H 2 O, NiCl} 2, TiCl 4, and the like.

Of these, chloroplatinic acid, a platinum-olefin complex, a platinum-vinylsiloxane complex and the like are preferred from the viewpoint of catalytic activity. These catalysts may be used alone or in combination of two or more.

The addition amount of the catalyst is not particularly limited, but in order to have sufficient curability and to keep the cost of the curable composition relatively low, 10 ^-1 to 1 ^-1 to 1 mol of SiH groups.
It is preferably in the range of ^0-8 mol, more preferably ^10-2 to
It is in the range of 10 ^-6 mol.

Further, a co-catalyst can be used in combination with the above-mentioned catalyst, and examples thereof include a phosphorus compound such as triphenylphosphine, a 1,2-diester compound such as dimethyl maleate, and 2-hydroxy-2-amine. Examples include acetylene alcohol compounds such as methyl-1-butyne, sulfur compounds such as simple sulfur, and amine 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 adhesive composition of the present invention or for adjusting the reactivity of the hydrosilylation reaction in the production of the adhesive. 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. As organic sulfur compounds, organomercaptans, diorganosulfides, hydrogen sulfide,
Benzothiazole, benzothiazole disulfide and the like are exemplified. Examples of the nitrogen-containing compound include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like. Examples of the tin compound include stannous halide dihydrate, stannous carboxylate, and the like. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

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.

The amount of the storage stability improver added is preferably in the range of 10 ^-1 to 10 ³ mol, more preferably 1 to 50 mol, per 1 mol of the hydrosilylation catalyst used.

As the adhesive composition of the present invention, various combinations can be used as described above, but from the viewpoint of good heat resistance, the Tg of the cured product obtained by curing the adhesive composition is as follows. Those having a temperature of 50 ° C. or higher are preferable, and those having a temperature of 100 ° C. or higher are more preferable.
Those having a temperature of at least ℃ are particularly preferred.

It is preferable to add an inorganic filler to the adhesive composition of the present invention, since it is effective in alleviating a thermal shock such as soldering, preventing the fluidity of the adhesive, and stabilizing or improving the adhesive strength. Can be used. As the inorganic filler, those having excellent electrical insulation and fine particles are preferable, and include alumina, aluminum hydroxide, fused silica, crystalline silica, ultrafine amorphous silica, hydrophobic ultrafine silica, talc, barium sulfate, and the like. Can be.

Further, various resins can be added for the purpose of modifying the properties of the adhesive composition of the present invention. Examples of the resin include, but are not limited to, 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.

Although the adhesive composition of the present invention can be cast or applied to a film as it is, the adhesive composition can be dissolved in an organic solvent to form a coating varnish. Solvents that can be used are not particularly limited, and specific examples thereof include hydrocarbon solvents such as benzene, toluene, hexane, and heptane, tetrahydrofuran, 1,4-dioxane, ether solvents such as diethyl ether, and acetone. , Methyl ethyl ketone and other ketone solvents, chloroform, methylene chloride, 1,2-
A halogen-based solvent such as 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 solvent used is
It is preferably used in the range of 0 to 10 mL, more preferably in the range of 0.5 to 5 mL, and particularly preferably in the range of 1 to 3 mL, per 1 g of the reactive (A) component used. 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 is likely to remain in the adhesive and cause problems such as thermal cracks, and also costs are reduced. Is disadvantageous, and the industrial utility value is reduced.

The adhesive composition of the present invention further comprises an antioxidant, a radical inhibitor, an ultraviolet absorber, an adhesion improver, a flame retardant, a surfactant, a storage stability improver, an ozone deterioration inhibitor, Stabilizers, thickeners, plasticizers, coupling agents,
Antioxidants, heat stabilizers, conductivity-imparting agents, antistatic agents, radiation blocking agents, nucleating agents, phosphorus-based peroxide decomposers, lubricants, pigments, metal deactivators, physical property modifiers, etc. It can be added within a range that does not impair the purpose and effect.

Since the adhesive composition of the present invention can have a relatively low viscosity, it may be difficult to form an adhesive layer (control the film thickness) when producing an adhesive using the adhesive composition of the present invention. . In such a case, for example, the moldability can be improved by adding a thickener or the like,
As a more practical method, the adhesive composition of the present invention is preliminarily mixed and then heated to react a part of the SiH group with the carbon-carbon double bond having reactivity with the SiH group in the composition. A method for producing an adhesive composition by adjusting the viscosity to an appropriate one may be mentioned. According to this method, the composition can be controlled to an arbitrary viscosity by controlling the reaction conditions, and addition of an additive or the like is not required, which is industrially advantageous.

