JP4185450B2 - Radiation curable silicone rubber composition, adhesive silicone elastomer film comprising the composition, structure using the composition, and method for producing the same - Google Patents

Description

  The present invention relates to a radiation curable silicone rubber composition, an adhesive silicone elastomer film obtained by forming the composition into a film, a silicone elastomer film covering using the same, and a cured product of the radiation curable silicone rubber composition. The present invention relates to a structure having an adhesive layer between substrates and a method for manufacturing the structure.

  Conventionally, epoxy adhesive films have been used for die bonding of semiconductor devices and for bonding TAB tapes. However, this epoxy-based adhesive film has problems that heat resistance is insufficient and low elasticity cannot be achieved (that is, in the case of a high elastic body, for example, an adhesive layer between two different substrates). When it is used as a laminate, it is difficult to relieve thermal and mechanical stress, and the reliability of the product is reduced). On the other hand, silicone-based adhesive films generally have high heat resistance and low elasticity, but have not yet been known what have sufficient adhesiveness and workability and can be easily manufactured.

  Although the present applicant has already proposed an improved adhesive silicone elastomer film (Patent Document 1), the adhesive strength is still unsatisfactory under severe conditions, for example, in a heat cycle test at -55 ° C to 150 ° C. In some cases, peeling due to poor adhesion may occur. In addition, there is a problem that it takes time to develop adhesiveness during die bonding (Patent Documents 2 and 3). Therefore, it has been desired that the adhesiveness at the time of die bonding is expressed quickly. Furthermore, since the preparation of the adhesive silicone elastomer film requires advanced technology and expensive equipment for the molding process, a simpler means has been required in the manufacturing process of semiconductor products.

JP 2000-234060 A Japanese Patent Application No. 2003-238808 Japanese Patent Application No. 2003-238809

  An object of the present invention is to provide an adhesive silicone elastomer that can streamline the process during use, has low elasticity, has sufficient heat resistance and strong adhesiveness, and has excellent workability in view of the above-described problems of the prior art. The object is to provide a film, a radiation curable silicone rubber composition suitable for producing such a film, a structure such as a semiconductor device using the composition, and a method for producing the structure.

The present invention, first,
(A) Organohydrogenpolysiloxane having one or more groups selected from the group consisting of acryloyl groups and methacryloyl groups and one or more hydrosilyl groups in one molecule: 5 to 100 parts by weight
(B) Oily organopolysiloxane having 2 or more groups selected from the group consisting of acryloyl group and methacryloyl group in one molecule and having no hydrosilyl group: 95-0 parts by weight
(However, the total content of the component (a) and the component (b) is 100 parts by weight.)
(C) At least one compound selected from the group consisting of alkoxysilane, partially hydrolyzed condensate of alkoxysilane, isocyanurate modified with organosilane, and isocyanurate modified with organosiloxane: 0 to 30 parts by weight ,
(D) Radiosensitizer: effective amount, and
(E) Platinum group metal catalyst: effective amount,
Radiation curable silicone rubber composition containing, preferably, 0.1 to 30 parts by weight of component (c) relative to 100 parts by weight of component (a) and component (b) A silicone rubber composition is provided.

  The present invention secondly provides an adhesive silicone elastomer film comprising the above composition, which is radiation-cured. That is, the adhesive silicone elastomer film obtained by shape | molding the said composition in a film form and carrying out radiation curing of the obtained film-form molded object is provided.

  Thirdly, the present invention provides a silicone elastomer film covering obtained by covering a part or all of a substrate with the above adhesive silicone elastomer film and then heating to adhere the film to the substrate.

  Fourthly, the present invention provides a structure having a first substrate, a second substrate, and an adhesive layer made of a cured product of the above composition, which is sandwiched between the two substrates and bonds the two substrates to each other. Provide the body. As an example, there is a structure obtained by sandwiching the adhesive silicone elastomer film between two substrates, then heating, curing by heating, bonding the film to both substrates, and bonding the substrates to each other. Can be mentioned. A typical example of the present invention is a semiconductor device in which either the first base or the second base is a support such as a lead frame or a package, and the remaining base is a semiconductor chip.

  Fifthly, the present invention provides a step of forming the above composition into a film form on a first substrate to obtain a film-like formed body, and an adhesive elastomer film by irradiating the film-like formed body with radiation. A method for manufacturing the above structure (Production Method A), comprising: a step of pressure-bonding a second substrate on the elastomer film; and a step of curing the elastomer film by heat treatment. .

  In the present invention, when the structure is a semiconductor device, either the first base or the second base is a support such as a lead frame or a package, and the remaining base is a semiconductor chip.

  Sixth, the present invention is such that the above adhesive silicone elastomer film is sandwiched between a first substrate and a second substrate, and then heated to bond the film to both substrates to bond them together. There is provided a method for producing the above-described structure (Production Method B).

  In the present invention, when the structure is a semiconductor device, either the first base or the second base is a support such as a lead frame or a package, and the remaining base is a semiconductor chip.

The radiation curable silicone rubber composition of the present invention provides a clean adhesive silicone elastomer film with a uniform shape by irradiation for a short time after molding.
This adhesive silicone elastomer film has the following advantages.
(1) Since the adhesiveness is strong and the workability is good by heating in a short time, a fixed adhesive layer can be formed by cutting.
(2) Since it has low elasticity, thermal and mechanical stress in bonding of two different substrates can be relaxed, and stability and reliability of a bonded product such as a covering or a structure can be improved.
(3) Since it is a cured product, it is easy to handle.
(4) Since it is supplied as a film-like molded product, the process at the time of use (process for producing a bonded product) can be rationalized.
(5) As an embodiment of the above structure, it is useful for manufacturing a semiconductor device by bonding a semiconductor chip to a support with the adhesive film.

  In addition, the curable composition can be radiation-cured after being applied to a substrate to form an adhesive silicone elastomer layer, and another structure can be bonded to the adhesive layer to produce the structure. In either case, the structure of the present invention has a simple manufacturing process. Furthermore, there is no problem with the physical properties of the cured silicone elastomer formed as the adhesive layer. For example, the adhesive is strong and has low elasticity so that it can be thermally and mechanically bonded to different substrates. Since the stress is relieved, a structure with high stability and reliability, for example, a semiconductor device can be obtained.

  Hereinafter, the present invention will be described in detail. In the following description, acryloyl and methacryloyl, acrylate and methacrylate are generally referred to as (meth) acryloyl and (meth) acrylate, respectively.

<Radiation curable silicone rubber composition>
The radiation-curable silicone rubber composition according to the present invention comprises the following components (a) to (e) (however, the component (c) is an optional component that may be appropriately blended as necessary). Is.

[(A) Organohydrogenpolysiloxane]
(A) An organohydrogenpolysiloxane having one or more groups selected from the group consisting of an acryloyl group and a methacryloyl group and one or more hydrosilyl groups (that is, SiH groups) in one molecule of the component (that is, ( (Meth) acryloyl group-containing organohydrogenpolysiloxane) is an essential component. This molecule is, for example, a (meth) acryloyloxy group-substituted monovalent carbon such as a (meth) acryloyloxyalkyl group such as a (meth) acryloyloxyethyl group, a (meth) acryloyloxypropyl group, or a (meth) acryloyloxybutyl group. The hydrogen group preferably contains at least one, preferably 1 to 10, more preferably 2 to 4 substituents bonded to one or more silicon atoms at the end of the molecular chain. In addition, this molecule contains at least one, preferably 2 to 200, hydrogen atoms bonded to silicon atoms at the end of the molecular chain and / or in the middle of the molecular chain (that is, a hydrosilyl group represented by SiH). It is desirable that the organohydrogenpolysiloxane. The degree of polymerization (or the number of silicon atoms in the molecule) is preferably about 2 to 10,000, more preferably about 10 to 1,000, and particularly preferably about 20 to 200.

  As the component (a), the following general formula (I):

（Ｉ）
〔ここで、基Ｒ’’は一価の炭化水素基であり、基Ｒ’’’は水素原子、一価の炭化水素基、または（メタ）アクリロイルオキシ基含有有機基であり、基Ｚは（メタ）アクリロイルオキシ基含有有機基である。

(I)
[Wherein the group R ″ is a monovalent hydrocarbon group, the group R ′ ″ is a hydrogen atom, a monovalent hydrocarbon group, or a (meth) acryloyloxy group-containing organic group, and the group Z is It is a (meth) acryloyloxy group-containing organic group.

Further, l, m, and n are integers of 0 ≦ l ≦ 8,000, 0 ≦ m ≦ 8,000, and 0 ≦ n ≦ 8, respectively. However, l + m + n is 1 to 10,000. When l = 0, at least one of two groups R ′ ″ is a hydrogen atom, and when n = 0, two groups R ′ ″ At least one is a (meth) acryloyloxy group-containing organic group. ]
What is represented by these, specifically, what is represented by the following formula | equation can be mentioned.

(1-1)
〔式中、ＲおよびＲ’は独立に水素原子またはメチル基であり、Ｒ’が水素原子のときは、ｌは０≦ｌ≦８，０００の整数、好ましくは１≦ｌ≦１，０００の整数、より好ましくは１≦ｌ≦２００の整数であって、Ｒ’がメチル基のときは、１≦ｌ≦８，０００の整数、好ましくは２≦ｌ≦１，０００の整数、より好ましくは２≦ｌ≦２００の整数である。ｍは０≦ｍ≦８，０００の整数、好ましくは０≦ｍ≦１，０００の整数、より好ましくは０≦ｍ≦２００の整数である。また、ｌ＋ｍは１〜１０，０００、好ましくは１０〜８，０００、特に好ましくは２０〜２００の整数であり、ｋは１〜４の整数であり、好ましくは１〜３の整数であり、特に好ましくは２である。〕

(1-1)
[Wherein, R and R ′ are independently a hydrogen atom or a methyl group, and when R ′ is a hydrogen atom, l is an integer of 0 ≦ l ≦ 8,000, preferably 1 ≦ l ≦ 1,000. An integer, more preferably an integer of 1 ≦ l ≦ 200, and when R ′ is a methyl group, an integer of 1 ≦ l ≦ 8,000, preferably an integer of 2 ≦ l ≦ 1,000, more preferably It is an integer of 2 ≦ l ≦ 200. m is an integer of 0 ≦ m ≦ 8,000, preferably an integer of 0 ≦ m ≦ 1,000, more preferably an integer of 0 ≦ m ≦ 200. L + m is an integer of 1 to 10,000, preferably 10 to 8,000, particularly preferably 20 to 200, k is an integer of 1 to 4, preferably an integer of 1 to 3, Preferably it is 2. ]

〔式中、Ｒは独立に水素原子またはメチル基であり、ｌは１≦ｌ≦８，０００の整数、好ましくは２≦ｌ≦１，０００の整数、より好ましくは２≦ｌ≦２００の整数である。ｍは０≦ｍ≦８，０００の整数、好ましくは０≦ｍ≦１，０００の整数、より好ましくは０≦ｍ≦２００の整数である。また、ｌ＋ｍは１〜１０，０００、好ましくは１０〜８，０００、特に好ましくは２０〜２００の整数であり、ｋは１〜４の整数であり、好ましくは１〜３の整数であり、特に好ましくは２である。〕

[Wherein, R is independently a hydrogen atom or a methyl group, and l is an integer of 1 ≦ l ≦ 8,000, preferably an integer of 2 ≦ l ≦ 1,000, more preferably an integer of 2 ≦ l ≦ 200. It is. m is an integer of 0 ≦ m ≦ 8,000, preferably an integer of 0 ≦ m ≦ 1,000, more preferably an integer of 0 ≦ m ≦ 200. L + m is an integer of 1 to 10,000, preferably 10 to 8,000, particularly preferably 20 to 200, k is an integer of 1 to 4, preferably an integer of 1 to 3, Preferably it is 2. ]

〔式中、Ｒの定義ならびにｋ、ｌおよびｍの範囲は、式（１−２）で定義したものと同様である。ｎの範囲は１≦ｎ≦８の整数であり、好ましくは１≦ｎ≦５、より好ましくは１≦ｎ≦３である。また、ｌ＋ｍ＋ｎは１〜１０，０００、好ましくは１０〜８，０００、特に好ましくは２０〜２００の整数である。〕

[Wherein, the definition of R and the ranges of k, l and m are the same as those defined in formula (1-2). The range of n is an integer of 1 ≦ n ≦ 8, preferably 1 ≦ n ≦ 5, more preferably 1 ≦ n ≦ 3. L + m + n is an integer of 1 to 10,000, preferably 10 to 8,000, particularly preferably 20 to 200. ]

〔式中、Ｒの定義ならびにｋ、ｌおよびｍの範囲は、式（１−２）で定義したものと同様である。〕

[Wherein, the definition of R and the ranges of k, l and m are the same as those defined in formula (1-2). ]

  The (meth) acryloyl group-containing organohydrogenpolysiloxanes exemplified above can be used singly or in combination of two or more.

  The component (a) is, for example, a diorganocyclosiloxane oligomer such as octamethylcyclotetrasiloxane, an organohydrogencyclosiloxane oligomer such as tetramethylcyclotetrasiloxane, and 1,3-bis (acryloyloxymethyl) -1,1, Produced by equilibrating a (meth) acryloyloxyalkyldiorganodisiloxane, which can be a terminal group such as 3,3-tetramethyldisiloxane, in the presence of a strong acidic catalyst such as trifluorosulfonic acid, for example, at room temperature. can do.

In addition, the component (a) may have at least one (meth) acryloyl group in the molecule, but when the composition does not contain the component (b) described later, (meth) Those having two or more acryloyl groups are preferably used.
Content of (a) component in this composition is 5-100 weight part, Preferably it is 20-100 weight part, More preferably, it is 20-90 weight part. (The total amount of the component (a) and the component (b) described later is 100 parts by weight.)

  Since the composition of the present invention contains the organohydrogenpolysiloxane of component (a), the adhesive silicone elastomer film formed on the substrate by the method described later is subjected to heat treatment after being bonded to various substrates. Or when thermocompression-bonded to various substrates at a high temperature, the two Si—H bonds contained in the component (a) are oxidatively polymerized to form Si—O—Si bonds, Since a number of Si-H bonds react with -OH groups, -H groups (active hydrogen groups), etc. that exist on the surface of a normal substrate to form chemical bonds (for example, -OSi-, -Si-Si-). The adhesion between the substrate and the film can be strengthened. In order to obtain this strong adhesiveness, the temperature during thermocompression bonding needs to be 120 ° C. or higher, preferably 150 ° C. or higher, more preferably 160 ° C. or higher.

[(B) Oily organopolysiloxane]
Examples of the oily organopolysiloxane having two or more (meth) acryloyl groups and no hydrosilyl group in one molecule of component (b) include those represented by the following general formula (II). it can.

(II)
〔式中、Ｒ¹は独立に非置換または置換の炭素原子数１〜９の１価炭化水素基であり、Ｌは８≦Ｌ≦１０,０００の整数、好ましくは１８≦Ｌ≦１,０００の整数、より好ましくは４８≦Ｌ≦５００の整数であり、Ｘは独立に下記一般式（III）：

(II)
[Wherein, R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 9 carbon atoms, and L is an integer of 8 ≦ L ≦ 10,000, preferably 18 ≦ L ≦ 1,000. An integer of 48 ≦ L ≦ 500, and X is independently the following general formula (III):

（III）
（式中、Ｒ²は炭素原子数２〜４の２価炭化水素基または酸素原子であり、Ｒ³は１〜３個の（メタ）アクリロイル基を有する炭素原子数４〜２５の１価有機基であり、Ｒ⁴は独立に置換または非置換の炭素原子数１〜９の１価炭化水素基であり、Ｒ⁵は独立に置換または非置換の炭素原子数１〜１８の１価炭化水素基であり、ｐは１≦ｐ≦３の整数であり、ｑは０≦ｑ≦２の整数であり、但し、ｐ＋ｑは１〜３である。）で表わされる基である。〕

(III)
(In the formula, R ² is a divalent hydrocarbon group having 2 to 4 carbon atoms or an oxygen atom, and R ³ is a monovalent organic having 4 to 25 carbon atoms having 1 to 3 (meth) acryloyl groups). R ⁴ is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 9 carbon atoms, and R ⁵ is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 18 carbon atoms. And p is an integer satisfying 1 ≦ p ≦ 3, q is an integer satisfying 0 ≦ q ≦ 2, where p + q is 1 to 3. ]

  The number of (meth) acryloyl groups in one molecule of the organopolysiloxane represented by the general formula (II) is preferably 3 or more, and more preferably 4 or more.