As a heating method in this case, the adhesive composition or a part thereof or a part of the reactive group in the mixture is reacted in advance, and if necessary, the remaining components are mixed and applied to the adherend. It can be applied, or a part of the reactive groups in the mixture can be reacted in advance by applying a heat treatment after applying the adhesive composition to the adherend. Various reaction conditions can be selected. For example, a part of the composition may be mixed, or the mixture of the entire composition may be mixed with 40 to 15 parts.
A method of preheating at 0 ° C. for about several seconds to one hour is applied.

As a specific example, using the adhesive composition of the present invention, for example, a flexible circuit board can be manufactured as follows. The adhesive composition of the present invention has a thickness of 20 to 100.
The adhesive is applied to a thickness of 20 μm to 100 μm using a roll, a reverse roll, a comma coater, or the like on a polymer resin film having a thickness of 20 μm, and then preliminarily cured in a hot air dryer. The film with the adhesive layer produced in this way is heated, pressed with a roll or a heated and pressed press to form a metal foil such as copper, aluminum, tin, etc.
Joining is performed at 200 ° C. at a temperature / pressure of 5 to 20 kgf / cm 2. The flexible circuit board manufactured in this way has 100 to 3
Heating is performed at 00 ° C. for 1 to 24 hours to accelerate the curing of the adhesive layer.

Examples of the polymer resin film include polyarylate, polysulfone, polyallylsulfone, thermosetting polyimide, aromatic polyimide, aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide,
Examples include polyallyl ether ketone and polyamide imide resin films. Further, it is preferable that the surface of the heat-resistant resin film has been subjected to a treatment for improving adhesiveness according to the purpose, such as a chemical treatment, a corona discharge treatment, and a low-temperature plasma treatment.

[0057]

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 stirring rod, a three-way cock, and a condenser were set in a 1 L three-necked flask. In this flask, 114 g of bisphenol A and 145 potassium carbonate were added.
g, allyl bromide 140 g, and acetone 250 mL 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.
26 g were obtained. ¹ H-NMR revealed that bisphenol A was an allylated bisphenol in which the OH group of the bisphenol A was allyl etherified. The yield was 82% and the purity was 95% or more.

Example 1 1.0 g of allylated bisphenol prepared in Synthesis Example 1, 1,3,5,7-tetramethylcyclotetrasiloxane (KF-99, manufactured by Shin-Etsu Chemical Co., Ltd.)
02) 0.58 g and 1 mL of methyl ethyl ketone as a solvent were added and mixed. After adding and mixing 4.7 mg of dimethyl malate, 4.7 mg of a platinum vinyl siloxane catalyst (manufactured by Degussa Japan, PTVTS-3.0X) was added and mixed.

Example 2 10 mL with a stirrer set
1.00 g of the allylated bisphenol produced in Synthesis Example 1 and 1,3,5,7-tetramethylcyclotetrasiloxane (KF-9902, manufactured by Shin-Etsu Chemical Co., Ltd.)
0.20 g and 1 mL of methyl ethyl ketone as a solvent
And mixed. Under stirring, a platinum vinyl siloxane catalyst (manufactured by Degussa Japan, PTVTS-3.0X) 4.7
mg was added. The mixture reacted with exotherm. After reacting for about 1 hour, 4.7 mg of dimethyl malate was added. 0.38 g of 1,3,5,7-tetramethylcyclotetrasiloxane was further added to and mixed with the obtained mixture to produce an adhesive composition having a controlled viscosity.

(Example 3) The adhesive composition prepared in Example 1 was applied to a polyimide resin (Apical, manufactured by Kanebuchi Kogyo Co., Ltd.) having a thickness of 25 µm to a thickness of 175 µm using a comma coater, and then heated to 100 ° C. Heated for 2 minutes in a conditioned hot air dryer. The thus-prepared film with an adhesive layer was bonded to a copper foil at a linear pressure of 2.5 kg by a heating / pressing roll adjusted to 120 ° C. Further, heating was performed at 200 ° C. for 3 hours. When the adhesive strength (peeling strength) of the thus obtained adhesive body was measured, it was 0.8 kg /
cm and a sufficient adhesive strength.
The adhesive strength was as strong as 5 kg / cm.

Example 4 The adhesive composition produced in Example 1 was applied to a polyimide resin (Apical, manufactured by Kanebuchi Kogyo Co., Ltd.) having a thickness of 25 μm to a thickness of 175 μm using a comma coater, and then the solvent was dried. And heating adjusted to 120 ° C
The copper foil was joined with a pressure roll at a linear pressure of 2.5 kg. Further, heating was performed at 200 ° C. for 3 hours. When the adhesive strength (peeling strength) of the thus obtained adhesive body was measured, it had a sufficient adhesive strength of 0.8 kg / cm.
Even at 100 ° C., the adhesive strength was as strong as 0.5 kg / cm.