In the above general formula (II), R ¹ is preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms. Specific examples of the monovalent hydrocarbon group include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, and 2-ethylhexyl group. Alkyl groups such as octyl group and nonyl group; cycloalkyl groups such as cyclohexyl group and cycloheptyl group; alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group and hexenyl group; phenyl group and tolyl An aryl group such as a group; an aralkyl group such as a phenylpropyl group such as a benzyl group, a phenylethyl group, or a 3-phenylpropyl group; or at least a part of hydrogen atoms bonded to carbon atoms of these groups, for example, a halogen atom Substituted with a substituent such as cyano group, chloromethyl group, cyanoethyl group, 3,3,3-trifluoropro And groups such as a trifluoropropyl group such as a pill group.

Among them, those in which the methyl group occupies 50 mol% or more of the total R ¹ , more preferably 80 mol% or more (ie 80 to 100 mol%), particularly 90 mol% or more (ie 90 to 100 mol%) are good. It is desirable that the phenyl group is 25 mol% or less, preferably 10 mol% or less (that is, 0 to 10 mol%) of the total R ¹ .
In a preferred embodiment, 50 mol% or more of R ¹ is a methyl group and 25 mol% or less is a phenyl group, and 80 mol% or more of R ¹ (that is, 80 to 100 mol%). In particular, 90 mol% or more (that is, 90 to 100 mol%) is a methyl group, and 10 mol% or less (that is, 0 to 10 mol%) is more preferably a phenyl group.

R ² in the general formula (III) is an oxygen atom or a divalent hydrocarbon group, and is preferably a divalent hydrocarbon group from the viewpoint of stability against hydrolysis and the like. Specific examples of the divalent hydrocarbon group include alkylene groups having 2 to 4 carbon atoms such as an ethylene group, a propylene group, a methylethylene group, and a tetramethylene group, and an ethylene group is preferable.

R ³ in the above general formula (III) has 1 to 3, preferably 2 to 3, more preferably 3 (meth) acryloyl groups (particularly, as (meth) acryloyloxy groups). Specific examples of the (meth) acryloyl group include CH ₂ ═CHCO— and CH ₂ ═C (CH ₃ ) CO—. Specific examples of R ³ include, for example, CH ₂ ═CHCOOCH ₂ CH ₂ —, [CH ₂ ═C (CH ₃ ) COOCH ₂ ] ₃ C—CH ₂ —, (CH ₂ ═CHCOOCH ₂ ) ₃ C—CH _{2 -, (CH 2 = CHCOOCH 2} ) 2 C (C 2 H 5) CH 2 - or the like, 1-3 acryloyloxy group or a methacryloyloxy group having 1 to 10 carbon atoms which is substituted with, preferably a carbon atom Examples thereof include an alkyl group of 2 to 6. Among them, preferably, CH ₂ = CHCOOCH ₂ CH _2- , [CH ₂ = C (CH ₃ ) COOCH ₂ ] ₃ C-CH _2- , (CH ₂ = CHCOOCH ₂ ) ₃ C-CH _2- , (CH ₂ = CHCOOCH ₂ ) ₂ C (C ₂ H ₅ ) CH _2- , CH ₂ = C (CH ₃ ) COOCH ₂ CH _2- , [CH ₂ = C (CH ₃ ) COOCH ₂ ] ₂ C (C ₂ H ₅ ) -CH ₂ - and _{(CH 2 = CHCOOCH 2) [} CH 2 = C (CH 3) COOCH 2] CH-, particularly _{preferably, [CH 2 = C (CH} 3) COOCH 2] 3 C-CH 2 -, (CH ₂ = CHCOOCH ₂ ) ₃ C-CH _2- , (CH ₂ = CHCOOCH ₂ ) ₂ C (C ₂ H ₅ ) CH ₂ -and (CH ₂ = CHCOOCH ₂ ) [CH ₂ = C (CH ₃ ) COOCH ₂ ] CH−.

R ⁴ in the general formula (III) is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 9 carbon atoms, preferably 1 to 6 carbon atoms. Specific examples of R ⁴ are the same as those exemplified as R ¹ in the general formula (II), but as in R ¹ , the methyl group is more preferably 50 mol% or more of the total R ^4. Preferably occupy 80 mol% or more (ie 80 to 100 mol%), particularly 90 mol% or more (ie 90 to 100 mol%), and the phenyl group is 25 mol% or less of the total R ⁴ , preferably 10 What is less than mol% (namely, 0-10 mol%) is desirable.
In a preferred embodiment, 50 mol% or more of R ⁴ is a methyl group and 25 mol% or less is a phenyl group, and 80 mol% or more of R ⁴ (that is, 80 to 100 mol%). In particular, 90 mol% or more (that is, 90 to 100 mol%) is a methyl group, and 10 mol% or less (that is, 0 to 10 mol%) is more preferably a phenyl group.

R ⁵ in the general formula (III) is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms. Specific examples of R ⁵ include, for example, methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, tert-butyl groups, pentyl groups, neopentyl groups and other alkyl groups; cyclohexyl groups, cycloheptyl groups and other cycloalkyl groups. Groups; aryl groups such as phenyl and tolyl groups; alkenyl groups such as allyl, propenyl, and butenyl. Preferred are those that are not aliphatic unsaturated groups such as alkenyl groups, and more preferred are alkyl groups, cycloalkyl groups, and aryl groups.

  Specific examples of the organopolysiloxane represented by the general formula (II) include the following.

および

and

〔上記式中、Ｒ’はメチル基、フェニル基または３，３，３−トリフルオロプロピル基を表し、Ｌは前記のとおり（すなわち、一般式（II）に関して定義したとおり）である。〕

[In the above formula, R ′ represents a methyl group, a phenyl group or a 3,3,3-trifluoropropyl group, and L is as defined above (that is, as defined in relation to the general formula (II)). ]

The organopolysiloxane of the component (b) represented by the general formula (II) has —OR ³ group as a radiation-sensitive group (that is, 2 to 18 in a molecule, preferably 3 to 12 And more preferably 4 to 12 (meth) acryloyl groups), and it is characterized by being easily cured by irradiation with ultraviolet rays or the like. These organopolysiloxanes can be used alone or in combination of two or more.

  The organopolysiloxane of the general formula (II) can be produced, for example, by a dehydrochlorination reaction between a corresponding chlorosiloxane and a (meth) acryloyl functional compound having an active hydroxyl group. Here, examples of the chlorosiloxane include those represented by the following formula.

  Examples of the (meth) acryloyl functional compound having an active hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and 2-hydroxy-1-acryloyloxy. Examples include -3-methacryloyloxypropane. Among them, since it is preferable that the target organopolysiloxane has a group containing 2 to 9 (meth) acryloyl groups bonded to the silicon atom at the end of each molecular chain, trimethylolpropane di (meth) acrylate, Pentaerythritol tri (meth) acrylate and 2-hydroxy-1-acryloyloxy-3-methacryloxypropane are preferred, and pentaerythritol tri (meth) acrylate is more preferred.

  Content of (b) component in this composition is 95-0 weight part, Preferably it is 80-0 weight part, More preferably, it is 80-10 weight part. (The total amount of the component (a) and the component (b) is 100 parts by weight.)

[(C) Alkoxysilanes]
(C) Alkoxysilane or a partially hydrolyzed condensate of alkoxysilane (that is, an organopolysiloxane (oligomer) having at least one, preferably two or more residual alkoxy groups in the molecule) as a component adheres to the substrate. In order to improve property, it is an arbitrary component which may be mix | blended as needed, As a specific example of this (c) component, the following compound can be mentioned, for example.

  That is, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetra (isopropoxy) silane, tetrabutoxysilane, tetra (isobutoxy) silane, tetra (tert-butoxy) silane; trimethoxysilane, triethoxy Trialkoxyhydrogensilanes such as silane, tripropoxysilane, tri (isopropoxy) silane, tributoxysilane, tri (isobutoxy) silane, tri (tert-butoxy) silane; methyltrimethoxysilane, methyltriethoxysilane, ethyltri Monovalent hydrocarbon groups such as methoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, etc., for example, lower alkyl , Organotrialkoxysilanes having aryl groups, etc., and partial hydrolysis condensates of these alkoxysilanes (ie, organopolysiloxanes (oligomers) having at least one, preferably two or more residual alkoxy groups in the molecule) In addition, the following organopolysiloxanes may be mentioned.

(上記式中、ｎは０≦ｎ≦１００、好ましくは０≦ｎ≦５０の整数である。)

(In the above formula, n is an integer of 0 ≦ n ≦ 100, preferably 0 ≦ n ≦ 50.)

  Similarly, the isocyanurate modified with the organosilane or organosiloxane of component (c) is an isocyanurate having 1 to 3 alkenyl groups such as vinyl and allyl groups (for example, triallyl isocyanurate) and a SiH bond. Can be synthesized by an addition reaction with an organosilane or organosiloxane having a hydrogen atom (Japanese Patent Publication No. 45-23354, US Pat. No. 3,821,218, US Pat. No. 3,517,001). reference). Examples of the isocyanurate modified with this organosilane or organosiloxane include 1 to 3 trialkoxysilyl group-substituted alkyl groups such as γ-trimethoxysilylpropyl group and γ-triethoxysilylpropyl group. Specific examples of the isocyanurates include those obtained by hydrolytic condensation of these alkoxysilyl groups (that is, siloxane-modified isocyanurates). Specific examples include those represented by the following formula.

（上記各式中、Ｒは独立に水素、アルキル基、アラルキル基、低級アルケニル基、またはアリール基である。）
この(c)成分は、１種単独でも２種以上を組み合わせても使用することができる。

(In the above formulas, R is independently hydrogen, an alkyl group, an aralkyl group, a lower alkenyl group, or an aryl group.)
This component (c) can be used alone or in combination of two or more.

  The content of the component (c) in the composition of the present invention is 0 to 30 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the total of the components (a) and (b). Preferably it is 0.5-20 weight part. By blending the component (c) with the composition of the present invention, the adhesive strength of the adhesive elastomer film under low temperature conditions can be improved, which is effective.

[(D) Radiosensitizer]
The radiation sensitizer of component (d) is not particularly limited, but is preferably a benzoyl compound (or phenyl ketone compound) such as benzophenone, particularly 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 A benzoyl compound having a hydroxy group on the α-position carbon atom of a carbonyl group such as -phenylpropan-1-one and 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (or Phenyl ketone compounds); organophosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bisacyl monoorganophosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide Benzoin ether compounds such as isobutyl benzoin ether; acetophenone Examples include ketal compounds such as diethyl ketal; thioxanthone compounds; acetophenone compounds and the like. These can be used singly or in combination of two or more.

  The content of the component (d) in the composition of the present invention is not particularly limited as long as it is an amount effective for curing by irradiation with radiation such as ultraviolet rays of the composition of the present invention as a radiosensitizer. The total amount of the component (a) and the component (b) is usually 0.5 to 10 parts by weight, preferably 1.0 to 5.0 parts by weight per 100 parts by weight.

[(E) Platinum group metal catalyst]
As described above, the platinum group metal catalyst of component (e) is subjected to oxidative polymerization of Si—H bonds contained in component (a) and groups present on the substrate surface (—OH group, —H, as described above) by heat treatment. It is a catalyst used for promoting a dehydrogenative condensation reaction with a group (active hydrogen group) or the like.

  In the composition of the present invention, the radiation functional group such as the (meth) acryloyl group contained in the component (a) and the component (b) is polymerized and cross-linked by radiation irradiation such as UV irradiation. A film is formed, but the SiH groups derived from the component (a) remaining in the film cross-linked by radiation irradiation are heat-treated, so that SiH groups are oxidatively polymerized. In addition to the increase, the OH group and SiH group at the deposition interface are dehydrogenatively condensed to form a siloxane bond (—O—Si—). As a result, adhesion to the adherend can be increased. .

As such a platinum group metal catalyst, a known catalyst used in hydrosilylation reaction can be used. Specific examples thereof include platinum group metals such as platinum (including platinum black), rhodium and palladium; H ₂ PtCl ₄ · nH ₂ O, H ₂ PtCl ₆ · nH ₂ O, NaHPtCl ₆ · nH ₂ O , KHPtCl ₆ · nH ₂ O, Na ₂ PtCl ₆ · nH ₂ O, K ₂ PtCl ₄ · nH ₂ O, PtCl ₄ · nH ₂ O, PtCl ₂ , Na ₂ HPtCl ₄ · nH ₂ O (in the above formula, n Is an integer from 0 to 6, preferably 0 or 6.) Alcohol-modified chloroplatinic acid (see US Pat. No. 3,220,972); platinum chloride Complexes of acids and olefins (see US Pat. Nos. 3,159,601, 3,159,662, and 3,775,452); platinum group metals such as platinum black and palladium are supported on alumina, silica, carbon and other carriers Loaded; Logi Chloro-tris (triphenylphosphine) rhodium (Wilkinson catalyst); platinum chloride, chloroplatinic acid or chloroplatinate and a vinyl group-containing siloxane, particularly a vinyl group-containing cyclic siloxane. These can be used singly or in combination of two or more.

  The content of the component (e) in the composition of the present invention is not particularly limited as long as it is an effective amount as a catalyst, but the platinum group relative to the total weight of the components (a) and (b). The metal atomic weight is usually about 0.01 to 2,000 ppm, preferably about 0.1 to 500 ppm.

[(F) Reaction control agent]
In the composition comprising the components (a) to (e) of the present case, as an optional component to be blended as necessary, (f) a reaction control agent at room temperature such as during storage and transportation It is preferable to be blended in order to suppress the curing reaction of the composition of the present invention and to ensure a sufficient pot life for work. As the component, for example, a heavy metal ionic compound (see US Pat. No. 3,532,649) and those used as an addition reaction control agent by a known hydrosilylation reaction can be used without limitation.

For example, polysiloxane (see Japanese Patent Publication No. 48-10947) containing CH ₂ ═CHRSiO units (wherein R represents a monovalent hydrocarbon group not containing an aliphatic unsaturated double bond), acetylene alcohol (for example, Acetylene compounds such as 1-ethynyl-1-cyclohexanol, 3-methyl-1-butyn-3-ol) (see US Pat. No. 3,445,420) and the like are preferably used. Of these, acetylene compounds are preferred.

  The content of the component (f) in the composition of the present invention is not particularly limited as long as it is an effective amount, but is usually 0 to 1 mol of the platinum group metal atom in the component (e). It is preferable to use an amount that is 1,000 times mol, preferably 1 to 1,000 times mol, more preferably 10 to 500 times mol, and still more preferably 30 to 300 times mol. If the content is too small, the storage stability of the composition of the present invention may be poor, and the adhesiveness may decrease during long-term storage. Conversely, if the content is too large, the adhesion rate of the composition of the present invention will be extremely slow. There is a case.

[Other ingredients]
The composition of the present invention includes the components (a) to (f) (provided that the components (c) and (f) In addition to the components being optional components, it is optional to add other additives.

  When the composition is used to form a thin film coating, the workability is improved, the coefficient of thermal expansion of the cured product is reduced, the thermal stability, weather resistance, chemical resistance, flame resistance or mechanical strength is increased. For the purpose of lowering the gas permeability, for example, a filler such as fumed silica, quartz powder, titanium oxide, calcium carbonate, or carbon black can be blended in an amount that does not interfere with film formation. Furthermore, if necessary to apply the composition of the present invention to the spin coating method or the screen printing method, a volatile organic solvent such as toluene, xylene, low molecular siloxane (dimethylsilicone oil) or the like is used to adjust the viscosity to the desired viscosity. May be added.

<Adhesive silicone elastomer film>
The adhesive silicone elastomer film of the present invention can be obtained by forming the radiation curable silicone rubber composition into a film and then curing it by irradiation with radiation. This radiation curable silicone rubber composition is in the form of a paste and can be continuously molded with a commercially available coater. Radiation irradiation conditions are as described later. Furthermore, the inside of the irradiation apparatus is preferably cooled by a fan or the like in order to avoid the influence of heat generation. This adhesive silicone elastomer film includes the case where it is a sheet. In addition, the thickness of this film is 5-1000 micrometers normally, Preferably it is 10-500 micrometers, More preferably, it is 20-200 micrometers.

<Manufacture of covering>
A covering can be obtained by covering part or all of the substrate with the adhesive silicone elastomer film obtained as described above, and then heating and bonding the film to the substrate. In this case, the heating temperature is preferably 80 to 250 ° C, more preferably 100 to 200 ° C. Examples of the substrate include Si, Al, Cu, Ni, Cr, Au, Ag and other various metals, and organic resins such as epoxy resin, bakelite, polyimide, polyester, and silicone resin.