Comparative Example 1 In a 500 mL flask, 50.00 g of methylphenyldivinylsilane and a platinum vinyl siloxane catalyst (PTVTS-3.
0X) 160 mL of a 591 mg toluene solution was charged. Under stirring, a solution of 50.70 g of 1,4-bis (dimethylsilyl) benzene in toluene (100 mL) was added to 3.
It was added dropwise over 5 hours. It was confirmed that the internal temperature rose to 44 ° C. during the dropwise addition. After 20 hours, the solvent was distilled off,
94.3 g of a highly viscous reactive silicon-based polymer was produced.
As a result of analysis by ¹ H-NMR, this compound was found to be 0.76
It contained 84 mol / g of vinyl groups. To 100 g of the obtained mixture, 6.9 g of 1,3,5,7-tetramethylcyclotetrasiloxane and T as a solvent were further added.
100 g of HF was added and mixed to produce an adhesive composition comprising a silicon-based polymer.

Comparative Example 2 The adhesive composition produced in Comparative Example 1 was applied to a polyimide resin (Apical, manufactured by Kaneka Corp.) having a thickness of 25 μm to a thickness of 175 μm using a comma coater, and then heated to 60 ° C. Heated for 1 minute in the adjusted hot air dryer. The film with the adhesive layer manufactured in this way is
1. Linear pressure of copper foil with heating / pressure roll adjusted to 180 ° C
Welded with 5 kg. Further, heating was performed at 150 ° C. for 3 hours. When the adhesive strength (peeling strength) of the thus obtained adhesive body was measured, it was found to be 1.2 kg / cm at room temperature.
Had sufficient adhesive strength, but at 100 ° C., 0.2
The bonding strength was as large as kg / cm.

[0065]

The adhesive composition of the present invention can be widely used as a rigid wiring board for semiconductor mounting, a flexible printed wiring board, and a peripheral material of a lead frame, and is excellent in high adhesive strength and heat resistance. .

Continued on the front page F-term (reference) 4J040 DA001 DA002 DB001 DB002 DF041 DF042 EB031 EB032 ED001 ED002 EE001 EE002 EG001 EG002 EK001 EK002 EK031 EK032 EL021 EL022 FA011 FA012 FA041 FA042 FA061 FA0612 GA101 GA102 FA01 GA03 HA216 HA246 HA266 HA306 HB02 HB07 HB09 HB22 HB32 HB41 HC02 HC15 HC19 HD02 HD05 HD19 HD20 HD22 HD23 HD30 HD43 KA14 KA17 LA01 LA06 LA08 LA09 MA01 MA02 NA20 QA01

Claims (8)

[Claims] (A) an organic compound having an organic skeleton containing at least two carbon-carbon double bonds reactive with a SiH group in one molecule; and (B) at least two organic compounds in one molecule. An adhesive composition comprising a SiH group-containing silicon compound and (C) a hydrosilylation catalyst as essential components, wherein the component (A) is a carbon compound having a reactivity with a SiH group.
0.001 mol of carbon double bond per 1 g of component (A)
An adhesive composition which is an organic compound contained above. (2) The component (A) is represented by the following general formula (I): (Wherein, R ¹ represents a group having 2 to 6 carbon atoms containing a carbon-carbon double bond reactive with a SiH group, or a hydrogen atom), and has a reactivity with a SiH group. The adhesive composition according to claim 1, which is an organic compound containing at least two carbon-carbon double bonds in one molecule. (A) an organic compound having an organic skeleton containing at least two carbon-carbon double bonds reactive with a SiH group in one molecule, and (B) at least two organic compounds in one molecule. An adhesive composition comprising a SiH group-containing silicon compound and a (C) hydrosilylation catalyst as an essential component, wherein Tg of a cured product obtained by curing the adhesive composition is obtained.
Is 50 ° C. or higher.
Item 10. The heat-resistant adhesive composition according to item 8. (4) The component (B) has the following general formula (II): (Wherein, R ² represents an organic group having 1 to 6 carbon atoms, and n represents 3 to
Represents the number 10. The adhesive composition or the heat-resistant adhesive composition according to any one of claims 1 to 3, wherein the adhesive composition is a cyclic polyorganosiloxane containing at least two SiH groups in one molecule represented by the following formula: . 5. The ratio of the number (X) of carbon-carbon double bonds reactive with SiH groups in the component (A) to the number (Y) of SiH groups in the component (B) is as follows: 5. The adhesive composition or the heat-resistant adhesive composition according to claim 1, wherein Y / X ≧ 1.2. 6. The method according to claim 1, further comprising (D) a curing retarder as an essential component, in addition to using the components (A) to (C) as an essential component. 3. The adhesive composition or the heat-resistant adhesive composition according to item 1. 7. The heat-resistant adhesive composition for electronic materials or the heat-resistant adhesive composition according to claim 1, wherein: 8. A carbon-carbon duplex which is preliminarily mixed with the adhesive composition or the heat-resistant adhesive composition according to claim 1, and has a reactivity with SiH groups in the composition. A method for producing an adhesive composition by reacting a bond with a part of a SiH group.