<Structure and its manufacture>
The structure of the present invention comprises a first substrate, a second substrate, and an adhesive layer between the two substrates. Examples of the substrate include Si, Al, Cu, Ni, Cr, Au, Ag and other various metals, various organic resins such as epoxy resin, bakelite, polyimide, polyester, and silicone resin, silicon oxide film, and photoresist film. , Copper plating film, gold plating film and the like.

  When the structure is a semiconductor device, either the first base or the second base is a support such as a lead frame or a package, and the remaining base is a semiconductor chip. Examples of the substrate include Si, Al, Cu, Ni, Cr, Au, Ag and other various metals, various organic resins such as epoxy resin, bakelite, polyimide, polyester, and silicone resin, silicon oxide film, and photoresist film. , Copper plating film, gold plating film and the like. The semiconductor chip contains a semiconductor such as silicone, GaAs, CdTe, Ge, or SiC, and includes semiconductor elements such as transistors, diodes, ICs, and LSIs. If necessary, the surfaces of these substrates may be covered with a silicon oxide film, a photoresist film, a copper plating film, a gold plating film, or the like.

-Manufacturing method A-
The manufacturing method A of the structure of the present invention will be described by taking the case where the structure is a semiconductor device as an example.
The manufacturing method of the semiconductor device is as follows:
(1) Forming the radiation-curable silicone rubber composition on a first substrate surface in a film shape to obtain a film-shaped molded body,
(2) irradiating the obtained film-shaped molded article with radiation to form an adhesive elastomer film,
(3) a step of pressing a second substrate onto the elastomer film to form a precursor structure, and
(4) At the same time as the step (3) or subsequent to the step, the obtained precursor structure is subjected to a heat treatment to heat cure the elastomer film. It can be obtained as a semiconductor device in which both substrates are bonded to each other through an adhesive layer made of a cured silicone elastomer.

Each step of the above method will be described in more detail below.
[(1) Film-like molded body forming step]
The first substrate may be either a semiconductor chip or its support.
The method for forming the composition of the present invention on the surface of the first substrate in the form of a film is not particularly limited. For example, the coating may be performed using a commercially available coater, but by spin coating or screen printing. Is preferred. According to the spin coating method, a film-like molded body can be efficiently formed with a uniform thickness over the entire surface of a substrate having a flat surface such as a wafer as in the case of applying a resist agent. In addition, a film-like molded product having a uniform thickness can be formed by the screen printing method, and a molded product having a specific shape can be formed on a part of the substrate as needed. .

When the spin coating method is employed, the composition of the present invention preferably has a relatively low viscosity. For example, at 25 ° C., 0.1 to 10 Pa · s, preferably 0.2 to 8 Pa · s, The viscosity is preferably adjusted to 0.5 to 5 Pa · s.
When employing the screen printing method, the composition of the present invention preferably has a relatively high viscosity, for example, 10 to 1,000 Pa · s, preferably 20 to 800 Pa · s at 25 ° C. More preferably, the viscosity is adjusted to 50 to 500 Pa · s. For screen printing, for example, a metal mask, a mesh mask, or the like can be used.

[(2) Radiation irradiation process]
Irradiation conditions for the film are as described below.

[(3) Crimping process]
A second substrate is pressure-bonded onto the adhesive elastomer film obtained in the above step (2) to obtain a precursor structure. In the manufacture of a semiconductor device, when the semiconductor chip is used as the first substrate in step (1), the support is used as the second substrate in the step. However, when the support is used as the first substrate in the step (1), the semiconductor chip is used as the second substrate in the step.
Also, for example, using a commercially available die bonding mounter and using a pressure tool with a semiconductor chip mounted, a precursor structure in which either the semiconductor chip or the support is pressure-bonded onto the adhesive elastomer film is used. You can also.

[(4) Heat curing process]
Simultaneously with the pressure-bonding step (3) or subsequent to the pressure-bonding step (3), the precursor structure is heat-treated to cure the elastomer film, and both the substrates are adhesive layers made of a cured silicone elastomer. Thus, a semiconductor device coupled to each other can be obtained.

-Manufacturing method B-
In the structure of the present invention, the above-mentioned adhesive silicone elastomer film crosslinked in advance by irradiation is sandwiched between a first substrate and a second substrate to form a precursor structure, and then the film is heated, Can be manufactured by bonding the two substrates together.

In any of the embodiments of the present invention, radiation curing can usually be performed as follows. A commercially available ultraviolet irradiation device (for example, a mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon mercury lamp, etc.) may be used. The amount of light energy to be irradiated varies depending on the thickness of the target film or layer, but is 200 to 10,000 mJ / cm ² , preferably 400 to 5,000 mJ / cm ² , more preferably 400 to 2,000 mJ / cm ^2. It is. Further, the illuminance is usually 40~1,000mW / cm ^2, preferably, 100~500mW / cm ^2, more preferably from to the 40~200mW / cm ^2. Furthermore, the inside of the irradiation apparatus is preferably cooled by a fan or the like in order to avoid the influence of heat generation.

  The heat treatment conditions during heat curing are 80 to 300 ° C, preferably 80 to 250 ° C, more preferably 100 to 250 ° C, still more preferably 120 to 240 ° C, and still more preferably 150 to 240 ° C. Most preferably, the temperature may be 160 to 230 ° C. As the heating device, for example, a commercially available die bonding mounter can be used.

  Hereinafter, the present invention will be described with reference to examples (and comparative examples). In the examples, parts represent parts by weight, Me in the formula represents a methyl group, Ph represents a phenyl group, and Et represents an ethyl group. The acryloyl functional organopolysiloxane of component (a) and component (b) was synthesized according to Japanese Patent Application Laid-Open No. 2000-234060.

[Synthesis Example 1] ((a) Synthesis of acryloxy group-containing methyl hydrogen polysiloxane)
A dropping funnel containing 1776 g of octamethylcyclotetrasiloxane, 360 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and 18 g of 1,3-bis (acryloxymethyl) -1,1,3,3-tetramethyldisiloxane And introduced into a reaction vessel equipped with a stirrer and stirred uniformly. Next, 6 g of trifluorosulfonic acid was added dropwise and stirred at room temperature (25 ° C.) for about 4 hours to equilibrate, and then 144 g of sodium carbonate was added, neutralized and filtered. Thereafter, 1,000 ml of toluene was added and washed with hot water to remove water in the reaction solution. Then, 0.2 g of BHT was added as a polymerization inhibitor, and stripping was performed at 100 ° C./30 mmHg while stirring. A transparent oily acryloxy group-containing dimethylsiloxane / methylhydrogensiloxane copolymer was obtained.

[Synthesis Example 2] (Synthesis of (b) (meth) acryloyl group-containing organopolysiloxane)
In a 1,000 ml reactor equipped with a stirrer, reflux condenser, dropping funnel, and dry air introducer, the following average formula:

で示されるクロロオルガノポリシロキサン５７１ｇ、２−ヒドロキシ−１−アクリロキシ−３−メタクリロキシプロパン（商品名：ＮＫエステル７０１−Ａ、新中村化学工業（株）製）４７ｇ、トルエン２００ｍｌ、トリエチルアミン２６ｇ、及び重合禁止剤としてジブチルヒドロキシトルエン２０００ｐｐｍを入れ、攪拌しながら、７０℃に昇温して７時間加熱し、反応させた。反応液を放冷後、濾過し、プロピレンオキサイド４ｇを添加し、室温で１時間攪拌し、次いで１００℃／３０ｍｍＨｇでストリップを行って下記式で示される透明なオイル状のオルガノポリシロキサンを得た。

Chloroorganopolysiloxane 571 g, 2-hydroxy-1-acryloxy-3-methacryloxypropane (trade name: NK ester 701-A, manufactured by Shin-Nakamura Chemical Co., Ltd.) 47 g, toluene 200 ml, triethylamine 26 g, and As a polymerization inhibitor, 2000 ppm of dibutylhydroxytoluene was added, and while stirring, the temperature was raised to 70 ° C. and heated for 7 hours to be reacted. The reaction solution was allowed to cool and then filtered, 4 g of propylene oxide was added, stirred at room temperature for 1 hour, and then stripped at 100 ° C./30 mmHg to obtain a transparent oily organopolysiloxane represented by the following formula. .

[Example 1]
(A) 20 parts of an acryloxy group-containing methylhydrogen polysiloxane having the following structure synthesized in Synthesis Example 1 above,

（式中、ｌ＝２０、ｍ＝８０）
（ｂ）上記の合成例２で合成した（メタ）アクリロイル基含有オルガノポリシロキサンを１００部、
（ｃ）下記構造のテトラメトキシシランの部分加水分解縮合物を３部、

(Where, l = 20, m = 80)
(B) 100 parts of the (meth) acryloyl group-containing organopolysiloxane synthesized in Synthesis Example 2 above,
(C) 3 parts of a partial hydrolysis-condensation product of tetramethoxysilane having the following structure,

（但し、上記部分加水分解縮合物は、上記式においてｍが１〜７の整数である化合物の混合物である）
（ｄ）２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オンを２部、
（ｅ）塩化白金酸のオクチルアルコール変性溶液０．１部（塩化白金酸中の白金金属原子／[(a)+(b)]（重量）＝17 ppm、白金金属原子量＝１×10^-5 モル）、
および
（ｆ）１−エチニル−１−シクロヘキサノールの５０重量％トルエン溶液０．１部（前記(e)成分中の白金金属原子量１モルに対する1-エチニル-1-シクロヘキサノールの量＝40倍モル）
を混合し、放射線硬化性シリコーンゴム組成物を得た。
（なお、重量基準で、（ｃ）／[（ａ）＋（ｂ）]＝２．５／１００）

(However, the partial hydrolysis-condensation product is a mixture of compounds in which m is an integer of 1 to 7 in the above formula)
(D) 2 parts 2-hydroxy-2-methyl-1-phenylpropan-1-one,
(E) 0.1 part octyl alcohol-modified solution of chloroplatinic acid (platinum metal atom in chloroplatinic acid / [(a) + (b)] (weight) = 17 ppm, platinum metal atom weight = 1 × 10 ⁻⁵ Mole),
And (f) 0.1 part of a 50 wt% toluene solution of 1-ethynyl-1-cyclohexanol (the amount of 1-ethynyl-1-cyclohexanol is 40 times moles relative to 1 mole of platinum metal atom in the component (e)) )
Were mixed to obtain a radiation curable silicone rubber composition.
((C) / [(a) + (b)] = 2.5 / 100 based on weight)

This composition was poured into a nickel-plated mold (length 100 mm × width 100 mm, depth 1 mm), and ultraviolet rays were placed in a conveyor furnace (illuminance: 400 mW / cm ² ) equipped with two metal halide mercury lamps for 2 seconds. (Irradiation amount: 800 mJ / cm ² ) and radiation-cured. The obtained adhesive silicone elastomer film having a thickness of 80 μm was taken out of the mold, and the hardness of the film was measured according to JIS K6301. The hardness was measured with a spring type A type testing machine. The results are shown in Table 1.

  Next, the above-mentioned silicone elastomer film is cut into 25 mm length × 10 mm width and sandwiched between two test pieces of aluminum, silicon wafer, polyimide film, glass or polycarbonate as a substrate (substrate), and this is crimped at 9.8 kPa. The structure was manufactured by heating and curing at 160 ° C. for 60 minutes, and the shear adhesive strength was measured. In addition, as shown in FIG. 1, the shear adhesive force sandwiches the film layer 3 having a thickness of 80 μm over one end of each of the test pieces 1 and 2 having a length of 100 mm, a width of 25 mm, and a thickness of 50 μm over a length of 10 mm. In the state where the test pieces 1 and 2 are overlapped, the both ends 4 and 5 of each test piece 1 and 2 are respectively measured by pulling them with a tensile tester in the direction of the arrow. The results are shown in Table 2.

[Example 2]
A composition was prepared in the same manner as in Example 1 except that 3 parts of an epoxy group-containing polyalkoxysiloxane having the following structure was used instead of 3 parts of the partial hydrolysis condensate of tetramethoxysilane as the component (c). An adhesive silicone elastomer film and a structure were produced using this composition, and the same test as in Example 1 was performed. The results are shown in Tables 1 and 2.

（式中、ｎ＝６）

(Where n = 6)

[Example 3]
A composition was prepared in the same manner as in Example 1 except that 1 part of a triisocyanurate silicone-modified compound having the following structure was used instead of 3 parts of the partial hydrolysis condensate of tetramethoxysilane as the component (c) ( In addition, on the basis of weight, (c) / [(a) + (b)] = 0.8 / 100), an adhesive silicone elastomer film and a structure were produced using this composition. The test was conducted. The results are shown in Tables 1 and 2.

[Example 4]
A composition was prepared in the same manner as in Example 1 except that 20 parts of acryloxy group-containing methyl hydrogen polysiloxane having the following structure was used instead of 20 parts of acryloxy group-containing methyl hydrogen polysiloxane of component (a). Then, an adhesive silicone elastomer film and a structure were produced using this composition, and the same test as in Example 1 was performed. The results are shown in Tables 1 and 2.

（式中、ｍ＝２０、ｎ＝２０）

(Where m = 20, n = 20)

[Example 5]
A composition was prepared in the same manner as in Example 1 except that 20 parts of the acryloxy group-containing methyl hydrogen polysiloxane as the component (a) was changed to 5 parts (note that (c) on a weight basis) /[(A)+(b)]=2.9/100), an adhesive silicone elastomer film and a structure were produced using this composition, and the same test as in Example 1 was performed. The results are shown in Tables 1 and 2.

[Example 6]
A composition was prepared in the same manner as in Example 1 except that the addition amount of 20 parts of the acryloxy group-containing methylhydrogen polysiloxane (a) was changed to 100 parts (note that, on the basis of weight, (c) /[(A)+(b)]=1.5/100), an adhesive silicone elastomer film and a structure were produced using this composition, and the same test as in Example 1 was performed. The results are shown in Tables 1 and 2.

[Example 7]
The (meth) acryloxy group-containing polysiloxane (100 parts) as the component (b) is not contained, and the addition amount of the acryloxy group-containing methylhydrogen polysiloxane as the component (a) is changed to 100 parts. Except for the above, a composition was prepared in the same manner as in Example 1 ((c) / (a) = 3/100 on a weight basis), and an adhesive silicone elastomer film and a structure were prepared using this composition. The same test as in Example 1 was conducted. The results are shown in Tables 1 and 2.

[Comparative Example 1]
A composition was prepared in the same manner as in Example 1 except that the platinum catalyst as the component (e) and the reaction control agent as the component (f) were not added in the above Example 1, and an adhesive silicone was prepared using this composition. Elastomer films and structures were produced and tested in the same manner as in Example 1. The results are shown in Tables 1 and 2.

[Comparative Example 2]
A composition was prepared in the same manner as in Example 2 except that the platinum catalyst as the component (e) and the reaction control agent as the component (f) were not added in the above Example 2, and an adhesive silicone was prepared using this composition. Elastomer films and structures were produced and tested in the same manner as in Example 1. The results are shown in Tables 1 and 2.

[Comparative Example 3]
A composition was prepared in the same manner as in Example 3 except that the platinum catalyst as the component (e) and the reaction control agent as the component (f) were not added in Example 3. The adhesive silicone was prepared using this composition. Elastomer films and structures were produced and tested in the same manner as in Example 1. The results are shown in Tables 1 and 2.

[Comparative Example 4]
A composition was prepared in the same manner as in Example 4 except that the platinum catalyst as the component (e) and the reaction control agent as the component (f) were not added in Example 4, and an adhesive silicone was prepared using this composition. Elastomer films and structures were produced and tested in the same manner as in Example 1. The results are shown in Tables 1 and 2.

<800mJ / cm ² hardness after irradiation>

注） ＪＩＳ Ｋ６３０１に規定されるスプリング式Ａ型試験機で測定

Note) Measured with a spring type A tester specified in JIS K6301

注）単位＝ＭＰａ

Note) Unit = MPa

[ Reference Example 1 ]
A radiation-curable silicone rubber composition was prepared in the same manner as in Example 1 except that 3 parts of the partial hydrolysis-condensation product of tetramethoxysilane as the component (c) was not blended, and an adhesive silicone was prepared using this composition. Elastomer films and structures were produced and tested in the same manner as in Example 1. The results are shown in Tables 3 and 4.

[ Reference Example 2 ]
A radiation-curable silicone rubber composition was prepared in the same manner as in Example 4 except that 3 parts of the partial hydrolysis condensate of tetramethoxysilane as the component (c) was not blended, and an adhesive silicone was prepared using this composition. Elastomer films and structures were produced and tested in the same manner as in Example 1. The results are shown in Tables 3 and 4.

[ Reference Example 3 ]
A radiation-curable silicone rubber composition was prepared in the same manner as in Example 5 except that 3 parts of the partially hydrolyzed condensate of tetramethoxysilane as the component (c) was not used, and an adhesive silicone was prepared using this composition. Elastomer films and structures were produced and tested in the same manner as in Example 1. The results are shown in Tables 3 and 4.

[ Reference Example 4 ]
A radiation curable silicone rubber composition was prepared in the same manner as in Example 6 except that 3 parts of the partial hydrolysis condensate of tetramethoxysilane as the component (c) was not blended, and this composition was used to form an adhesive silicone. Elastomer films and structures were produced and tested in the same manner as in Example 1. The results are shown in Tables 3 and 4.

[ Reference Example 5 ]
A radiation-curable silicone rubber composition was prepared in the same manner as in Example 7 except that 3 parts of the partial hydrolysis-condensation condensate of tetramethoxysilane as the component (c) was not blended, and an adhesive silicone was prepared using this composition. Elastomer films and structures were produced and tested in the same manner as in Example 1. The results are shown in Tables 3 and 4.

<800mJ / cm ² hardness after irradiation>

注）単位：ＭＰａ

Note) Unit: MPa

[Example 8 ]
(a1) 20 parts of an acryloyloxy group-containing methyl hydrogen polysiloxane having the following structure:

（式中、ｌ＝20、ｍ＝80）
(b)下記構造の(メタ)アクリロイルオキシ基含有オルガノポリシロキサン 100部、

(Where, l = 20, m = 80)
(b) 100 parts of a (meth) acryloyloxy group-containing organopolysiloxane having the following structure,

(c)下式構造のテトラメトキシシランの部分加水分解縮合物 ３部（なお、(c)／[(a1)+(b)]（重量比）＝2.5/100）、

(c) 3 parts of a partial hydrolysis condensate of tetramethoxysilane having the following structure (where (c) / [(a1) + (b)] (weight ratio) = 2.5 / 100),

（但し、上記部分加水分解縮合物は、上記式においてｍが１〜７の整数である化合物の混合物である）
(d) 2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン ２部、
(e)塩化白金酸のオクチルアルコール変性溶液 0.1部（塩化白金酸中の白金金属原子／[(a1)+(b)]（重量）＝17 ppm、白金金属原子量＝１×10^-5 モル）、および
(f) 1-エチニル-1-シクロヘキサノールの 50重量％トルエン溶液 0.1部（前記(e)成分中の白金金属原子量１モルに対する 1-エチニル-1-シクロヘキサノールの量＝40倍モル）
を混合し、粘度が５Pa・sの硬化性シリコーンゴム組成物を得た。

(However, the partial hydrolysis-condensation product is a mixture of compounds in which m is an integer of 1 to 7 in the above formula)
(d) 2 parts 2-hydroxy-2-methyl-1-phenylpropan-1-one,
(e) Octyl alcohol modified solution of chloroplatinic acid 0.1 part (platinum metal atom in chloroplatinic acid / [(a1) + (b)] (weight) = 17 ppm, platinum metal atom weight = 1 × 10 ⁻⁵ mol) ,and
(f) 0.1 parts of 1-ethynyl-1-cyclohexanol in 50% by weight toluene solution (amount of 1-ethynyl-1-cyclohexanol = 40 times mole per 1 mole of platinum metal atom in component (e))
Were mixed to obtain a curable silicone rubber composition having a viscosity of 5 Pa · s.

When this composition was applied to the center of a silicon wafer (5 inches in diameter) and treated at a rotational speed of 1,000 rpm for 60 seconds using a spin coater, a uniform resin layer having a thickness of 20 μm could be formed. Next, irradiation with ultraviolet rays (irradiation amount: 800 mJ / cm ² ) was performed for 2 seconds in a conveyor furnace (illuminance: 400 mW / cm ² ) equipped with two metal halide mercury lamps to cure the radiation. The hardness of the adhesive silicone elastomer film on the silicon wafer was measured according to JIS K 6301 (measuring instrument: spring type A tester). The measurement results are shown in Table 5.

  Next, the silicon wafer whose surface is coated with the adhesive silicone elastomer film is cut into a shape of 25 mm in length and 10 mm in width with a dicing machine, and the other side of the obtained rectangular silicon wafer is bonded to the surface on the side of the adhesive silicone elastomer film. Aluminum, silicon wafer, polyimide film, glass or polycarbonate was stacked as a substrate (substrate) of this, and pressure-bonded at a pressure of 9.8 kPa, and then heated and cured at a temperature of 160 ° C. for 60 minutes to produce a structure. Using this structure, shear adhesive strength (unit: MPa) was measured. The shear adhesive force was measured with a push-pull measuring machine. The results are shown in Table 6.

[Example 9 ]
Instead of component (c) described in Example 8, (c2) except for using 3 parts of an epoxy group-containing polyalkoxysiloxane having the following structure, a composition was prepared in the same manner as in Example 8, the composition An adhesive silicone elastomer film and a structure were produced using the above, and the same test as in Example 8 was performed. The results are shown in Tables 5 and 6.

（式中、ｎ＝６）

(Where n = 6)

[Example 10 ]
Instead of component (c) described in Example 8, (c3) a except for using 1 part of tri-isocyanurate silicone-modified compound of the following structure, the composition in the same manner as in Example 8 was prepared (Note that ( c3) / [(a1) + (b)] (weight ratio) = 0.8 / 100), an adhesive silicone elastomer film and a structure were produced using this composition, and the same test as in Example 8 was performed. . The results are shown in Tables 5 and 6.

[Example 11 ]
Instead of the component (a1) described in Example 8, (a2) a except for using 20 parts acryloyloxy group-containing methylhydrogenpolysiloxane of the following structure, a composition was prepared in the same manner as in Example 8, An adhesive silicone elastomer film and a structure were produced using this composition, and the same test as in Example 8 was performed. The results are shown in Tables 5 and 6.

（式中、ｍ＝20，ｎ＝20）

(Where m = 20, n = 20)

[Example 12 ]
A composition was prepared in the same manner as in Example 8 except that 20 parts of the component (a1) described in Example 8 was changed to 5.0 parts (note that (c) / [(a1) + (b)] (weight ratio) = 2.9 / 100), an adhesive silicone elastomer film and a structure were produced using this composition, and the same test as in Example 8 was performed. The results are shown in Tables 5 and 6.

[Example 13 ]
A composition was prepared in the same manner as in Example 8 except that 20 parts of the component (a1) described in Example 8 was changed to 100 parts (note that (c) / [(a1) + (b)] (weight ratio) = 1.5 / 100), an adhesive silicone elastomer film and a structure were produced using this composition, and the same test as in Example 8 was performed. The results are shown in Tables 5 and 6.

[Example 14 ]
A composition was prepared in the same manner as in Example 8 except that the component (b) described in Example 8 was not used, and the addition amount of the component (a1) 20 parts was changed to 100 parts (note that , (C) / (a1) (weight ratio) = 3/100), an adhesive silicone elastomer film and a structure were produced using this composition, and the same test as in Example 8 was performed. The results are shown in Tables 5 and 6.

[Example 15 ]
(a3) 20 parts of an acryloyloxy group-containing methyl hydrogen polysiloxane having the following structure,

（式中、ｌ＝100、ｍ＝400）
(b)下記構造の(メタ)アクリロイルオキシ基含有オルガノポリシロキサン 100部、

(Where, l = 100, m = 400)
(b) 100 parts of a (meth) acryloyloxy group-containing organopolysiloxane having the following structure,

(c)下式構造のテトラメトキシシランの部分加水分解縮合物 ３部（なお、(c)／[(a3)+(b)]（重量比）＝2.5/100）、

(c) 3 parts of a partial hydrolysis condensate of tetramethoxysilane having the following structure (where (c) / [(a3) + (b)] (weight ratio) = 2.5 / 100),

（但し、上記部分加水分解縮合物は、上記式においてｍが１〜７の整数である化合物の混合物である）
(d) 2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン ２部、
(e)塩化白金酸のオクチルアルコール変性溶液 0.1部（塩化白金酸中の白金金属原子／[(a3)+(b)]（重量）＝17 ppm、白金金属原子量＝１×10^-5 モル）、および
(f) 1-エチニル-1-シクロヘキサノールの 50重量％トルエン溶液 0.1部（前記(e)成分中の白金金属原子量１モルに対する 1-エチニル-1-シクロヘキサノールの量＝40倍モル）
を混合し、粘度が 80Pa・sの硬化性シリコーンゴム組成物を得た。

(However, the partial hydrolysis-condensation product is a mixture of compounds in which m is an integer of 1 to 7 in the above formula)
(d) 2 parts 2-hydroxy-2-methyl-1-phenylpropan-1-one,
(e) 0.1 part of octyl alcohol-modified solution of chloroplatinic acid (platinum metal atom in chloroplatinic acid / [(a3) + (b)] (weight) = 17 ppm, platinum metal atom weight = 1 × 10 ⁻⁵ mol) ,and
(f) 0.1 parts of 1-ethynyl-1-cyclohexanol in 50% by weight toluene solution (amount of 1-ethynyl-1-cyclohexanol = 40 times mole per 1 mole of platinum metal atom in component (e))
Were mixed to obtain a curable silicone rubber composition having a viscosity of 80 Pa · s.

This composition was screen-printed on a silicon wafer (5 inches in diameter) to form a uniform resin layer having a thickness of 30 μm. Next, irradiation with ultraviolet rays (irradiation amount: 800 mJ / cm ² ) was performed for 2 seconds in a conveyor furnace (illuminance: 400 mW / cm ² ) equipped with two metal halide mercury lamps to cure the radiation. The hardness of the obtained adhesive silicone elastomer film was measured in the same manner as in Example 8 . The measurement results are shown in Table 5.
Next, using the above silicon wafer, a structure was produced in the same manner as in Example 8, and the shear adhesive force was measured. The results are shown in Table 6.

[Example 16 ]
A composition was prepared in the same manner as in Example 15 except that the component (b) described in Example 15 was not used, and the addition amount of the component (a3) 20 parts was changed to 100 parts (note that (c) / (a3) (weight ratio) = 3/100), using this composition, an adhesive silicone elastomer film and a structure were produced in the same manner as in Example 15. The same test as in Example 8 was conducted. went. The results are shown in Tables 5 and 6.

[Comparative Example 5]
Except not using component (e) described in Example 8 (a platinum group metal catalyst) and component (f) (reaction control agent), to prepare a composition in the same manner as in Example 8, the composition An adhesive silicone elastomer film and a structure were produced using the above, and the same test as in Example 8 was performed. The results are shown in Tables 5 and 6.

[Comparative Example 6]
A composition was prepared in the same manner as in Example 9 except that the components (e) and (f) described in Example 8 were not used, and an adhesive silicone elastomer film and structure were prepared using this composition. The same test as in Example 8 was performed. The results are shown in Tables 5 and 6.

[Comparative Example 7]
A composition was prepared in the same manner as in Example 10 except that the components (e) and (f) described in Example 8 were not used, and an adhesive silicone elastomer film and structure were prepared using this composition. The same test as in Example 8 was performed. The results are shown in Tables 5 and 6.

[Comparative Example 8]
A composition was prepared in the same manner as in Example 11 except that the components (e) and (f) described in Example 8 were not used, and an adhesive silicone elastomer film and structure were prepared using this composition. The same test as in Example 8 was performed. The results are shown in Tables 5 and 6.

注）単位＝ＭＰａ

Note) Unit = MPa

It is a perspective view of the state which bonded together the test piece used for the measurement of a shearing adhesive force.

Explanation of symbols

1. Test piece 2. 2. Test piece Film layer4. Edge 5. end

Claims (11)

(A) The following general formula (I):

[Wherein the group R ″ is a monovalent hydrocarbon group, the group R ′ ″ is a hydrogen atom, a monovalent hydrocarbon group, or a (meth) acryloyloxy group-containing organic group, and the group Z is It is a (meth) acryloyloxy group-containing organic group. Further, l, m, and n are integers of 0 ≦ l ≦ 8,000, 0 ≦ m ≦ 8,000, and 0 ≦ n ≦ 8, respectively. However, l + m + n is 1 to 10,000. When l = 0, at least one of two groups R ′ ″ is a hydrogen atom, and when n = 0, two groups R ′ ″ At least one is a (meth) acryloyloxy group-containing organic group. ]
Organohydrogenpolysiloxane having one or more groups selected from the group consisting of acryloyl group and methacryloyl group and one or more hydrosilyl groups in one molecule represented by : 5 to 100 parts by weight,
(B) Oily organopolysiloxane having 2 or more groups selected from the group consisting of acryloyl group and methacryloyl group in one molecule and having no hydrosilyl group: 95-0 parts by weight
(However, the total content of the component (a) and the component (b) is 100 parts by weight.)
(C) At least one compound selected from the group consisting of alkoxysilane, partially hydrolyzed condensate of alkoxysilane, isocyanurate modified with organosilane, and isocyanurate modified with organosiloxane: 0.5 to 20 Parts by weight,
(D) Radiosensitizer: The total amount of component (a) and component (b) 0.5 to 10 parts by weight per 100 parts by weight , and
(E) Platinum group metal-based catalyst: 0.01 to 2,000 ppm as platinum group metal atomic weight with respect to the total weight of components (a) and (b) ,
A radiation curable silicone rubber composition containing The component (b) is represented by the following general formula (II):

                            (II)
[In the formula, R ¹ Is independently an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a group in which at least a part of hydrogen atoms bonded to carbon atoms of these groups is substituted, and L is 8 ≦ L ≦ 10,000, and X is independently the following general formula (III):

                    (III)
(Wherein R ² Is a divalent hydrocarbon group having 2 to 4 carbon atoms or an oxygen atom, and R ^Three Is a monovalent organic group having 4 to 25 carbon atoms having 1 to 3 (meth) acryloyl groups, and R ^Four Is independently an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a group in which at least a part of hydrogen atoms bonded to the carbon atoms of these groups is substituted; ^Five Is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 18 carbon atoms, p is an integer of 1 ≦ p ≦ 3, and q is an integer of 0 ≦ q ≦ 2, provided that p + q Is 1-3. ). ]
Is an organopolysiloxane represented by
  The composition according to claim 1, wherein the content of the component (a) is 5 to 90 parts by weight, and the content of the component (b) is 95 to 10 parts by weight. Further, (f) with respect to platinum group metal atoms of 1 mol in the reaction control agent component (e), A composition according to claim 1 or 2 containing 0 to 1,000 moles. An adhesive silicone elastomer film obtained by forming the radiation curable silicone rubber composition according to any one of claims 1 to 3 into a film and then crosslinking the composition by radiation irradiation . A silicone elastomer film covering obtained by covering part or all of a substrate with the adhesive silicone elastomer film according to claim 4 and then heating the substrate at 80 to 250 ° C to adhere the film to the substrate. The adhesive silicone elastomer film previously cross-linked by irradiation according to claim 4 is sandwiched between a first substrate and a second substrate to form a precursor structure, and then the film is heated to bond both substrates A structure obtained by bonding the two substrates together . A structure according to claim 6 , wherein either one of the first base or the second base is a semiconductor chip, and the remaining base is a support for the semiconductor chip. Structure. A step of molding the curable silicone rubber composition according to any one of claims 1 to 3 into a film shape on a first substrate to obtain a film-shaped molded body, and radiation to the film-shaped molded body. The structure according to claim 6 , comprising a step of irradiating to an adhesive elastomer film, a step of pressure-bonding a second substrate on the elastomer film, and a step of curing the elastomer film by heat treatment. Body manufacturing method. 9. The manufacturing method according to claim 8 , wherein one of the first base and the second base is a semiconductor chip, and the remaining base is a support for the semiconductor chip. The adhesive silicone elastomer film according to claim 4 is sandwiched between a first substrate and a second substrate, and then heated to bond the film to both substrates, thereby bonding the substrates to each other. A method for producing the structure according to claim 6 . 11. The method according to claim 10 , wherein one of the first substrate and the second substrate is a semiconductor chip, and the remaining substrate is a support for the semiconductor chip.

Images